notes.fluorine1.runotes.fluorine1.ru/fluor_conf_06/pdf/posters1_100_en.pdf · 2012-06-18 · 7th...

7th All-Russian Conference “Fluorine Chemistry” dedicated to the centenary of I. L. Knunyants, June 5-9, 2006, Moscow, Russia

Р-01

REACTIONS OF POLYFLUOROAROMATIC COMPOUNDS, CONTAINING A –N=CCL GROUP, WITH ARENES IN THE

PRESENCE OF ALCL3 - THE ROUTE TO FLUORINATED N-HETEROCYCLIC DERIVATIVES

T. D. Petrova, V. E. Platonov

N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the RAS,

9 Lavrentiev Avenue, Novosibirsk , 630090, Russia Е-mail: [email protected]

It is shown that reactions of polyfluoroaromatic compounds, containing a –N=CCl group,

with arenes in the presence of AlCl3 make possible an expansion of the possibility for the synthesis of the fluorinated 5- and 6-membered N-heterocyclic derivatives.

The peculiarities and mechanistic details of these reactions including the formation of electrophilic intermediates of the nitrilium cation type are discussed.

N

N

O

Cl

F

F

H

O

NN

O

Cl ClCl

Cl

N

N

N

O

N

O

O

NN

O

ClCl

N

O

N

C6F5N=CCl2

+ + C6F5

C6F5

(Cl)

C6HF5

C6F5F5C6

C6H5H5C6

F5C6

C6F5N=C(Cl)CCl3 C6H5CN

C6F5N=CClC6F5NAlCl3

CCl

C6F5

ArCOR

C6F5F5C6

C6F5

C6F5

+

1,4-C6H2F4

,

,


Р-02

DI(4,5,6,7-TETRAFLUOROBENZOTHIAZOL-2-YL)DISULFIDE: SYNTHESIS AND REACTIONS WITH AMINES

N. A.Orlovaa, M. A. Shuvaevab, E. F. Kolchinaa, V. V. Shelkovnikova

aNovosibirsk N. N. Vorozhtsov Institute of Organic Chemistry SB RAS,

Acad. Lavrentiev Prosp., 9, 630090, Novosibirsk, Russia bNatural Sciences Faculty, Novosibirsk State University,

Pirogova str., 2, 630090, Novosibirsk, Russia E-mail: [email protected]

To search a new fluorinated initiators of polymerization we have synthesized the

polyfluorosubstituted derivatives of “captax” (I) - 4,5,6,7-tetrafluoro-3Н-benzothiazol-2-thione (II)1, containing the aliphatic and cycloaliphatic amine moieties.

Thione (II) does not react with piperidine and morpholine being refluxed in ethanole and DMF with potassium carbonate. The oxidation of (II) with aq.Н2О2 in ethanol leads to di(4,5,6,7- tetrafluoro-3Н-benzothiazol-2-yl)disulfide (III); the latter reacts easily with primary and secondary aliphatic amines, benzylamine, piperidine and morpholine to give sulfenylamides (IV).

S SN

S

F S

NFS

S

N

F

H

NR1R2 = NHBu, NBu2, NHCH2Ph,

N N O,

IIIII

H2O240%

EtOH, 20oC

S N S

NF

R1

R2

IV

EtOH, 20oCHNR1R2

Unfluorinated compounds of type (IV) may be obtained directly from 3Н- benzothiazol-2-

thione (I) and amines at presence of strong oxidants (NaClO, Cl2, I2). We have shown that disulfide, obtained from thione (I), does not react with amines by reflux in ethanole.

The investigation was supported by Interdisciplinary Integral Projects of Fundamental Researches of the SB RAS No.15, No.17, and No.33.

1 Zhu L. et al. J. Org. Chem. 2004, 69, 7371-7374.


Р-03

REACTIONS OF PENTAFLUOROPHENYL SUBSTITUTED PYRYLIUM SALTS WITH HYDRAZINE HYDRATE.

POLYFLUOROPYRIDOCYANINES

I. Yu. Kargapolova, N. A. Orlova, V. V. Shelkovnikov

Novosibirsk N. N. Vorozhtsov Institute of Organic Chemistry SB RAS, Acad. Lavrentiev Prosp., 9, 630090, Novosibirsk, Russia

E-mail: [email protected] We have studied the interaction of pentafluorosubstituted pyrylium salts, containing active methyl or methylene group, with hydrazine hydrate (EtOH, 20oC).

Tetrahydrobenzopyrylium perchlorate (I) forms diazepine (II) as a main product. At the same conditions pyrylium salt (III) gives diazepine (IV) and 1-aminopyridinium perchlorate (V). The latter was condensed with p-dimethylaminobenzaldehyde, forming pyridocyanines (VI) and (VII); the structure of dye depends on the addition of potassium carbonate to the reaction mixture.

N

Ph

C6F5 CH=CH

NH2ClO4

N(CH3)2

III

NH2NH2.H2O

EtOH, 20oCO

Ph

C6F5 CH3

ClO4

OHC N(CH3)2

Ac2OAc2O/AcONa

N

Ph

C6F5 CH3

NH2ClO4

CH3C6F5

Ph

N-N

IVV

OHC N(CH3)2

N

Ph

C6F5 CH3

N

CH

ClO4

N(CH3)2

VI

VII

OC6F5

Ph

ClO4

Ph

NC6F5 N

NH2NH2.H2O

EtOH, 20oC

III

563 nm

378 nm

The investigation was supported by Interdisciplinary Integral Projects of Fundamental Researches of the SB RAS No.65.


P-04

ELECTROPHILIC FLUORINATION OF AROMATIC COMPOUNDS WITH F-TEDA-BF4 IN SOLID STATE

G. I. Borodkina,b, P. A. Zaikina,b, V. G. Shubina

aNovosibirsk N. N. Vorozhtsov Institute of Organic Chemistry SB RAS,

Acad. Lavrentiev Ave. 9, 630090, Novosibirsk, Russia bDepartment of Natural Sciences, Novosibirsk State University,

Pirogov St. 2, 630090, Novosibirsk, Russia E-mail: [email protected]

Rapidly growing interest in fluoroaromatic compounds, dictated by an ever-increasing

demand for fluorinated pharmaceuticals, agrochemicals, dyestuffs, liquid crystals and polymers has placed importance on the development of ecologically acceptable fluorination methods2. In the last two decades, various types of N-fluoro reagents have been found to be appropriate fluorine sources for milder and selective fluorination of organic compounds3.

We have found that electrophilic fluorination of aromatic amines, phenols and their ethers can be carried out with 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoro-borate) (F-TEDA-BF4) 1 in a solid state. The main products of the fluorination are given below:

N+

N+

F

CH2Cl

NHAcF

OMe

COOH

OH OH

+

FOHOH

F

OH

OH

OH

OH

FF F

O +

1

FBr

NHAc

Br

OMe

COOH

OMe

HO

OMe

O

OMe

HO

FX

Y

+

X = F, Y = H; X = H, Y = F

F

2 BF4-

Structures of the compounds obtained have been confirmed by 1H, 19F NMR and GC-MS. Mechanism of this reaction and some peculiarities in chemical behaviour of phenols under

electrophilic fluorination are discussed.

2 Kirsch P. Modern Fluoroorganic Chemistry. Synthesis, Reactivity, Applications. Weinheim: Wiley-VCH Verlag, 2004, p. 203-277. 3 Taylor S.D. et al. Tetrahedron. 1999, 55(43), 12431-12477.


Р-05

SELECTIVE REDUCTIVE HYDRODEFLUORINATION OF POLYFLUORO-N-ACETANILIDES BY ZINC-COPPER COUPLE IN

AQUEOUS AMMONIA

L. Yu. Gurskayaa, G. A. Selivanovaa, V. D.Shteingartza,b

aN. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Ac. Lavrentjev Avenue, 9, 630090, Novosibirsk, Russia

bNovosibirsk State University, Pirogova Str., 2, 630090, Novosibirsk, Russia E-mail: [email protected]

ortho-Nonsubstituded polyfluorinated arylamines are universal starting materials for the

synthesis of fluorinated benzoazoheterocycles, which are of great interest as core structural units for the design of potentially biologically active compounds. Therefore the development of effective approaches to these compounds is an important problem. The most concise is a route based on selective ortho-hydrodefluorinaton of perfluorinated acetanilides by the action of zinc in aqueous ammonia, salt additives accelerating this process.1

We have shown the copper salt additive to accelerate and deepen the hydrodefluorinaton of pentafluoroacetanilide 1 by action of zinc in aqueous ammonia, allowing to obtain trifluoroacetanilides 4 and 5 which are products of hydrodefluorinaton of originally formed tetrafluoroacetanilides 2 and 3 respectively.

NHAc

F

NHAc

F

H

H

NHAc

F

H

H+ +Zn + CuCl2

NH3 aq.

1 2 3 4 5

NHAc

F

H

NHAc

F

H

Compounds 4 and 5 were employed for the synthesis of 5,6,8- and 5,7,8-trifluoroquinolines respectively.

NHAc

F

H

H

NHAc

F

H

H

Skraupreaction

F

H N

Skraupreaction

FH

N

4 5

The copper salt additive allowed to carry out for the first time hydrodefluorinaton of perfluoro-4-acetamidobiphenyl 7, that was a key stage in the synthesis of amine 9.

NHAcFFZn + CuCl2

NH3 aq., EtOH

FFHNH2FAc2O

benzenNH2FFH

EtOH9

6 7 8

HClNHAc

Thus, the copper salt additive allows to expand the scope of applicability of reductive system such as zinc in aqueous ammonia for the synthesis of inaccessible partially fluorinated arylamines, in particular new polyfluorinated ortho-unsubstituted anilines. _____________________ 1 Laev S.S. et al. J. Fluorine Chem. 2001, 110, 43-46.


Р-06

SYNTHESIS OF 5,7,8-TRIFLUOROQUINOLINE-6-CARBOXYLIC ACID AND POLYFLUORINETED QUINOLINES ON ITS BASE

L. Yu. Gurskayaa, S.S. Laev, G. A. Selivanovaa, V. D.Shteingartza,b

aN. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences,

Ac. Lavrentjev Avenue, 9, 630090, Novosibirsk, Russia bNovosibirsk State University, Pirogova Str., 2, 630090, Novosibirsk, Russia

E-mail: [email protected]

Benzoazoheterocycles polyfluorinated in the benzene ring are potentially biologically active compounds. The general approach to their synthesis consists in heterocyclization reactions of polyfluorinated arylamines nonsubstituded at ortho-position or the products of their modifications at this position providing expanded opportunities of of azoheterocycle construction.

Involving 2,3,5-trifluoro-4-trifluoromethylacetanilide, prepared by the selective ortho-hydrodefluorinaton of its precursor with completely fluorinated benzene ring, in the Skraup reaction allowed to obtain 6-trifluoromethyl-5,7,8-trifluoroquinoline 1, being an universal building block for synthesis of 6-substituted 5,7,8-trifluoroquinolines. So, hydrolysis of CF3-group in quinoline 1 under action of oleum leads to 5,7,8-trifluoroquinoline-6-carboxylic acid 2, decarboxylation of which by heating in DMF gives 5,7,8-trifluoroquinoline 3. From the acid 2 obtained is the acyl chloride 4, which gives with methanol the methyl ester and with ammonia - the amide of 5,7,8-trifluoroquinoline-6-carboxylic acid 5,6. Involving the latter into the Hoffmann rearrangement leads to 6-amino-5,7,8-trifluoroquinoline 7.

oleumN

HOOCF

SOCl2

N

ClOCF

DMF to

N

HF

N

MeOOCF

N

H2NF

MeOH

Br2NaOHNHAc

CF3

HF

mNBSA

glicerol

N

F3CF

NH3

N

H2NOCF

58 %

60 %

69 %

56%83%

68%

NHAc

CF3

FZn

NH3-H2O

12

3

45 6

7

H2SO4

Thus, the transformations providing an access to a base set of starting compounds for synthesis of 6-functionalized quinolines with a fluorinated benzene ring have been performed.


Р-07

1,3,5-TRIS(FLUOROSULFONYL)BENZENE, IT’S DERIVATIVES AND THEIR SELECTIVE REACTIONS

WITH NUCLEOPHILIC AGENTS

V. N. Boiko, A. A. Filatov, O. N. Kamoshenkova, Yu. L.Yagupolskii

Institute of Organic Chemistry NAS of Ukraine Murmanskaya St. 5, 02094, Kyiv, Ukraine


Simple and effective methods of synthesis of 2,4,6-tris(fluorosulphonyl)phenol4, −aniline, –chlorobenzene and 1,3,5-tris(fluorosulpholnyl)benzene were developed. Some of their selective reactions with nucleophilic agents were investigated.

Acidity of 2,4,6-tris(fluorosulphonyl)phenol and electroconductivity of it’s salts were investigated. Lithium salt was proposed as a salt component for chemical current source electrolytes.

FSO2

SO2F

SO2FOH

FSO2 SO2F

SO2F

FSO2

SO2F

SO2FCl

FSO2

SO2F

SO2FO

ClSO2 SO2Cl

SO2Cl

OH

FSO2 SO2F

SO2F

NH2

FSO2 SO2F

SO2F

Nu

FSO2 SO2F

SO2F

NuH

ClSO2 SO2Cl

SO2Cl

NH2

SO2FSO2

SO2F

FSO2 SO2F

SO2SC6H4NO2

SC6H4NO2

COOEt

COCH3

CHCOCH3

COOEt

кип.CH3OH

_

Nu-

при Nu = SC6H4NO2

Nu = SO3Na, CH(COOEt)2, CH(COCH3)COOEt

Nu = F, NHPh, SC6H4NO2, SCH2Ph, морфолил

- Kt+

KF

KF

2 NH3 Nu-

Zn

при Nu =

Nu-

PCl5

Kt = металлы, Alk4N

4 Boiko V.N. et al. Patent of Ukraine №72649 (2005).


Р-08

NEW TRIFLUOROMETHYLTIO-, SULFOXY- AND SULFONYLIMINO ETHYLENE DERIVATIVES

L. V. Sokolenko, I. I. Maletina, L. M. Yagupolskii

Institute of Organic Chemistry, National Academy of Sciences of Ukraine,

Murmanskaya st. 5, UA-02094, Kiev, Ukraine. E-mail: [email protected]

We developed a new method of trifluoromethylvinylsulfoxide (5) preparation from

2-mercaptoethanol (1) (Scheme 1).

OHSH OH

SCF3

ClS

CF3

SCF3

O

(5) 60%

ClS

CF3

O

(4) 70%

SOCl2, Py

MCPBA, -200C, 24 h DBU, Et2O, 00C

CF3I, HCOONa, Na2SO3

DMF, 250C(1) (2) 65% (3) 57%

Scheme 1

Reactions of trifluoromethylvinylsulfoxide (5) with N-, O- and S-nucleophiles were studied

(Scheme 2).

SCF3

O

(5)

ArNH2, CH3COOH, 1200CArNHCH2CH2SOCF3

RSH, NaH RSCH2CH2SOCF3

ROH, NaHROCH2CH2SOCF3

Scheme 2

A new derivative of trifluoromethylvinylsulfoxide (5) with

trifluoromethylsulfonyliminogroup at the sulfur atom was obtained (Scheme 3) and characterized.

ClS

CF3

(3)

SCF3

NSO2CF3

ClS

CF3

NSO2CF3CF3SO2NCl2

82%250C, 24 h

SiO2, PhCH3, 800C

(7) 70%(6)

Scheme 3


Р-09

SYNTHESIS OF NEW SUPER ACIDS – N-(TRIFLUOROMETHYLSULFONYL) DERIVATIVES OF

TRIFLUOROMETHANESULFONIC ACID.

R. Yu. Garlyauskayte a*, A. V. Bezdudny a, C. Michot b,

M. Armand b, Yu. L. Yagupolskii a, L. M. Yagupolskii a

a Institute of Organic Chemistry, National Academy of Sciences of Ukraine, 02094, Murmanskaya 5, Kiev, Ukraine; b Laboratoire International sur les Matériaux Électrocatifs CNRS 2289, Université de

Montréal, C.P.6128, , Montréal QC H3C 3J7 Canada

E-mail: [email protected] The attractive physical and chemical properties of trifluoromethansulfonic acid (Tf-OH)

and its derivatives have led to a wealth of new compounds and applications in many fields of chemistry. There has been recently a sustained interest in bis(perfluoroalkylsulfonyl)imides derivatives, as Lewis acid catalysts, fluorination reagents of aromatic compounds, electrolytes for lithium batteries and fuel cells, even bioactive molecules.

In the course of our study to find new organic super acids we have developed an interestingly simple yet efficient method for the synthesis of the sulfoximidoyl fluorides CF3SO2N=SO(CF3)F. This compound is novel reagent as synthon for introduction of super attractors groups. 1

We developed methods for the synthesis of salts of imides containing such sufoximidoyl groups. Novels organic super acids are prepared and some properties of this compounds are presented.

_________________________________________ 1Romute Yu. et al. J.Chem.Soc., Perkin Trans. I, 2002, 1887-1889.

SF3CSO2N O S

CF3

F3CSO2N- OCl2/F-

S

CF3

F3CSO2N OF

CF3SiMe3/F-

S

O

N

HN

CF3 S

O

CF3

NSO2CF3S

NSO2CF3

NSO2CF3

OHCF3

CF3SO2


Р-10

1-ARYLOXY-2CHLORO-1,2-DIFLUOROETHENES AND SOME THEIR REACTIONS

A. I. Mushta, M. M. Kremlev

Institute of Organic Chemistry, National Academy of Sciences of Ukraine,

Murmanskaya st. 5, UA-02094, Kiev, Ukraine. E-mail: [email protected]

We elaborated convenient method of preparation of 1-aryloxy-2-chloro-1,2-

difluoroethenes (1 a-h) by the treatment of substituted phenols with 1,2-dichloro-1,2-difluoroethene in the presence of potassium hydroxide in a N,N-dimethylformamide or N,N-dimethylacetamide.

The chlorine atom of compounds (1 a,c,d) can be substituted with lithium using n-butyllithium. Treatment of lithium derivatives with carbon dioxide or trimethylchlorosilane leads to the formation of 3-aryloxy-2,3-difluoroacrylic acids (2 a,c,d) or substituted trimethylsilanes (3 a,c,d).

Dimerisation of lithium derivatives of compounds (1 a,c) in the presence of copper chloride (II) led to formation of 1,4-di(aryloxy)perfluoro-1,3-butadienes (4 a,c).

(1-Phenyloxy-1,2-difluoroethenyl)trimethylsilane reacts with substituted benzaldehydes in the presence of fluoride ion to give the corresponding phenyl-α-fluorocinnamates (5 a,b). Hydrolysis of the lasts led to formation of the corresponding α-fluorocinnamic acids (6 a,b). This way we elaborated convenient method of synthesis of α-fluorocinnamic acid derivatives which can be a synthons for the preparation of biologically active compounds.

CFCl=CFClRC6H4OH RC6H4OCF=CFCl

1a-hR=H (a), 3-CH3 (b), 4-CH3 (c), 4-OCH3 (d), 3-NHCOCH3 (e), 4-Br (f), 3-F (g), 4-F (h).

+

O

OH

RC6H4OCF=CF-CF=CFOC6H4R

RC6H4OCF=CFCl

n-C4H9Li

-850CRC6H4OCF=CFLi

CO2

RC6H4OCF=CFC

Me3SiCl

RC6H4OCF=CFSiMe3

2 a,c,d 4 a,c

R=H (a), 4-CH3 (c), 4-OCH3 (d).

4- -4

CuCl2

3 a,c,d


P-11

SYNTHESIS AND CHEMICAL PROPERTIES OF 4(5)-POLYFLUOROALKYL-1,2,3-TRIAZOLES

Yu. P. Bandera, O. S. Kanishchev, V. M. Timoshenko, Yu. G. Shermolovich

Institute of Organic Chemistry of the National Academy of Sciences of Ukraine,

Murmanska st. 5, 02094, Kyiv, Ukraine E-mail: [email protected]

1,2,3-Triazoles have attracted significant attention due to their wide spectrum of biological

activity. We have developed the convenient method for preparation of fluoroalkyl substituted triazoles 1 based on the reaction of 1,1-dihydropolyfluoroalkylsulfones with trimethylsilylazide in the presence of tertiary amines1.

RFSO2Ar

F

F

+ Me3SiN3 C6H6

DABCO

NNH

N

SO2ArRF

RF = CF3, HCF2, H(CF2)3; Ar = p-Tol, Benzyl(1)

N-Chloro derivatives of compounds 1 appeared good reagents for the synthesis of different N-substituted triazoles.

NNH

N

SO2ArRF

NaHgMeOH

NNH

N

HRF

NaOCl

NN

N

SO2ArRF

Cl

NNK

N

ClRF

NaOCl

NN

N

HRF

NN

N

HRF

Cl

+

O

NN

N

SO2ArRF

OCl

NN

N

ClRF

Cl

O

NN

N

HRF

NN

N

HRF

+

O

O

Cl Cl

NN

N

SO2ArRF

P(OEt)3

NN

N

SO2ArRF

O

KF/Cl2

KF/Cl2

(1)

NNH

N

ClRF

HCl

NaOClt-BuOK

Cl

____________________________________________ 1 Timoshenko V.M. et al. Khimia Geterotsikl. Soed. 2001, 4, 518–524.


Р-12

THE SYNTHESIS OF THE NEW 1,2,4-BENZOTHIADIAZINE DERIVATIVES WITH THE USAGE OF MORPHOLINOSULFUR

TRIFLUORIDE

Yu. G. Shermolovich, V. E. Pashinnik, N. P. Kolesnik, N. V. Bryukhovetska

Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Murmanska Street, 5, Kiev-94, 02660, Ukraine


1,2,4-benzothiadiazine derivatives (1) which contain double S = N endocyclic bond, show high biological activity being effective plant growth regulators and fungicides.

SN

N

X

R

1

1, R = CCl3, C6H5; X = Cl, NR'R''; n = 1-4

Cln

We proposed the new method of the synthesis of 1,2,4-benzothiadiazine derivatives, which consists in the reaction of N-phenylamidines with morpholinosulfur trifluoride1. This method allows to obtain the derivatives of 1,2,4-benzothiadiazine without chorine atoms in benzene ring in opposite to the known methods of these compounds synthesis. The reaction of 1-morpholino-3-trifluoromethyl-1,2,4-benzothiadiazine with dry hydrogen chloride leads to the formation of 1-choro-3-trifluoromethyl-1,2,4-benzothiadiazine which can be used for the synthesis of 1-amino-1,2,4-benzothiadiazines new derivatives.

N

RNH2

R2NSF3

R

N

N S

NR2

F

SN

N R

NR2

N O

SN

N R

Cl

+NaF(excess), CH3CN

- 2NaF . HF

- NaF . HF

R = CF3,CCl3, C6H5;

NR2 =

HCl

______________________________________

1 Kolesnik N.P. et al.Ukr.Khim. Zhurn. 2002, 11, 44-47.


Р-13

S-ARYL- AND S-(BENZOTHIAZOLYL-2)-S-(DIALKYLAMINO)-SULFUR DIFLUORIDES

V. E. Pashinnik, V. N. Kozel, Yu. G. Shermolovich

Institute of Organic Chemistry NAS of Ukraine,

Murmanskaya St. 5, 02094, Kiev, Ukraine E-mail: [email protected]

The interaction of aryl- and benzothiazolyl-2-sulfur trifluoride I with

dialkylaminotrimethylsilanes leads to the formation of S-aryl- or S-(benzothiazolyl-2)-S-(dialkylamino)sulfur difluorides II. The reactions of difluorides II with p-arenesulfonamides and their hydrolisis have been investigated.

R = C6H5; 4-CH3C6H4; 4-FC6H4; 4-O2NC6H4; бензтиазолил-2

I II

R SF2 NAlk2

H2O

S N

NAlk2

SO2 Tol-p

R S NAlk2

O

III

IV

- Me3Si-F

Alk = Me, Et; Alk2 = (CH2)4, O(CH2)4

RH2N-SO2-Tol-p

R SF3 + Alk2N SiMe3

Difluorides II are unstable compounds wich are easily decomposed. The nature of the group R has an appreciable effect on the direction of the decomposition. Pathway a leads to the formation of 1-fluoro-4-nitrobenzene or 2-fluorobenzothiazole and amino-fluoro-sulfanes V which is converted into dialkylaminosulfur trifluoride and disulfides. Pathway b consists in the disproportionation into arylsulfur trifluoride and arylbis(dialkylamino)sulfonium fluorides VI.

- R FV

Alk2N-S-F

FR SF3 + R S

NAlk2

NAlk2

b: R = C6H5; 4-CH3C6H4; 4-FC6H4

VI

Alk2N-SF3 + (Alk2N-S)2

a: R = 4-O2NC6H4; бензтиазолил-2

a

bII

R SF2 NAlk2


Р-14

FLUORINATED 3Н-1,2-DITHIOLE-3-THIONES: SYNTHESES OF FLUORO-SULFUR-CONTAINING COMPOUNDS

I. M. Fesun, V. M. Timoshenko, Yu.G. Shermolovich

Institute of Organic Chemistry NAS of Ukraine, Murmanska St., 5, 02094 Kyiv-94, Ukraine

E-mail:[email protected]

3H-1,2-Dithiole-3-thiones have attracted a significant attention due to their wide spectrum of biological activity. They are also interesting as starting materials for the synthesis of new sulfur-containing compounds. The presence in the molecule of 1,2-dithiole-3-thiones 1 of fluorine atom together with polyfluoroalkyl substituent gives a possibility for a great variety of synthetical applications of such compounds in organic synthesis. A number of heterocyclic as well as acyclic fluoro-sulfur-containing derivatives were obtained used cycloaddition, reduction and opening-ring reactions1,2.

SS

RF F

S

RF = CF3, (CF2)2H

S

RF F

SS

EE

F

SS

EE

S

RF

SS

SRF F

E

EEE

SS

F

N

RF

R

SS

F

X

X

RF

AlkS

RF F

SNR2

R2NH

RF

S

H

NR2R2N

Na2S

SSS

F FSH

S

SHFF

S

Na2S

DMADDMAD

R2NH, ∆X

X

H2N R

S

S

S E

EE

E

OHRF

E = COOMeX = CN, COOEt

1

___________________________ 1 Timoshenko V.M. et al. Tetrahedron Lett. 2002. 43(33), 5809-5812. 2 Timoshenko V.M. et al. Eur. J. Org. Chem. 2003. 13, 2471-2474.


Р-15

NEW SYNTHESIS OF 2-POLYFLUOROALKYL SUBSTITUTED IMIDAZOLINES, 1,4,5,6-TETRAHYDROPYRIMIDINES AND 4,5,6,7-

TETRAHYDRO-1H-1,3-DIAZEPINES.

A. V. Rudnichenko, V. M. Timoshenko, E. I. Kaminskaya, Yu. G. Shermolovich

Institute of Organic Chemistry of National Academy of Sciences of Ukraine, Murmanskaya Street, 5, 02094 Kiev-94, Ukraine


A new efficient method for the preparation of 2-polyfluoroalkyl substituted imidazolines1, 1,4,5,6-tetrahydropyrimidines and 4,5,6,7-tetrahydro-1H-1,3-diazepines by the reaction of polyfluoroalkylthiocarboxylic acids amides and aliphatic diamines is presented. In opposit to known methods, described in literature, new method have except the usage of toxic regents (trifluoroacetonitrile or tetrafluoroethylene) and high or low temperature using.

___________________________________________ 1 Rudnichenko A.V. et al. Zhurn. Org. Pharm. Khimii (Ukr). 2006, in press.

RF NH2

S NH2

NH2

(n)

NH2

NH2

(n)

NH

NRF

N

NH

RF

NH

NRF

n = 0, 1, 2

Et2O, 15-20 OC

- NH3

_ * H2S

+n = 1

n = 2

78 - 95.3 %

55 - 72.3 %

RF = CF3, HCF2, C2F5, H(CF2)2, C3F7, H(CF2)4

2

68 - 94 %

n = 0


Р-16

SYNTHESIS OF ETHYL-2-ARYLAMINOMETHYLIDENE- 3-OXO-3-POLYFLUOROALKYLPROPIONATES

M. V. Pryadeina, Ya. V. Burgart, V. I. Saloutin

Institute of Organic Synthesis UD RAS,

S. Kovalevskoy/Akademicheskaya Str., 22/20, 620219, Ekaterinburg, Russia E-mail: [email protected]

Ethyl-2-ethoxymethylidene-3-oxo-3-polyfluoroalkyl-propionates I react with equimolar

amount of arilamines (aniline, p-anisidine, p-toluidine, benzylamine) or aryldiamines (o-phenylenediamine, p-phenylenediamine) at the ethoxymethylidene substituent to give ethyl-2-arylaminomethylidene-3-oxo-3-polyfluoroalkylpropionates II. The compounds II can be obtained by tree-component reaction of 3-oxo ester III, triethylorthoformiate and monoamines. Examination of NMR spectra of the esters II shows that they exist in the solution as a mixture of Z- и Е-isomers. Data of crystal X-ray analysis demonstrate that esters II have Е-isomer form stabilized by intramolecular hydrogen bond between amine group and polyfluoroacyl fragment.

Esters I react with o-phenylenediamine or p-phenylenediamine in a ratio of 2 : 1 to form phenylene-N,N’-bis-(ehtyl-3-amino-2-polyfluoroacylprop-2-enoates) IV and V. The reactions of propionates II having a free aminogroupe with esters I may be used for the preparation of bis-products IV and V.

I

fR

O O

OEt

OEt N

R

H

O O

ROEt

Rf= HCF2, CF3, H(CF2)2, C3F7; R= Ph, 4-Me-C6H4, 4-MeO-C6H4, Ph-CH2, 2-NH2-C6H4, 4-NH2-C6H4;i: C6H6 (Et2O), 20 oC; ii: EtOH, Тboil; iii: EtO, 20 oC ; iv: EtOH, Тboil

II

+ HC(OEt)3

R

NH2

iif

f

f

N

N

H

H

O

R

O

CO2Et

CO2Et

R

N

N

O

R

R

CO2Et

CO2Et

H

H

O

f

f

R

NH2

fR

O O

OEt

i

iii (iv)

III

IVV

I (II)

The obtained propionates II, IV, V can be used as polyfunctional blocks for new compounds synthesis or as ligands for complexation.

This work was supported by Russian Foundation for Basic Research (grant № 05-03-32384).

.


Р-17

OXIDES OF TERMINAL AND INTERNAL PERFLUOROOLEFINS IN SYNTHESIS OF NOVEL FLUOROCONTAINING

N, S-HETEROCYCLES

L. V. Saloutina, A. Ya. Zapevalov, M. I. Kodess, V. I. Saloutin, O. N. Chupakhin

I. Ya. Postovsky Institute of Organic Synthesis, Urals Branch of the RAS, 22/20 S. Kovalevskoy/Academicheskaya, 620219 Ekaterinburg, Russia

E-mail: [email protected] It is found that on interaction of terminal and internal perfluoroolefins (I) with 2-aminothiophenol (ATP) unexpected products, 1,5-diaza-7,8-dithia-3-perfluoroalkyl-1,6(1,2)-dibenzenecycloocta-4-ones (II) and 2,3-bis(perfluoroalkyl)-3,4-dihydro-2H-benzothiazin-2-ols (III) (mainly in anti form), respectively, are formed. Formation of heterocycle (II) occurs, obviously, as a result of addition of two molecules of ATP to oxirane (I, R1 = F, R2 = perfluoroalkyl) at NH2 group of the nucleophile with subsequent reduction of the C=N bond and oxidation of SH groups in the intermediate (A). In the case of internal oxiranes (I, R1, R2 = perfluoroalkyl), the reaction also begins with an attack of the NH2 group of the nucleophile at one of the epoxide carbon atoms with following ring opening and formation of the intermrdiate (B). The latter is reduced to benzothiazine (III) under the action of ATP; at the same time, ATP is oxidized to give 2,2'-diaminodiphenyldisulfide (IV). The effect of a solvent nature on the direction of reactions studied is discussed. The structure of compounds obtained was confirmed by 1H, 19F, 13C NMR, IR spectroscopy, mass spectrometry, elemental analysis and X-ray analysis.

O

RF

F

N S

R

OHR

NH S

R

OH

H

RS

S

NH2

NH2

SH

NO

N

H

SH

S

NN

O H

SH R

H

SH

NH2

SH

NH2

SH

NH2

(B) (III)

+

(IV)

R1, R2 = перфторалкил

(A)

2

(II)

2

R1 = F

R2 = перфторалкил

1

1

2

2

22

(I)

R1

R2

Работа выполнена при финансовой поддержке Государственной Программы поддержки ведущих научных школ Российской Федерации (проект № НШ-9178.2006.3).


Р-18

SYNTHESIS OF FLUOROCONTAINING N,O-HETEROCYCLES FROM OXIDES OF INTERNAL PERFLUOROOLEFINS

L. V. Saloutina, A. Ya. Zapevalov, M. I. Kodess, V. I. Saloutin, O. N. Chupakhin

I. Ya. Postovsky Institute of Organic Synthesis, Urals Branch of the RAS, 22/20 S. Kovalevskoy/Academicheskaya, 620219 Ekaterinburg, Russia


Oxides of internal trans-, cis-perfluoroolefins 1 have been shown to react with urea in polar aprotic solvents yielding a new type of glycolurils – 2,4,6,8-tetraaza-1,5-bis(perfluoroalkyl)bi-cyclo[3.3.0]octan-3,7-diones 2.

Unexpected heterocyclic products, 2-amino-4-hydroxy-4,5-bis(perfluoroalkyl)oxazolines 3 (predominantly in trans form), are formed at change of conditions of the interaction between oxiranes 1 and urea. Asymmetrical perfluoro-2,3-epoxyalkanes 1 with urea yield mixtures of regioisomeric heterocycles 3 which can be separated by crystallization.

The alternative synthetic route to the glycolurils prepared by the above method is the reaction of urea with 1,2-diketones 4 or 4,5-dihydroxy-4,5-di(perfluoroalkyl)imidazolidin-2-ones 5.

The heterocycles synthesized are of interest as biologically active substances.

NH NH

NHNH

O

O

OOR

NH NH

O

OHR

OH

O N

OH

NH2

F RF2

RF1

(R )F

1

(R )F2

FCO

CFR1RF RF1 22 1RF

F

F

RF

RF

21

i : NH2CONH2

1

2

3

4

5

2F

i

i

i i

i

The research has been financially supported by the State Programme for supporting leading scientific schools of Russian Federation (grant No НШ-9178.2006.3).


P-19

THE INVESTIGATION OF GEOMETRIC ISOMERISM OF FLUOROALKYL-CONTAINING 1,2,3-TRIKETONES 2-ARYLHYDRAZONES AND THEIR BIS-DERIVATIVES

O. G. Khudina, Ya. V. Burgart, E. V. Shchegol’kov,

I. V. Shchur, M. I. Kodess, V. I. Saloutin


S. Kovalevskoy/Akademicheskaya Str., 22/20, 620219, Ekaterinburg, Russia Е-mail: [email protected]

We have studied the isomeric structure of fluoroalkyl-containing 1,2,3-triketones 2-

arylhydrazones 1 and their bis-derivatives 2 by the methods of IR, NMR spectroscopy and X-Ray diffraction analysis. Based on these data we have drawn a conclusion about predominant existence of compounds 1, 2 in crystals and СDCl3, (СD3)2CO solutions as the isomer (A) with intramolecular hydrogen bounded carbonyl group at non-fluorinated substituent.

N

N

H

X R

O

R

O

N

N

H

X

R

O

R

O

Rf = HCF2, CF3, H(CF2)2, C3F7, H(CF2)4, C4F9; R = Me, Ph, Bu, CF3; X = H, Me, OMe

BA

N

N

H

R

O

R

O

N

N

H

R

O

R

O

N

N

H

R

O

R

O N

N

H

R

O

R

O

f

f

f

f

f f

1

2

For trifluoroalkyl-containing 1,2,3-triketones 2-arylhydrazones 1 and their bis-derivatives 2 we have found the considerable differences in the coupling constants and the chemical shifts of the fluorine nuclei in NMR spectra 19F and 13С.

СF3-С=O 1JC-F, Hz 2JC-F, Hz 4JC-F, Hz δF, ppm free 292 (CDCl3,

(CD3)2СO) 31-34 (CDCl3, (CD3)2СO)

1 (CDCl3) 91-92 (CDCl3) 93-94 ((CD3)2СO)

intramolecular hydrogen bounded

287 (CDCl3) 40 (CDCl3) 1 (CDCl3) 87-88 (CDCl3) 89-90 ((CD3)2СO)

This work was supported by Russian Foundation for Basic Research (grant 05-03-32384а),

the State Programme for supporting leading scientific schools of Russian Federation (grant 9178.2006.3).


P-20

INTERACTION OF FLUOROALKYL-CONTAINING 2-ARYLHYDRAZONO-3-OXO ESTERS WITH METHYLAMINE

E. V. Shchegol’kov, Ya. V. Burgart, V. I. Saloutin


S. Kovalevskoy/Akademicheskaya Str., 22/20, 620219, Ekaterinburg, Russia E-mail: [email protected]

The interaction of fluoroalkyl-containing 2-arylhydrazono-3-oxoesters 1 with methylamine

in ethanol at 20 oC was found to give amides 2 as a result of the amine condensation at ester fragment. However, that process was not the only in the case of ester 1 having bulky nonafluorobutyl substituent. So it was accompanied by the amine addition to the carbonyl group at fluorinated substituent following by the haloformic decomposition and elimination of fluoroalkane to form diamide 3. It is due to the formation of more stable outgoing carbaniones in the case of the compounds having long polyfluorinated substituents. The compounds 2, 3 were described in IR-spectra, 1H, 19F–NMR. The microanalyses were carried out.

NN

O

R

Ar

H

O

OAlk

1

f MeNH2

EtOH

NN

N

O

OMeH

R

H

Ar

2

Rf = HCF2; H(CF2)2; C3F7; C4F9; Alk = Me; Et; Ar = C6H4-Me-4; C6H4-OMe-4.

NN

N

O

MeH

N

Me

H

H

O

C6H4-OMe-

3

Rf= C4F9

- HC4F9

- HOAlk

20 oC4

f

- HOAlk

The obtained amides 2, 3 can be used for metalocomplexes synthesis. This work was supported by Russian Foundation for Basic Research (grant № 05-03-

32384).


P-21

PERFLUOROEPOXYOXOLANES IN THE SYNTHESIS OF FLUORINE-CONTAINING HETEROCYCLES

T. I. Filyakova, A. Ya. Zapevalov, M. I. Kodess, V. I. Saloutin

Institute of Organic Synthesis, Ural Division of Russian Academy of Sciences.

S. Kovalevskoy Str. 22, Ekaterinburg, Russian Federation. E-mail: [email protected]

Continuing our study on reactivity of perfluoroepoxides, we have investigated the reactions

of perfluoro-3,4-epoxyoxolan (I) and 2-trifluoromethylpentafluoro-3,4-epoxyoxolan (II) with series of bifunctional nucleophilic reagents. The epoxyoxolanes (I,II) which contain both oxirane and oxolane cycles were synthesized by hypohalogenite method from corresponding perfluorooxolenes5, their reactivity has not been studied.

The compounds (I,II) were found to react readily with nucleophiles giving epoxide ring-opened products. As a result of interaction of epoxyoxolanes (I,II) with thiourea, benzene-1,2-diamine and 2-aminophenol new fluorine-containing heterocycles - perfluorotetrahydrofuro- and 2-(trifluoromethyltrifluorotetrahydrofuro)[3,4-d](2-amino-4-hydroxy-5-fluoro-1,3-thiazolines) (III,IV), perfluorotetrahydrofuro- and 2-(trifluoromethyltrifluorotetrahydrofuro)[3,4-b]quinoxalines (V,VI) and perfluorotetrahydrofuro[3,4-b]benzoxazin-3a(2H)-ol (VII) were synthesized.

O

O

XF

(NH2)2C=SO

OH

X

N

S

F

NH2F

X = F (I), CF3 (II)

X = F (III), CF3 (IV)

X = F (V), CF3 (VI)

NH2

NH2

O

N

O F

NH2

OH

OH

N

N

O F

X

VII

The structure of the compounds (III-VII) was confirmed by IR, 1H, 19F, 13C NMRspectroscopy and elementary analysis data.

5 Filyakova T.I. et.al. Zh. Org. Khim. 2003,39(7), 1073-1078.


P-22

REACTIONS OF POLYFLUOROCONTAINING GLYCIDYL ETHERS WITH ALCOHOLS UNDER PHASE TRANSFER CATALYSIS

D. N. Bazhin, T. I. Gorbunova, A. Ya. Zapevalov, V. I. Saloutin

I. Ya. Postovsky Institute of Organic Synthesis of the Ural Branch of the RAS,

S. Kovalevskaya st., 22, 620219, GSP-147, Ekaterinburg, Russia; E-mail: [email protected]

It has been earlier shown, that fluorocontaining glycidyl ethers are monomers for the

preparation of polymeric materials with different properties and present particular interest from the point of the view of transformations of the oxirane’s ring under action of the various reagents. In the literature has been described reactions in which fluorocontaining oxiranes in processes with the nucleophilic reagents reveal significant disposition to hydrolisys and oligomerization. Such behavior of the oxiranes are connected with conditions of carrying out of the process (temperature, time, type of solvent, the order of loading of reagents), and also with the nature of nucleophiles.

We are shown that interaction of the synthesized glycidyls ethers (1,2) with different alcohols (i-PrOH, MeOH, PhOH, 2,2,3,3-tetrafluoropropanol) in base medium results to the products of the regioselective ring-opening of oxirane (1 a-c, 2 a-d). Formation of the corresponding 1, 2 - diol (3) in reaction of the oxirane (1) with the isopropanol is revealed.

O

OR

OHRFO RFO

i, ii

1,2 1 a-c, 2 a-d, 3

1: RF = H(CF2)2CH2; R = Me (a), Ph (b), H(CF2)2CH2 (c);2: RF = C3F7OCF(CF3)CF2OCF(CF3)CH2; R = Me (a), Ph (b), H(CF2)2CH2 (c), (CH3)2CH (d);3: RF = H(CF2)2CH2 , R = Hi : ROH, KOH, Et2O-H2O, Bu4N

+Br, to, 2 h ii: H2O, HCl

-

The structures of the synthesized compounds affirmed data of the elemental analysis, IR,

NMR spectroscopy and mass-spectrometry. This work was supported by Russian Foundation for Basic Research (project № 04-03-

96109).


P-23

FLUORINATED ACIDS AND THEIR DERIVATIVES IN THE SYNTHESIS OF TRIAZOLES AND THIADIAZOLES

E. B. Letovaa, L.P. Sidorovab, V.I. Filyakovaа, V.N. Charushinа

a I.Y. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian

Academy of Sciences, 620219, Yekaterinburg, S. Kovalevskoy st., 22 Е-mail: [email protected]

bUral State Technical University, 620002, Yekaterinburg, Mira st., 19. E-mail: [email protected]

Condensations of acids, their esters and halogen anhydrides with thiosemicarbazides may

result in the formation of triazolinethiones and/or thiadiazoles. It has been found that condensation of fluoroacetic acids with 4-substituted

thiosemicarbazides (TSC) 1 results in a mixture of compounds 2 and 3. Monitoring of the reaction mixtures by means of NMR 19F spectroscopy has shown that isomerisation of thiadiazole 2 into a more stable triazolinethione 3 takes place in the course of the reaction.

NH

N

N S

R

R

NH

S

NH

NH2R

NN

SR NHR

N

N4-FC6H4, 4-CF3OC6H4, 4-CF3C6H4, Ph,

4-CH3C6H4, 3-ClC6H4, 4-CH3OC6H4, 2-FC6H4

+RFCOOH FF+

2

R = , ,

1 3

∆

Triazolinethiones 3 and their S-methylation products 4 are formed from the reaction of

fluorinated esters TSC 1.

RNH

NH

NH2

S

O

ROEt

NH

N

N S

R

RF

NN

N SCH3

R

RF++

3 4

CH3ONaF

1

∆H+

H2O

Model thiadiazoles 5 were obtained to elucidate diagnostic features enabling one to control

routes of the reaction.

S

NH

NH2

NNN

SF3C N

N N O N N=, ,

5

CF3COOH +∆

Analysis of IR, NMR 1H, 13C и 19F spectra of compounds 2,3 and 5 has shown that chemical shifts of CF3 and HCF2 groups in the NMR 19F spectrum to be of diagnostic value to determine which type of compounds (2 or 3) is formed. Thiadiazoles 2: δCF3 102 p.m., δHCF2 ~ 47 p.m. Triazolinethiones 3: δCF3 ~ 98 p.m., δHCF2 ~ 44 p.m. (C6F6 – internal standard).


P-24

SYNTHESIS OF FLUORINATED BENZAZOLES

S. K. Kotovskayaa, V. N. Charushinb, O. N. Chupakhinb

aUrals State Technical University, Mira 19, Ekaterinburg, 620219, Russia,

E-mail: [email protected] bInstitute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,

S. Kovalevskaya/ Academicheskaya st. 22/20, 620219 Ekaterinburg, Russia

During the last decades the chemistry of fluorinated compounds became one of the most developing branches of organic synthesis. Not only the family of fluoroquinolones which are well-recognized at the world pharmaceutical market as highly efficient antibacterials, but also other classes of fluorinated heterocycles have gained attention of chemists and biologists, since many fluorine-containing compounds demonstrate a high biological potency due to their ability to inhibit specific enzymes, good solubility in lipids and an easy penetration throw cell membranes. Due to the recently discovered ability of fluorinated arenes to form F…H hydrogen bond with DNA bases, fluorinated benzazoles can be regarded as intriguing subjects for medicinal chemistry1.

In continuation of our research studies2,3 we wish to report on synthetic approaches to such fluorinated benzazoles, as indoles (1), benzimidazoles (2), N(1)- and N(2)-substituted benzotriazoles (3 and 4), benzofuroxans (5) and benzofurazans (6).

N

R3

R2

F

N

N

R3

R2

F

R1

NN

N

R2

F

R1

N

O

N

O

F

R1

N

O

NF

R1N

N

N

R2F

R1

R1

1

+

_

2 3

4 5 6

Tautomerism and reactivity of fluorinated benzazoles (1-6), as well as their ability to be

transformed into other heterocyclic systems will be discussed. The data of biological studies, including a remarkable antiviral activity exhibited by a number of compounds of these series will be presented.

The research was supported financially by the Russian Foundation for Basic Research (Projects No 04-03-08103ofi-a, 05-03-32792a).

________________________________ 1 Evans T.A. et al. Chem. Comm, 1997, 2023-2024. 2 Kotovskaya S.K. et al. J. Fluorine Chem. 2004, 125, 421-428. 3 Kotovskaya S.K. et al. Synth. Comm. 2004, 34, 2531-2537.


P-25

EFFECTIVE METHOD FOR AMINATION OF FLUORINATED 1,3-DIKETONES

D. L. Chizhov, V. N. Charushin

I. Ya. Postovskii Institute of Organic Synthesis, Ural Branch of the RAS,

S. Kovalevskoy/ Akademicheskaya Str. 22/ 20, 620219, Ekaterinburg, Russia. E-mail: [email protected]

Fluoroalkylated β-aminoenones are important and versatile reactants to form complexes

with ions of metals, as well as for the synthesis of various mono- and fused heterocycles (4-aminopyridines, quinolines, 1,5-benzheteroazepines etc.).

One of the synthetic route to these compounds is the reaction of amines with fluoroalkylated 1,3-diketones, however this approach has some limitations: amines with low basicity do not afford aminoenones and reactions of diketones with amines bearing additional functionalities (e.g. 1,2-diaminobenzene) frequently can not be stopped for desired β-aminoenones resulting in heterocyclic products. Application of fluoroalkyl β-alkoxyenones, that are formally enol ether of corresponding 1,3-diketones, decides the pointed problems. Therefore, facility of preparation of various fluoroalkylated 1,3-dicarbonyl compounds via the Claisen condensation keeps 1,3-diketones more preferable to the creation of various fluorinated β-aminoenones.

We have found, that fluoroalkylated 1,3-diketones 1 react with amines of various basic character in the presence of one equivalent of B(OEt)3 affording fluoroalkylated β-aminoenones 2 in good yields (Scheme 1), even in those cases were additional functionalities are present in aminocompounds.

RF R1

O O

RF R1

O HNR2

CH2Cl2, RT

NH2R2/ B(OEt)3

RF= CF3, HCF2FC2, C3F7

R1= Me, i-Pr, cyclo-Pr, Ph, 4-MeOPh, 4-NO2Ph, 3-Py, 4-Py

R2= Me, Bz, Ph, 2-NO2Ph, 2,4-Cl2Ph

1 2

69-95 %

Scheme 1.

Amination time in these conditions is varied from some minutes to three days and depends on substituent R1 and R2, while a length of the fluoroalkyl groups has no effect on the reaction time.

The performance of B(OEt)3 is supposed to be conditioned by two factors: 1. Activation of one of two carbonyl groups in 1 for the addition of nucleophiles owing to a coordination of B(OEt)3 with 1,3-diketones. 2. Fast and irreversible hydrolysis of B(OEt)3 by water formed in course of the reaction. In summary, a facile and effective approach to a wide range of fluoroalkylated β-

aminoenones via the reaction of fluoroalkylated 1,3-diketones bearing alkyl, aryl and hetaryl groups with various alkyl-, aryl- and hetarylamines in the presence of B(OEt)3 has been developed.


P-26

SPECIFIC CHARACTERISTICS OF MASS-SPECTRA OF FLUORINATED HYDROXYDIETHERS

V. E. Kirichenko, M. G. Pervova, D. N. Bazhin, T. I. Gorbunova, A.Ya. Zapevalov, V.I. Saloutin

I. Ya. Postovskii Institute of Organic Synthesis, Ural Branch of the RAS,

S. Kovalevskoy/ Akademicheskaya Str. 22/ 20, 620219, Ekaterinburg, Russia. E-mail:[email protected]

For the first time the mass-spectra of products of interaction of glycidyl 2,2,3,3-

tetrafluoropropyl ether with alcohols were studied.

H(CF2)2CH2OCH2CH CH2

O

R = CH3 (I), CH(CH3)2 (II), CH2CH=CH2 (III), CH2(CF2)2H (IV), C6H5 (V)

1. RONa, ROH, dioxane

2. HCl, H2O CH2

OR

H(CF2)2CH2OCH2CH

OHI - V

Gas chromatography/mass spectrometer «Fisons MD 800» in electron ionization mode (70

eV) with HP-5 column was used. The mass-spectra confirmed the structure of fluorinated hydroxydiethers (I-V). The fragmentation and relative intensivities of MS peaks were affected by R nature significantly. The peak M+• was registrated only for V with R = Ph. Characteristic peaks m/z 175 [C5H7F4O2]

+, m/z 145 [C4H5F4O]+ and [CH2OR]+ were registrated always. These fragments are formed during α-cleavage in regard to hydroxygroup. Characteristic peak m/z 57 [C3H5O]+ was present in all mass-spectra, as it have been shown for glycidol derivatives with CF2CH2OCH2-group. The peaks of ions m/z 45, 44, 43 were registrated at the different ratio.

The feature of I consisted in the presence of small intensive peak [M-H2O]+• (< 1 %), the base peak m/z 45 [C2H5O]+ was the product of α-cleavage.

For II the peaks of ions [M-CH3]+ and [M-OCH(CH3)2]

+ with the intensivity 1 and 5 % were registrated. The base peak m/z 43 included the ions [CH(CH3)2]

+ and [C2H5O]+. The peak m/z 73 [CH2OCH(CH3)2]

+ had the high intensivity too. Similar to II, ionization of III gave the ion [M-OCH2CHCH2]

+ with maximum mass, the ion m/z 41 [CH2CH=CH2]

+ with maximum intensivity and ions m/z 71 [CH2OCH2CHCH2]+, m/z

43. Ionization of IV with two H(CF2)2CH2-groups gave the ions [M-H2O]+•; the base ion m/z

175 and intensive ion m/z 43. The peaks of fluorocontaining fragments were the most intensive among the similar peaks of the studied compounds (m/z 145, 51 et al.).

The diether V gave the M+• with 17 % intensivity and the base peak m/z 94 [C6H5OH]+. The intensivities of other peaks were below 30 %, characteristic peaks had m/z 107 [C6H5OCH2]

+, m/z 77 [C6H5]+, m/z 51 [CF2H]+. The peak m/z 175 had the minimum intensivity

among the similar peaks of the studied compounds. The research was supported financially by Russian Foundation for Basic Research

(Project № 04-03-96109).


Р-27

NMR IDENTIFICATION OF REGIOISOMERIC α- AND γ-FLUOROALKYL-CONTAINING

N-HETEROCYCLES

M. I. Kodess, E. G. Matochkina, N. S. Boltacheva, O. G. Khomutov, V. I. Filyakova, V. N. Charushin

Institute of Organic Synthesis of RAS (Ural Division),

22/20, S.Kovalevskoy/Akademicheskaya St., Ekaterinburg, 620219, Russia E-mail: [email protected]

19F NMR Spectroscopy has a number of special features which make it a powerful tool for

the fine structural studies. Such peculiarities of 19F NMR spectroscopy as the broad range of chemical shifts; the high values of F-F, F-H, F-C spin-coupling constants together with the ability of fluorine nuclei to participate in long-range spin-couplings transferred both through-bond and through-space; have been applied in the present study for the structural identification of α- and γ-fluoroalkylsubstituted heterocyclic compounds 1 and 2 obtained as a result of interaction between fluorinated cyclic β-diketones (or their Li-enolates) and α-naphthylamine1. Heterocycles 1 and 2 were obtained as individual isomers or their mixtures depending on the reaction conditions and the substrate nature.

N

CF2X

N

CF2X

X = F, n = 1 (1a, 2a); n = 2 (1b, 2b)X = H, n = 1 (1c, 2c); n = 2 (1d, 2d)

1a-d

n

2a-d

n

Complete assignment of 1H and 13C resonances was performed using 2D COSY, NOESY, HSQC, and HMBC homo- and heteronuclear experiments. 1H and 13C chemical shifts of these regioisomers do not have any characteristic properties making it possible to identify the structure. Long-range coupling constants of fluorine atoms with cyclic carbon and hydrogen atoms can serve as the diagnostic indicators. In particular, in the structures of 1 type we observed 5JHF and 4JCF constants with CH2 group of saturated cycle, whereas in structures 2 5JHF constant with the aromatic proton appeared in addition to the same coupling. The structure of compound 1b was confirmed by X-ray crystallographic data.

Comparison of 19F chemical shifts for tri- and difluoromethyl groups in the compounds studied with the literature data2 for pyridines and quinolines with CF3 group at α- or γ-positions to nitrogen atom makes it possible to reveal the regularity general for N-heterocycles, i.e. the resonances of fluoroalkyl substituents at γ-position are shifted to lower field as compared with the resonances of the same substituent at α-position.

The work was partially financially supported by Rosnauka (State Contract No 02.451.11.7062).

__________________________ 1 Karpenko N.S. et al. Russ. Chem. Bull. 2003, 52(5), 1215-1216. 2 Gerus I.I. et al. Ukr. Khim. Zh. 1993, 59(4), 408-411.


Р-28

REACTIONS OF 3-NITRO-2-TRIHALOMETHYL-2H-CHROMENES WITH C-NUCLEOPHILES

V. Yu. Korotaev, I. B. Kutyashev, V. Ya. Sosnovskikh

A.M. Gorky Ural State University,

Lenina ave. 51, 620083, Ekaterinburg, Russia Е-mail: [email protected]

We have recently shown1 that the reaction of activated trifluoro(or trichloro)methyl

substituted alkenes with salicylaldehydes in the presence of triethylamine gives 3-benzoyl- and 3-nitro-2-trihalomethyl-2H-chromenes in good yields. In continuation of this work and in view of the biological significance of some chroman derivatives, we now wish to report that interaction of 3-nitro-2-trihalomethyl-2H-chromenes 1a–f with C-nucleophiles (nitroalkanes, acetylacetone, and acetoacetic ester) proceeds in a conjugated manner at the C-4 atom to be obtained 2,3,4-trisubstituted chroman derivatives 2 and 3 (scheme 1).

O CX3

NO2R

O CX3

NO2R

NO2R1

O CX3

NO2RR2

R1CH2NO2 AcCH2COR2

NaH, THFK2CO3

3a-k2a-h 1a-f

OH

O

R = R1 = H, X = F (1a, 2a); R = R1 = H, X = Cl (1b, 2b); R = Br, R1 = H, X = F (1c, 2c);

R = Br, R1 = H, X = Cl (1d, 2d); R = H, R1 = Me, X = F (1a, 2e); R = H, R1 = Me, X = Cl (1b, 2f);

R = Br, R1 = Me, X = F (1c, 2g); R = Br, R1 = Me, X = Cl (1d, 2h); R = H, R2 = Me, X = F (3a);

R = H, R2 = Me, X = Cl (3b); R = Br, R2 = Me, X = F (3c); R = Br, R2 = Me, X = Cl (3d);

R = MeO, R2 = Me, X = Cl (1e, 3e); R = NO2, R2 = Me, X = Cl (1f, 3f); R = H, R2 = OEt, X = F (3h);

R = H, R2 = OEt, X = Cl (3i); R = Br, R2 = OEt, X = F (3j); R = Br, R2 = OEt, X = Cl (3k)

Scheme 1.

Chromenes 3a–e were reacted with hydrazine hydrate in ethanol at ~20 °C, affording the trans-trans 4-(3,4-dihydro-2-trihalomethyl-3-nitro-2H-1-benzopyran-4-yl)-3,5-dimethyl-1H-pyrazoles 4a–e without change of a relative configuration of pyran ring; at the same time, the reaction of compound 3f results in the formation of trans-cis isomer 4f (scheme 2).

O CX3

NO2RN2H4

3a-fO CX3

NO2R

N

4a-f

NH

EtOH

OH

O

Scheme 2.

The research was supported financially by Russian Foundation for Basic Research (Project

No. 04-03-32463). _______________________ 1 V.Yu. Korotaev et al. Heteroat. Chem. 2005, 16(6), 492–496.


P-29

SYNTHESIS AND REACTIVITY OF N-SUBSTITUTED 2-(POLYFLUOROALKYL)QUINOLINE-4(1H)-THIONES

B. I. Usachev, I. A. Bizenkov V. Ya. Sosnovskikh

aA. M. Gorky Ural State University, Lenina ave. 51, 620083, Ekaterinburg, Russia

Е-mail: [email protected]

2-(Polyfluoroalkyl)-4(4H)-chromene-4-thiones (1) prepared by us for the first time1 by the treatment of 2-(polyfluoroalkyl)chromones (2) with P2S5 showed essential difference in the reactivity in comparison with (2) due to change of the reactive centers activity C(2) and C(4) to nucleophiles. Owing to the selective nucleophilic attack at the C(4) atom and easy substitution of the thionic sulfur atom in the compounds (1) a series of new 2-(polyfluoroalkyl)chromenazomethines (3) have been synthesized. It turned out, that the compounds (3) easily capable of cyclization into pyrazole and isoxazoline derivatives1.

We have shown, that the N-substituted 2-(polyfluoroalkyl)quinolones (4), being synthetically available analogues of (2)2,3, enough quickly reacted with P2S5 giving the corresponding 2-(polyfluoroalkyl)quinolin-4(1H)-thiones (5) in high yields. We have found that the compounds (5) like thionechromones (1) reacted with hydrazine, phenyl hydrazine, and hydroxylamines to produce the azomethines (6) in ca. 80-90 % yields.

.

O

S

RFO

O

RF

P2S5

1 2

34 XNH2

X = NH2, PhNH, OH, ArO

NX

RF

12 3

RF = CF2H, CF3, CF2CF2H

N

O

RF

R

P2S5

N

S

RF

R

XNH2

-H2S

-H2S

X = NH2, PhNH, OHN

NX

RF

R4 5 6

R = Me, Ph

Fig. 1. 2-(Polyfluoroalkyl)-4(4H)-chromene-4-thiones (1) and 2-(polyfluoroalkyl)quinoline-4(1H)-thiones (5)

in the reactions with N-nucleophiles The compounds (6) are advanced materials for the preparation of novel fluorine-containing

heterocycles, especially for the synthesis of substances containing a pharmacophoric fragment of quinolone.

The research was supported financially by CRDF (Project No. Y1-005-04).

_______________________ 1 Usachev B.I. et al. Rus. Chem. Bull. 2004, (10), 2285–2293. 2 Usachev B.I. et al. J. Fluorine Chem., 2004, 125(9), 1393–1395. 3 Sosnovskikg V. Ya. et al. Izv. AN, Ser. Khim. 2002, (11), 1954–1960.


Р-30

THE INTERACTION OF N,N-DICHLOROTRIFLAMIDE AND TRIBROMOETHENE

E. V. Kondrashov, I. B. Rozentsveig, G. G. Levkovskaya, A. N. Mirskova

Irkutsk Institute of Chemistry named after A. E. Favorsky SB RAS,

1, Favorsky st., 664033, Irkutsk, Russia E-mail: [email protected]

Reactions of N,N-dichlorosulfonamides and polyhalogenethenes are convenient way to a

number of sulfonylimines of polyhalogenaldehydes1, including N-2,2,2-trichloroethyliden- and N-2,2-dichloroethyliden triflamides2,3. They are high reactive building blocks for organic synthesis.

Developing suitable methods for obtaining of highly electrophilic trifluoromethylsulfonyl imines of polyhalogenaldehydes we studied the reaction of N,N-dichlorotriflamide (I) with excess of tribromoethene. The interaction begins under the room temperature on sun light and is accompanied by strong exothermic effect, especially on sharp sun light. We found the reaction yield either trifluoromethylsulfonyl imine of dibromochloroacetic acid (II) or mixture of (II) and imine of tribromoacetic acid (III) depending on reaction conditions.

The imine of dibromochloroacetic acid (II) is formed under the temperature lower then 40 оС in 85% yield. When the reaction mixture is heated up to 100 оС or higher, the mixture of imines (II) and (III) is produced in equal imine mole relation.

CF3SO2NCl2

-Br2, -Cl2II

CF3SO2NCl + Cl

+ BrCH=CBr2 CF3SO2N CH CBr2

Cl Br

A

A

B

I

CF3SO2N CH CBr2Cl

Cl Br

CF3SO2N CH CBr2Cl

CB

CF3SO2NCl2

Cl

-CF3SO2NCl

CF3SO2N=CH CBr3

III-Cl

Br2

BrCl-Br CF3SO2N CH CBr3

Cl BrD

<40oC

-Br2, -Cl2

Under the temperature <40 оС we suppose a quantitative addition of (I) to tribromoethene is

likely to occure to give saturated product (C), accordingly4, which is further slowly dehalogenated to yield imine (II). Under heating adduct (C) is quickly dehalogenated to yield (II), so that radical (B) could interact with bromine or bromine chloride formed to give (III) through (D) formation.

Taking into account the experimental data obtained it is necessary to revise of reactions of N,N-dichlorobenzenesulfonamide or N,N-dichlorourethane with tribromoethene described earlier1. These reactions are proceed only at the elevated temperature.

So, we developed the fine synthetic path to trifluoromethylsulfonyl imine of dibromochloroacetic acid – high reactive amidoalkylating agent, precursor to N-polyfunctionally substituted triflamide derivatives. The reactions chemoselectivity dependence of the temperature was found.

1Levkovskaya G. G. et al. Russ. Chem. Rev. (Engl. Transl.). 1999, 68(7), 581-595. 2Rozentsveig I. B. et al. Russ. J. Org. Chem (Engl. Transl.). 2001, 37(11), 1559-1563. 3Kondrashov E. V. et al. Mendeleev Commun. 2003, 13(1), 25-27. 4Kondrashov E. V. et al. Russ. J. Org. Chem (Engl. Transl.). 2003, 39(10), 1418-1420.


Р-31

OXYMETHYLATION REACTIONS OF TRIFLUOROMETHANESULFONAMIDE

AND TRIFLUOROACETAMIDE

V. I. Mescheryakov, Yu. S. Danilevich, M. Yu. Moskalik, N. Yu. Stetsjura, B. A. Shainyan

A. E. Favorsky Irkutsk Institute of Chemistry Siberian Division RAS,

Favorsky St. 1, 664033, Irkutsk, Russia Е-mail: [email protected]

Oxymethylation of trifluoromethanesulfonamide (TFMSA) with formaldehyde leads to a

whole bunch of linear and cyclic products6. Here we report on the results of oxymethylation of trifluoroacetamide as well as of TFMSA in the presence of other amides.

Unlike TFMSA, trifluoroacetamide does not give cyclic products of oxymethylation, the only product was methylenebis(trifluoroacetamide) (CF3CONH)2CH2.

Oxymethylation of the mixture of TFMSA and methanesulfonamide affords, in addition to the already known linear product (CF3SO2NH)2CH2, the product of heterocyclization, 1-methylsulfonyl-3,5-bis(trifluoromethylsulfonyl)-1,3,5-triazinane. The latter compound showed an interesting stereochemical behavior which was studied by low-temperature dynamic NMR.

Unexpectedly, the three-component reaction of TFMSA, malonamide, and paraform gave 1-(trifluoromethylsulfonyl)dihydro-4,6(1H,5H)pyrimidine dione, probably, as a result of condensation of oxymethylated TFMSA with malonamide followed by intramolecular cyclization.

The transformations studied can be summarized as in the Scheme below:

N N

N

SO2CF3

SO2CF3CF3SO2

CH3CONH2

(in conc. H2SO4)

CF3SO2NH2 CH2ON N

N

SO2CH3

SO2CF3CF3SO2

CH3SO2NH2

CF3CONH2H2SO4

CH2O CF3CONHCH2NHCOCF3

CH2(CONH2)2

N NHCF3SO2

OO

NH

N

N

N

NN

CH2NHSO2CF3

Fig. 1. Oxymethylation and amidomethylation of trifluoroacetamide and trifluoromethanesulfonamide

6 V. I. Mescheryakov et al. Russ. J. Org. Chem. 2005, 41(9), 1381-1386.


Р-32

SUPRAMOLECULAR STRUCTURE OF N-METHYLTRIFLUORO-METHANESULFONAMIDE IN PROTOPHILIC MEDIA

I. V. Sterkhova, B. А. Shainyan, N. N. Chipanina, V. K. Turchaninov

A. E. Favorsky Irkutsk Institute of Chemistry Siberian Division RAS, Favorsky St. 1, 664033, Irkutsk, Russia


The presence of perfluoroalkyl substituents in the molecules of sulfonamides substantially increases their acidity and lipophilicity as an important factor of biological activity. Thus, perfluoroalkanesulfonamides CF3SO2NH2, C2F5SO2NH2, CF3SO2NHCH3 are NH-acids with pKа in Н2О equal to 6-8.

We have studied the solvate complexes of N-methyltrifluoromethanesulfonamide CF3SO2NHCH3 with aprotic protophilic solvents (Solv) by the use of IR spectroscopy and quantum chemical calculations (B3LYP/6-31G*) with the aim to elucidate how the specific solvation with the molecules of aprotic solvent affects the homoassociates of this compound, in particular, do they destroy to heteroassociates with the solvent, what is the structure of these associates and the type of hydrogen bonding in them.

According to our data, the system amide – protophilic medium can be described by the model which includes the equilibrium between the solvate H-complexes of the monomeric amide and its linear dimer with three-centered (bifurcational) hydrogen bond (BHB). In concentrated solutions of N-methyltrifluoromethanesulfonamide a two-component absorption band is observed in the region of ν(NH) 3050-3350 cm-1 regardless of the nature of the protophilic solvent (ketones, amides, ethers, esters, nitriles, etc.). The low-frequency component of this band belongs to the superimposed bands of the H-complex of monomer and H-complex of the linear dimer linked via its free NH group. The high-frequency component is due to stretching vibrations of the bridge NH group of the linear dimer. The hydrogen bond in these complexes is either conventional two-centered or bifurcational (three-centered).

N

Me

HCF3SO2

... N

Me

HCF3SO2

.O S

O

CF3

N H

Me

........

Solv

Solv

Solv

In H-complexes of the monomer the hydrogen bond with the solvent is two-centered and close to linear. The H-complex of the linear dimer with two molecules of the solvent (1:2) has BHB and exists as an individual species. Under certain conditions which are determined by the protophilicity of the solvent and, consequently, the stability of the H-complex it can transform into the H-complex of the linear dimer of the 1:1 composition or to the H-complex of the monomer. The formation of strong BHB results in weakening of the bridge and terminal H-bonds in the linear dimer. Therefore, homoassociates of N-methyltrifluoromethanesulfonamide which exist in its solutions in inert media are converted by specific solvation with protophilic molecules into heteroassociates: solvate H-complexes of the linear dimer of the 1:1 composition with two-centered hydrogen bond and of the 1:2 composition with bifurcational (three-centered) hydrogen bond..


Р-33

FLUORINATED SILICON-CONTAINING PHOSPHORAMIDES

N. F. Lazareva, A. I. Albanov, B. A. Shainyan, V. A. Pestunovich

A. E. Favorsky Irkutsk Institute of Chemistry Siberian Division RAS,

Favorsky St. 1, 664033, Irkutsk, Russia Е-mail: [email protected]

The first N-silylmethylated phosphoramides of the general formula

O=P(Me2N)m[NMe(CH2SiMen(OEt)3-n]3-m (m, n = 0, 2) have been synthesized by the reaction of the silylated amines MeNHCH2SiMen(OEt)3-n with (Me2N)mP(O)Cl3-m:

Et3N . HCl

Et3N; Et2O; 0 oC O=P(Me2N)m[NCH2SiMen(OEt)3-n]3-m

Me

MeNHCH2SiMen(OEt)3-nO=P(NMe2)mCl3-m

Under the Todd-Atherton reaction conditions the α-silylamines MeNHCH2SiMen(OMe)3-n (n = 0, 2) react with (MeO)2P(O)H to afford N-methyl-N-trimethoxysilylmethyl and N-methyl-N-dimethyl(methoxy)silylmethylamides of dimethyl phosphoric acid:

(MeO)2PO

HMeNHCH2SiMen(OMe)3-n

CCl4, Et3N, C6H6 (MeO)2PO

NCH2SiMen(OMe)3-n

Me

The Si-O bond in the synthesized compounds is splitted and replaced by the Si–F bond under mild conditions with BF3

. Et2O to give the corresponding fluorinated silicon-containing phosphoramides. According to 19F, 29Si, 31P NMR, the N-methyl-N-(trifluorosilylmethyl)amides of phosphoric acids exist in the chelate form with the P=O→Si intramolecular coordination bond:

BF3 Et2OR2PO

NCH2Si(OMe)3

Me

R2P

NSi

O

Me

FF

F

R = Me2N, MeO This is in compliance with the known fact that the coordination bonding in pentacoordinate

silanes is strengthened with the number of the fluorine atoms at silicon1. This type of bonding is practically not investigated unlike the intramolecular С=O→Si bonding in the pentacoordinate silicon compounds. So far there are only several examples of compounds with the intramolecular coordinate bond P=O→M (M = Si, Ge, Sn). To elucidate the nature of the P=O→Si bond and to compare the donating ability of the P=O and C=O groups we have calculated at the B3LYP/6-311+G(d,p) theoretical level a series of N-silylmethylated N-acylamides of phosphoric acids R2P(O)N(CH2SiX3)C(O)R’ potentially capable of competing between the P=O→Si and C=O→Si coordination.

The authors are grateful to the Russian Foundation of Basic Research for financial support (Grant 04-03-32673).

1 Schoeller W. W. et al., Inorg. Chem. 2000, (2), 375 - 381.


Р-34

CLEAVAGE OF Si-O-Si, Si-OR AND Si-NH-Si GROUPS WITH ORGANYLFLUOROSILANES AND -GERMANES

M. G. Voronkov, S. V. Basenko, I. A. Gebel, M. N. Kuranov

Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,

1 Favorsky Sir., 664033 Irkutsk, Russia E-mail: [email protected]

Hexamethyldisiloxane is cleaved with organyltrifluoro- or diorganyldifluorosilanes as low

as 20°C in the absence of catalysts to form earlier unknown 1,1,1-trimethyl, 3-organyl-3,3-difluoro- or 1,1,1-trimethyl-, 3,3-diorganyl-3-difluorodisiloxanes with the general formula R4-nSiFn-1OSi(CH3)3 (n = 2-3) in 57-97% yield.

RSiF3 + (CH3)3SiOSi(CH3)3 → RSiF2OSi(CH3)3 + FSi(CH3)3 (1) RR'SiF2 + (CH3)3SiOSi(CH3)3 → RR'SiFOSi(CH3)3 + FSi(CH3)3 (2) R, R’ = CH3, C1CH2, CH2 = CH, CH2 = CH —CH2, C6H5

The Si-O bond in 1,1,3,3-tetramethyldisiloxane is broken with organyltrifluoro- or diorganyldifluorosilanes in a similar manner but more slowly to give 1,1-dimethyl-, 3-organyl-, 3,3-difluoro- or 1,1-dimethyl, 3,3-diorganyl-, 3-fluorodisiloxanes with the general formula R4-nSiFn-1OSiH(CH3)2 (n = 2-3) in 50-70% yield. RSiF3 + (CH3)2HSiOSiH(CH3)2 → RSiF2OSiH(CH3)2 + FSiH(CH3)2 (3) RR'SiF2 + (CH3)2HSiOSiH(CH3)2 → RR'SiFOSiH(CH3)2 + FSiH(CH3)2 (4) R,R' = CH3, C1CH2, CH2=CH, C6H5

The reaction of phenyltrifluorosilane and –germanes with 1,1,1,3,3,5,5,5-octa-methyltrifluorosiloxane leads to 1,1,1,3,3-pentamethyl-, 5,5-difluoro-, 5-phenyltrisiloxane and –germoxane

C6H5MF3 + (CH3)3SiOSi(CH3)2OSi(CH3)3 → C6H5MF2OSi(CH3)2OSi(CH3)3 + (CH3)3SiF (5) M = Si, Ge whereas the reaction with tetrakis(trimethylsiloxy)siloxane gives tri(trimethylsiloxy)difluoro(phenyl)silane.

C6H5SiF3 + [(CH3)3SiO]4Si → С6H5SiF2OSi[OSi(CH3)3]3 + (CH3)3SiF (6)

Even under normal conditions of storage, the cleavage products disproportionate readily in different directions. The ability of these compounds to disproportionation depends on the nature of the substituents attached to the silicon atom and the number of fluorine atoms in the molecule. (CH3)3SiOSiFRR' → (RR'FSi)2O + RR'Si[OSi(CH3)3]2 + RR'SiF2 + RSi[OSi(CH3)3]3 + + [(CH3)3SiOSiRR']2O + [(CH3)3Si]2O + (CH3)3SiF (7) R,R' = CH3, C1CH2, CH2 = CH, CH2=CHCH2, C6H5

We thank the Found of President of Russian Federation (Science Schools’ Grant – 4575.2006.3) for financial support.


Р-35

PREPARATION OF ELECTRON-DEFICIENT PHOSPHINE LIGANDS BY NUCLEOPHILIC SUBSTITUTION OF FLUORINE

V. I. Sorokina, M. Nieuwenhuyzenb, G. C. Saundersb

a Department of Organic Chemistry, Rostov State University, 7 ul. Zorge, 344090 Rostov-on-Don,

Russia. Fax: +7 (863) 2974156. E-mail: [email protected] b School of Chemistry and Chemical Engineering, Queen’s University Belfast, David Keir Building, Stranmillis Road, Belfast BT9 5AG, UK. Fax: +44 (28) 90976524. E-mail: [email protected]

Chelating diphosphines bearing electron-donating and electron-withdrawing substituents are

important, versatile ligands for transitional metals, enabling the catalysis a vast array of reactions 1,2.

We wished to develop the potentially powerful methodology of nucleophilic attack on fluoroarenes to prepare chelating diphosphine ligands with electron-withdrawing arene backbones. Through the judicious placement of electron-withdrawing substituents (CN, NO2 …), which are firstly para-directing, then ortho-directing, and substituents (H, CF3 …) which cannot be substituted by nucleophiles, attack by phosphides can be directed to give the desired 1,2-diphosphinoarene products.

CN

FR

R1

R

R1

F

F

NC

NC

1 R = R1 = F2 R = R1 = P(Ph)25 R = SPh, R1 = F6 R = SPh, R1 = P(Ph)2

3 R = R1 = F4 R = R1 = P(Ph)27 R = SPh, R1 = F8 R = R1 = SPh

109

P

P

Ph Ph

Ph Ph

Pt

Cl

Cl

R P

P

Ph Ph

Ph Ph

Rh

R

2

Treatment of benzonitrile 1 with two equivalents of potassium diphenylphosphide in THF

gave the desired disubstituted derivative 2 in 47% yield. Further substitution was not observed. The reaction between 3 and diphenylphosphide was much more vigorous and even at low

temperature intractable tars were produced. Treatment of 3 with two equivalents of the milder nucleophile diphenylphosphine gave the desired product 4 in 60% yield. The substitution pattern was proved by a single-crystal X-ray diffraction study of diphosphines 2 and 4.

The chelating ability of 2 and 4 was confirmed by trial reactions with (CH3CN)2PtCl2 and Rh2(CO)4Cl2 in dichloromethane, giving complexes of type 9 and 10 for platinum and rhodium correspondingly.

Suggested approach allows to prepare “mixed” ligands. Thus treatment of benzonitrile 1 with 1 eq of PhSSiMe3 lead to formation of para-substituted product 5, it subsequent reaction with (Ph)2PSiMe3 give “mixed” ligand 6. In case of 3, reaction with PhSSiMe3 in different solvents leads to a mixture of mono- 7 and disubstituted 8 products.

The research was supported financially by Royal Society International Incoming Short Visit Fellowship Grant (2005/R2). _________________________ 1 Brandsma L. et al. Application of transition metal catalysts in organic synthesis, Springer, Berlin Heidelberg, 1999, p. 335. 2 Wursche R. et al. Eur. J. Inorg. Chem. 2000, 2063.


Р-36

ELECTROCHEMICAL SYNTHESIS OF FLUORINE-CONTAINING β-DIKETONATES OF COBALT, CHROMIUM AND COPPER

V. I. Potkin, V. L. Shirokii, I. I. Vinokurov, N. N. Kostyuk,

A. N. Ryabtsev, V. A. Azarko

Institute of Physical Organic Chemistry of Belarus National Academy of Sciences, 13, Surganov Str., 220072, Minsk, Republic of Belarus


Fluorine-containing β-diketonates of transition metals are highly volatile without decomposition under vacuum, which allows their use in a number of important technological processes. The electrochemical route of their preparation appears to be promising.

We have shown that the electrolysis of trifluoroacetylacetone (TFAA), thenoyl trifluoroacetone (TTFA) or pivaloyl trifluoroacetone (PTFA), conducted in 0.1 N tetraethylammonium bromide solution in acetonitrile using a nickel cathode and an anode of cobalt or chromium, results in formation of the respective β-diketonates of the corresponding transition metals (Co or Cr) in yields of 75 – 90 %. The electrolysis was performed with DC under argon atmosphere.

Electrolysis of TFAA, TTFA or PTFA, as well as hexafluoroacetylacetone, using a copper anode under the conditions described above did to lead to formation of the respective copper β-diketonates. Instead, formation of elemental copper in powder form was observed on the cathode. However, when electrolysis of the same β-diketones was conducted under conditions of bubbling a moderate air flow through the solution, the respective copper β-diketonates did form in almost quantitative yields (80-90 %). The yields of copper β-diketonates, calculated with respect to the current passed, was considerably higher than 100 %, which may be explained by non-electrochemical interaction of the β-diketones with copper powder that deposited on the cathode during electrolysis.

The electrolysis scheme: Anode: М – ne- → М n+ Cathode: n RCOCH2COR′ + ne- → n RCOCHCOR′ -

_________________________________________________________________________

М n+ + n RCOCHCOR′ - → М(RCOCHCOR′ )n Cо, Cu: n = 2; Сr: n = 3 R = CH3 , R

′ = CF3 ; R = CF3 , R′ = С4 Н4 S , С(СН3)3

It has been shown that thermal evaporation of the fluorine-containing β-diketonates of cobalt or copper under vacuum (10-4 – 10-5 torr) results in formation of mirror-like films with good adhesive properties to quartz, semiconductor or ceramic supporting materials. Under irradiation of these films with UV light generated by mercury lamps, or a laser beam (λ = 266, 337, or 351 нм.), a hidden image is produced. Treatment of these films with a focused laser beam results in deposition of metallic layers.


Р-37

SYNTHESIS OF 2-PERFLUOROALKANOYLCYCLOHEXANE-1,3-DIONES

T. S. Khlebnicova, V. G. Isakova, F. A. Lakhvich

Institute of Bioorganic Chemistry of National Academy of Sciences of Belarus,

acad. Kuprevicha Street 5/2, 220141 Minsk, Belarus Е-mail: [email protected]

Cyclic β,β׳-triketones are widely spread in a nature and possess unique biological properties.

On the other hand 2-acylcycloalkane-1,3-diones and their heterocyclic analogues are used in an organic synthesis, including a synthesis of bioactive compounds, due to high synthetic possibilities of the polyfunctional tricarbonyl system. A development of methods of synthesis of fluoro-containing cyclic β,β׳-triketones are considered as perspective because of it’s known that an incorporation of fluorine atoms or fluorinated substituents into a molecule can cause remarkable changes in the physico-chemical properties and a biological activity of the compounds.

NNCORF ,

NNH , CHCl3

(RFCO)2O , NNH , CHCl3

NN

NN

O

O

O

R1

R

R2

RF

OO

O

R1

R

R2

A)

C)

B)

R = H, CH3; R1 = H, CH3, C6H5, 4-CH3OC6H4, R2 = H, CO2CH3, RF = CF3, C2F5, C3F7

, CHCl3

1 2

RFCOOH ,

2-Trifluoroacetylcyclohexane-1,3-diones 2 (RF = CF3) were synthesized by the treatment of an equimolar mixture of cyclohexane-1,3-diones 1 and imidazole with 10% excess of isolated N-trifluoroacetylimidazol in chloroform at room temperature in 71-90% yields (Method A). A number of 2-perfluoroalkanoylcyclohexane-1,3-diones 2 (RF = CF3, C2F5, C3F7) were prepared by C-acylation cyclohexane-1,3-diones 1 with N-acylimidazol generated in situ from perfluorocarbonic acid anhydrides and imidazole (Method B) or perfluorocarbonic acids and 1,1’-carbonyldiimidazole (Method C) in high yields (69-98%). A structure of compounds synthesized are confirmed by the IR spectra, 1H, 13C and 19F NMR and GC-MS spectra.


Р-38

THE FIRST EXAMPLES OF TRIFLUOROMETHYLATION IN A SERIES OF ECDYSTEROIDS

V. N. Odinokov, S. R. Afonkina, R. G. Savchenko

Institute of Petrochemistry and Catalysis RAS, pr. Oktyabrya, 141, 450075, Ufa, Russia


A methyl group change by trifluoromethyl group, which is slightly differed by its size and but possessed highly electronegative and lipophilic, gives the new physical, chemical and biological properties for organic compound. A great number of methods for introduction of trifluoromethyl group into organic compounds is well known, but the use of (trifluoromethyl)trimethylsilane as nucleophylic trifluoromethylating reagent is shown to be the most perspective. The reagent is applied for various types of organic compounds including steroid ketones, however the examples of trifluoromethylation in a series of ecdysteroids was not known.

We succeded in including diacetate (1) and 14-O-(trimethylsilyl)poststerone acetonide (2), and 2,3-diacetate-20,22-acetonide (3) and 2,3:20,22-diacetonide of 14-O-(trimethylsilyl)-25-oxo-27-nor-ponasterone (4) to the reaction of trifluoromethylation. The interaction of 1-4 compounds with (trifluoromethyl)trimethylsilane in the presence of tetrabutylammoniumfluoride gives the corresponding products of nucleophylic addition of CF3 group on ketogroup in a side chain – 5-8 compounds. The further hydrolysis (alkaline – for acetates and acid – for acetonides and trimethylsilyl ether) led to ω-trifluoromethyl-containing analogs of poststerone 9 and 20-hydroxyecdysone 10.

CF3CH3

HO

OH

OH

OH

H

H

OHCF3CH3

HO

R O

OSiMe3

R O

H

H

OSiMe3

1

2

OCH3

HO

R O

OSiMe3

R O

H

H

CF3

CH3

OO

HO

OH

OH

OH

H

H OH

OO

O

HO

R O

OSiMe3

R O

H

H

1

2

CF3

CH3

OO

HO

R O

OSiMe3

R O

H

H OSiMe3

1

2

1, 2 5, 6

a b

9

1

2

3, 4 7, 8 10

a b

R1=R2=Ac (1, 3, 5, 7); R1+R2=Me2C (2, 4, 6, 8)

a. Me3SiCF3/Bu4N+F-; b. NaOH/MeOH; 5% HCl/Bu4N

+F-

The work was financially supported by the RFFI (Project № 04-03-33103).


Р-39

PECULIARITIES OF THE REACTIONS OF 2,2-DICHLORO(DIBROMO)-2-FLUOROBENZO[d]-1,3,2-DIOXAPHOSPHOLES WITH ALK-1-YNES.

THE SYNTHESIS OF 4-ALKYL-2-FLUOROBENZO[e]-1,2-OXAPHOSPHORININ-2-ONE DERIVATIVES

E. N. Varaksina, V. F. Mironov, A. V. Nemtarev, R. Z. Musin, A. I. Konovalov

A.E.Arbuzov Institute of Organic and Physical Chemistry, Arbuzov str. 8,

Kazan, Russia 420088, E-mail:[email protected]

We have shown earlier that 2,2,2-trihalobenzo[d]-1,3,2-dioxaphospholes form the benzo[e]-1,2-oxaphosphorinine derivatives with high yields in the reactions with arylacetylenes1, propargylhalogenides and hex-1-yne2. These compounds are the P-analogues of the widespread natural heterocycles – coumarines and α-chromens3. The reactions of fluorophospholes 1a,b with hex-1-yne and hept-1-yne have investigated here for the first time. The reactions give only the compounds of benzophosphorinine nature: 3-5а (X = Cl) и 3-5b, 6 (X = Br). Phosphorinines 3 are the preferred isomers in all cases (> 50 %). The diminution of the halogenation regioselectivity of the benzo-fragment and a predominance of the 7-substituted isomers among the minor reaction products 4a,b are the peculiarities of these processes. Fluorine atom does not migrate in benzo-fragment. The unusual allylic shift of the proton from С9 to С3 atom partially occurs to give the compounds 7 and 8.

8 7a,b5a,b

4a,b X = Cl (a), Br (b)

R = Me , Et

F

OP

O

R

+

6

346

9

F

OP

O

R

+X

F

OPO

R

346

9

++

XF

OP

O

R

344a5

67

8 8a

9 10

11

X

F

OP

O

R

7

8X

R

OP

O

F

1a,b

+O

PO

FX

X

3a,b

R(CH2)3C CH

+

Hydrolysis and the following fractional crystallization of the reaction mixtures gives phosphonic acids 9, 10. Their structure was confirmed by the 1H, 31P, 13C NMR as well as by mass-spectroscopy and IRS. 109

ClOH

OP

O

R

BrOH

OP

O

R

The work is supported financially by “Russian Science Support Foundation”.

1 Mironov V.F. et.al. Zh. Obshch.Khim. (Rus. J. Gen. Chem.). 1998, 68(9), 1482-1509. 2 Nemtarev A.V. et al. XIV Internat. Conf. on Chemistry of Phosphorus Compounds. Book of Abstracts. Kazan, Russia, June 27-July 1, 2005, P98. 3 Nikolova R.D. et al. Phosphorus, Sulfur, Silicon and Relat. Elem. 2004, 179, 2131.


Р-40

THE REACTIONS OF 2-PHENYL-4,4-BIS(TRIFLUOROMETHYL)-BENZO[d]-1,3,2-DIOXAPHOSPHEPIN-5-ONE WITH CARBONYL

COMPOUNDS

V. F. Mironova,b, Yu.Yu. Borisovab, L. M. Burnaevab, D. B. Krivolapova, A. B. Dodrynina, I. A. Litvinova, I. V. Konovalovab

aA.E.Arbuzov Institute of Organic and Physical Chemistry, Arbuzov str. 8, Kazan, Russia 420088, Е-mail:

[email protected]. bKazan State University, Kremlevskaya str. 18, Kazan, Russia 420008, Е-mail: [email protected]

2-Phenyl-4,4-bis(trifluoromethyl)benzo[d]-1,3,2-dioxaphosphepin-5-one 1 containing a

nucleophilic phosphorus atom and electrophilic carbonyl group in the γ-position to phosphorus easily reacts with chloral, hexafluoroacetone, phenanthrenequinone and dibenzoyl to form various P(V) derivatives. So, the unusual propeller-like structures 2, 3 were obtained in the reaction of 1 with chloral and hexafluoroacetone. These structures contain three small cycles, annelated along the phosphorus–carbon bond. The phosphorus atom and endocyclic carbonyl group take part simultaneously in the course of the reaction. The interaction of 1 with phenanthrenequinone and dibenzoyl leads to the formation of spirophosphoranes 4, 5 containing seven-membered cycle.

OO

4

OP

OO

CF3

PhO

O

F3C

31

(CF3)2CO CCl3CHO OP

Ph

O

CF3 CF3

O

OCCl3

O PO

O CF3CF3

Ph

PhC CPh

O OO

PO

OCF3

PhO

O

F3C

Ph

Ph5

2

OP

Ph

O

CF3 CF3

O

O CF3CF3

1 23

45

6

78

910

F

F

F

P1

O9

O4

C6

C5

C15F

F

C3

C7

O2

O8

C10

C

C

C

C

C

C

CF

F

F

F

FF

F

Fig. 1. The geometry of molecule 2.

FF

FP1

O9

O4

C6

C5

Cl

F

FC3

C7

O2

O8

C10

C

Cl

Cl

C

CC

C

F

C15

Fig. 2. The geometry of molecule 3.

The structures of 2,3 were confirmed by the NMR and X-ray diffraction (fig. 1, 2). The

phosphorus has the distorted trigonal bipyramid configuration. The unusual peculiarity of this geometry is an axial position of the P1–C5 and P1–C15 bonds, that does not agree with the apicophilicity rule (three oxygens O2, O8 and O9 are in the base of the trigonal bipyramid).


Р-41

HEXAFLUOROACETONE IN THE REACTIONS WITH PHOSPHORUS DERIVATIVES CONTAINING FUNCTIONALIZED SUBSTITUENT

IN γ-POSITION. THE SYNTHESIS OF PHOSPHORANES WITH THE PHOSPHORUS–CARBON BOND

V. V. Mironov, L. M. Abdrakhmanova, T. A. Baronova,

M. N. Dimukhametov, A. I. Konovalov

A.E.Arbuzov Institute of Organic and Physical Chemistry, Arbuzov str. 8, Kazan, Russia 420088, Е-mail: [email protected]

It is recognised that the Р(III) derivatives, containing such group as NCO, NCS, C≡CR,

RC=CR2 bonded with phosphorus, easily react with carbonyl compounds to give various P-heterocycles1,2. The formation of the intermediate P–C–O– or P–O–C– bipolar ions is postulated in these reactions. Then the intramolecular attack of anionic moiety on unsaturated substituent at phosphorus proceeds and leads to the final P-heterocycles. Here we attempted to extend this approach to the Р(III) derivatives, containing a substituent not bonded directly with phosphorus. Such compounds as 2-benzylideneaminophenyl- and 2-benzylideneaminoethyl- and 2-(2-oxo-1,2-diphenyl)ethoxybenzo[d]-1,3,2-dioxaphospholes 1-3, which are stable and do not exhibit any tendency towards intramolecular cyclization, were thereto used.

O

N

O

N

A

CF3CCF3

O

N=CHPh

PO

OO

1,2 3, 4O

N= (1, 3), (2, 4)

+

_N

Ph CF3CF3

O

OP

O

O

CF3

CF3

PhO

O

NP

OO

CF3CCF3

O

PO

OO

Ph

OPh

PO

O O Ph

O

PhOCF3 CF3

+

_

PO

O O Ph

OPh

OCF3 CF35

6B

The reactions of compounds 1, 2, 5 with hexafluoroacetone were proved to lead to the

formation of spirophosphoranes with phosphorus–carbon bond 3, 4, 6. It is obvious, that the intramolecular attack of an oxygen on the exocyclic carbonyl or imino group in intermediate bipolar ions A, B proceeds faster than the P–C–O– → P–O–C– rearrangement.

1 Pudovik A.N. et al. Synthesis. 1986, (10), 793-804. 2 Mironov V.F. et al. Uspekhi Khim. (Rus. Chem. Rev.). 1996, 65(11), 1013-1051.


Р-42

CYCLIC PHOSPHORUS CONTAINING DERIVATIVES OF PAMOIC AND 2,5-DIHYDROXYTEREPHTHALIC ACIDS IN THE

REACTIONS WITH HEXAFLUOROACETONE

L. M. Abdrakhmanovab, V. V. Mironova,b, L. M. Burnaevab, I. V. Konovalovab

aA.E.Arbuzov Institute of Organic and Physical Chemistry, Arbuzov str. 8, Kazan, Russia 420088, Е-mail: [email protected].

bKazan State University, Kremlevskaya str. 18, Kazan, Russia 420008

The reactions of 2-R-benzo-1,3,2-dioxaphosphorin-4-ones with hexafluoroacetone, as we have shown earlier1,2, leads to formation of seven-membered heterocycles – 2-R-4,4-bis(tri-fluoromethyl)benzo[d]-1,3,2-dioxaphosphepin-2,5-diones, which can be used further in synthesis of fluorinated functionally substututed ketons3,4. Here we attempt to extend this approach to the sufficiently complex phosphorylated derivatives of pamoic and 2,5-dihydroxyterephthalic acids 1, 2. These compounds were obtained by the reaction of ethyldichlorophosphite with trimethylsilyl derivatives of the corresponding hydroxycarboxylic acids. The reactions of compounds 1, 2 with a hexafluoroacetone excess proceed under mild conditions to give the diastereoisomeric diphosphepines 3, 4 (d, l- and meso-).

OPO

OP O

O

OF3C

CF3

CF3CF3

OOEt

OEtO

OPOO

P O

O

O

OEt

EtO

CH2O

PO

OPO

O

O

OEt

OEtCH2

O PO

OPO

O

O

CF3CF3

CF3CF3

OOEt

OOEt

CF3CCF3

O

CF3CCF3

O

1

2

3

4 The structure of compounds 3, 4 was confirmed by the NMR with help of the COSY 1H-1H,

HSQS and HMBC techniques. There are two singlets (δР –12.1 and –12.3 ppm) in 31Р NMR spectrum (121.42 МHz, CDCl3) of compound 3. Four quartets of non-equivalent CF3 groups (δF –71.73 and –73.32, 4JFCCF 9.4; δF –71.40 and –73.49 ppm, 4JFCCF 9.2 Hz), corresponding to two diastereoisomers, are present in the 19F NMR spectrum (282.4 MHz, CDCl3). Two signals with δF –72.31 and –73.09 ppm (quartets, 4JFCCF 9.2 Hz) belong to the isolated diastereoisomer of compound 4 in 19F NMR spectrum (282.4 MHz, CDCl3).

1 Мironov V.F. et al. Zh. Obshch. Khim. (Rus. J. Gen. Chem.). 1991, 61(10), 2150-2154 2 Mironov V.F. et al. Zh. Obshch. Khim. (Rus. J. Gen. Chem.). 1995, 65(12), 1986-1990. 3 Mironov V.F. et al. Zh. Org. Khim. (Rus. J. Org. Chem.). 1996, 32(3), 403-405. 4 Mironov V.F. et al. Izv. Akad. Nauk. Ser. Khim. (Rus. Chem. Bull.). 2004, (8), 1640-1646.


Р-43

Х-RAY AND QUANTUM-CHEMICAL INVESTIGATION OF AN ELECTRONIC STRUCTURE OF A LINE FLUOROSUBSTITUENT

BENZENES

N.V. Davydovaa V.D. Yumatov,b

aPedagogical University, Department of Chemistry, 28 Vilyuyskaya st., 630126, Novosibirsk, Russia E-mail: [email protected]

bInstitute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 prosp. Akad. Lavrent'eva, 630090 Novosibirsk, Russia

The electronic structure of fluorosubstituent benzenes line (С6Н5F, C6F6, C6F5NO2,

C6F5OH; C6F5Cl e. a.) has been investigated by X-ray spectroscopy and quantum-chemical calculations. The compounds in gas phase obtained electron impact methods on X-ray spectrometer “Stearate” (Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk). Has been investigated the transitions: МО—→С1s (CKα-spectra); МО—→F1s (FKα-spectra); МО—→O1s (CKα-spectra); МО—→N1s (NKα- spectra). Using the data ESCA, all x-ray spectra are given in a uniform power scale of ionization potentials. Further x-ray spectra are combined in the given scale with photoelectronic spectra. On the basis of such picture we receive distribution of electronic density on molecular orbitals.

The experimental spectra are compared with theoretical, which are under construction on the basis of quantum-chemical accounts, as semi-empirical MNDO (program MOPAC), and not empirical (program MONSTERGAUSS-81). As a rule, semi-empirical accounts reproduce structure of x-ray spectra better, than accounts ab initio. The research of electronic structure fluorosubstituent benzenes was carried out (spent) together with study of distribution of electronic density monosubstituent benzenes. And, if in monosubstituent benzenes the electronic structure the highest occupied orbital coincides with structure of molecule benzenes, that introduction of fluorine atoms essentially does not change such picture.

Fig. 1. X-Ray spectra of fluorobenzene

In the basic interaction F—C occurs on σ-bondes in deeper valents orbitals. Such distribution specifies also experiment (see fig. 1). Really, the spectrum of fluorine moves in the party of increase of energy of communication (connection) concerning a spectrum of carbon.


Р-44

DIOXOCOMPLEXES OF MOLYBDENUM AND TUNGSTEN (VI) WITH FLUORINE SUBSTITUTED HYDROXAMIC ACIDS

Z. Ch. Kadirova

Institute of General and Inorganic Chemistry of AcSci Republic Uzbekistan H.Abdullaev st., 77а, 700170, Tashkent, Uzbekistan


Coordination compounds of the fluorine substituted hydroxamic acids (HA) have pronounced antitumour activity7. Series of new d-metal coordination compounds (Mo(VI), W(VI)) with the fluorine substituted benzhydroxamic acid were synthesized – 4-fluoro-benzoHA and 4-trifluoromethyl-benzoHA.

Initial ligands were obtained by condensation of corresponding fluorocarboxylic acids ethyl esters and benzoylchlorides with hydroxylamine. According spectroscopic data the solution of the fluorine substituted benzoHA is characterized by keto-enolic equilibrium. On base of the quantum-chemistry calculated values of heat of formations (PM3, ab initio) the keto tautomer form of 4-trifluoromethyl-benzoHA (∆Hf=-748 kJ/mol) is preferred than enolic form (∆Hf=-720 kJ/mol). In case of 4-fluoro-benzoHA, the enolic form (∆Hf=-241 kJ/mol) is more energy-stable in comparison with keto-form (∆Hf=-222 kJ/mol).

Synthesis of complex compounds was carried out from water-alcohol solutions using different pH. The consistence and structure were established on base of IR, 1H NMR data and derivatographic, element and X-ray phase analyses.

Coordination compounds of common type (1 : 2) (metal:ligand) were isolated and the following coordination mode was proposed. In case of compounds (I), synthesized at pН<7, the disappearance of the hydroxamic group stretching vibrations bands νОН in IR spectra, the low frequency shifts νС=О bands of ligands to 1600-1580 см-1, νNH to 3080 см-1 prove the formation of five-membered chelate ring and coordination of ligand in keto tautomer form. At рН>7 the ligand molecule in complex exists in enolic form (II), it is confirmed by the disappearance of vibration bands νОН, NH and appearance of νС=N band.

O

C R

HNO

O

M

O

ONH

R C

O O

HN

RCO

O

M

O

ONH

R C

O

2-

I pH<7 II pH>7

R=F-, CF3- M= Mo, W

Fig. 1. Structure of dioxocomplexes fluoro-benzoHA and 4-trifluoromethyl- benzoHA.

In 1H NMR spectra of Mo(VI) diamagnetic complexes in (CD3)2SO besides broad signal δ 12.5 [s, br, 2H,NH] the lower field chemical shift of aromatic protons are observed, the coupling constants of ring are changed, that confirm proposed coordination mode.

1 Li Q. et al. J. Organomet. Chem. 2004, 689(24), 4584 - 4591.


Р-45

SYNTHESIS AND APLICATION OF CF3-CONTAINING BUILDING-BLOCKS BASED ON ENAMINES

D. A. Sibgatulin, D. M. Volochnyuk, A. N. Kostyuk

Institute of Organic Chemistry NAS of Ukraine, Murmanska St. 5, 02094, Kyiv, Ukraine

e-mail: [email protected]

Interaction of “push-pull” enamines having a methyl group at α-position with a set of trifluoromethyl containing ketones 1 has been studied. It was shown that the reaction proceeds not at β-position of the enamine, but at the methyl group affording polyfunctionalized trifluoromethyl containing building blocks 7.

F3C

O

R

Alk2NEWG

MeNAlk2

EWG

CF3OH

R

O

EWG

CF3OH

R

N ONNAlk2 = a: b:

EWG = CN, CO2Et, COMe, COPhR = a: Me, b: CO2Me,

N

N

Me

c:O

N

e:S

N

d:

+

2-5 a,b 1 a-e 6 7

Use of N-substituted imines of methyl trifluoropyruvate 8 a,b in the reaction with enamines 2-5 a,b afforded polyfunctionalized 1,3-dicarbonyl compounds bearing protected α-trifluoromethylated α-aminoacid 10.

N

F3C CO2Me

PG NAlk2CF3NH

MeO2C

PGR

O OCF3NH

MeO2C

PGR

O

R = OEt, Me, PhPG = a: CO2Et, b: Boc

+2-5 a,b

8a,b 9 10

These trifluoromethyl containing building blocks 7 and 10 were also demonstrated to be useful starting materials in the synthesis of trifluoromethyl containing heterocycles.

S

N

NH

N

CF3

OH

Me

NNH

O

CF3EtO2C

NHPG

NNH

O

CF3EWG

NH

N

NH

R

MeO2C CF3

PG

NH

N

OH

MeO2C

R

CF3

EWG = CN, CO2Et

R = Me, PhR = OH, Ph

PG = CO2Et, Boc

PG = CO2Et, Boc

OO

O

N

F3C

MeO2C

OH

O NH

CF3

CO2Et

NNH

O

R CF3

R = Alk, Ar

1. Sibgatulin D.A. et al. Synlett, 2005, 1907. 2. Sibgatulin D.A. et al. Synthesis, in press


Р-46

FLUOROLACTONIZATION OF NORBORNENECARBOXYLIC ACIDS AND THEIR METHYL ESTERS WITH F-TEDA-BF4 AND XeF2

L.F. Lourie, Y.A. Serguchev, M.V. Ponomarenko, G.V. Shevchenko

Institute of Organic Chemistry, NAS of Ukraine 5, Murmanskaya str., 02094, Kyiv, Ukrainе.


The development of simple one-pot synthesis of fluorinated lactones is important as these compounds are similar in structure to biologically active fluorinated carbohydrates.

Here we reported the fluorination of 5-norbornen-endo-2-carboxylic acid, its methyl ester, cis-5-norbornen-endo-2,3-dicarboxylic acid (1a), its dimethyl ester (1b) and monomethyl ester, and 4-phenyl-3-butenic acid with 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (F-TEDA-BF4) and XeF2.

The reactions of acid 1a and its methyl ester 1b with F-TEDA-BF4 or XeF2 proceed in a non-selective manner to give fluorolactonozation, addition and rearrangement products.

The selective fluorolactonization was achieved by treatment of 1a and 1b with F-TEDA-BF4 or XeF2

81.

COOR1a,ba R = R' = Hb R = R' = CH3

COOR

F-TEDA-BF4

CH3CN, r.t.

F

OO

F

COOR+

2a 73%2b 71%

3b 4%

COORCOOR

COORCOOR

+F

H3C(O)CHN

4b 4%

XeF2, BF3. OEt2

CH2Cl2, -78 oC

+

F

COOCH3

F

5b 7% 6b 6%

+

F

COOCH3F

COOCH3 COOCH3

24 h

2b 45%

Scheme 1.

A number of cyclic fluorocontaining γ-lactons and lactams has been obtained by the reaction of 4-phenyl-3-butenic acid with F-TEDA-BF4

2.

PhCH=CHCH2CO2HF-TEDA-BF4

CH3CN. NO O HN N

O OO OO

Ph F Ph Ph F PhPhF F

+ ++ +O O

13% 8% 15% 13% 16%

3

Scheme 2.

It is show that basic factor responsible for selectivity of the fluorolactonization is the presence of two endo-oriented carboxyl groups in the substrate molecule. The electrophilicity and type of the fluorinating agent is of secondary importance in this regard. It is postulated that the fluorolactonization of unsaturated acids and their methyl esters with F-TEDA-BF4 or XeF2 is realized mainly via “open” fluorocarbocation intermediates which in the reaction with XeF2 are postulated as the tight ion pairs.

1 L.F. Lourie, Y.A. Serguchev, G.V. Shevchenko, M.V. Ponomarenko, et al. J. Fluorine Chem. 2006 (in Press).


P-47

REACTION OF ARYL-N-(p-TOLUENESULFONYL)-SULFINIMIDOYL FLUORIDES WITH TRIPHENYLPHOSPHINE

V. E. Pashinnik, A. V. Borovikov, Yu. G. Shermolovich

Institute of Organic Chemistry NAS of Ukraine, Murmanskaya St. 5, 02094, Kiev, Ukraine. E-mail:

[email protected]

Aryl-N-(p-toluenesulfonyl)-sulfinimidoyl fluorides 2 were synthesized by the treatment of arylsulfur trifluoride 1 with p-toluenesulfonamide in the presence of potassium fluoride .

The reaction of aryl-N-(p-toluenesulfonyl)-sulfinimidoyl fluoride with triphenylphosphine have been investigated. This reaction proceeds via two pathways. Pathway a leads to the formation of iminophosphorane 3, diaryl disulfides and difluorotriphenylphosphorane. Pathway b leads to the formation of phosphonium salts 4 and difluorotriphenylphosphorane. These phosphonium salts 4 are easily hydrolyzed by the atmospheric moisture to the corresponding sulfinimidoyl amides 5, triphenylphosphine oxide and thiophenols.

Ar S

F

N SO2-Tol-p

Ar SF3 + NH2 SO2-Tol-p2KF

2KHF2

1 2Ar : Ph , p-Tol , p-NO2C6H4 .

Ar S

F

N SO2-Tol-p

+ Ph3P

2

+ Ph3PF2 + (ArS)22 Ph3P=N-SO2-Tol-p

Ph3P-SAr Ar S

N SO2-Tol-p

+ Ph3PF2

N SO2-Tol-p

H2O

Ar : Ph , p-Tol , p-NO2C6H4 .

3

4

Ar S

N SO2-Tol-p

HN SO2-Tol-p

5

+ Ph3P=O + Ar SH

a

b


Р-48

N-ALKYL(ARYL)AMIDES TRIFLUOROACETIC ACID IN SYNTHESIS OF 1,3,2-λ5-OXAZAPHOSPHETANES

A. D. Sinitsa, A. A. Shalimov, L. I. Nesterova, D. M. Malenko

Institute of Organic Chemistry NAS Ukraine, 02094, Kiev-94, Murmanskaya 5


Based on N-alkyl(aryl)trifluoroacetamides, their N-chloro-, N-trimethylsilyl- (I, IV) and N-PIII-phosphorylated (II, V) derivatives, convenient synthetic methods for previously practically unknown, oxazaphosphetanes with trifluoromethyl group and pentacoordinated phosphorus atom (III, VI) have been developed.

CF3

O

NR

X

O PR12

NCI

CF3

R

Cl

R12PCI

I

III

CF3

O

NR

PR12

CI2

II

R= Me, Pr-i, Bu, Ar

R1= Cl, Ph, OPh

X= Cl

X= H, SiMe3

CF3

ONH HN

CF3

O PCI3

CF3

ON N

CF3

OPCI

CI2

O PN

N

CF3

CI

CI CI

OCF3

IV V VI

2B -

Presence trifluoromethyl or other polygalogenalkyl groups is a condition for formation and stabilization of oxazaphosphetanes.

For the first time, it was shown that oxazaphosphetanes are intermediate products during synthesis of trifluoroacetimidoylchlorides out of N-substituted trifluoroacetamides and PCl5.


Р-49

SPIROCYCLIC 1,3,2-λ5-OXAZAPHOSPHETANES WITH A TRIFLUOROMETHYL GROUP

A. D. Sinitsa, A. A. Shalimov, L. I. Nesterova, D. M. Malenko

Institute of organic chemistry NAS Ukraine, 02094, Kiev-94, Murmanskaya 5


N-Methyltrifluoroacetamid and its N-PIII-phosphorylated (II, IV) derivatives are convenient precursors for spirocyclic oxazaphosphetanes (III, V, VI) with C-trifluoromethyl group 1.

CF3

O NMe

P

3

CF3CON(CI)Me

CI2

X= H, SiMe3CF3

O

NMe

X

I

OPCl

O

CF3

O

NMe

OP

O

N

OP

MeCl

CF3CI

O

O

II III

CI2

O

NP

O

N CF3

N

N

CF3

Me

Me Me

Me

COCF3

CF3COCI

O

NP

O

N CF3

N

Cl

CF3

Me

Me MeCOCF3

CI

V

VI

IV

Formation of spirophosphoranes (V, VI) is accompanied by P→C triad migration of one (V) or two (VI) N-methyltrifluoracetamide groups. Stabilization of spirocyclic derivatives is favored by electron-acceptor trifluoromethyl and trifluoromethylamide groups. The structure of spirophosphoranes was confirmed by spectral data and for compound (VI) also by X-ray analysis.

1 Sinitsa A.D. et. al. J. Gen. Chem. 1995, 65(2), 232-239.


Р-50

DERIVATIONS OF 5,5,6-ТRIFLUORO-7-ОXABICYCLO[2.2.1]- HЕPТ-2-ЕNE-6-EXО-CARBOXYLIC ACID

K. N. Gerasimov, А. F. Еleev, V. S. Кuzmin, S. S. Khokhоv

State Research Institute of Organic Chemistry & Technology 23, Shosse Entuziastov, 111024 Moscow, Russian Federation


The synthesis of derivations of 5,5,6- trifluoro -7-оxabicyclo[2.2.1]-hept-2-еne-6-exo-

carboxylic acid was realized for research of their antituberculous activity, while searching the potential ingibitors of Shikimate kinase , where a substratum of this compound is shikimic acid. Two isomers of nitrile 5,5,6-trifluoro-7-оxabicyclo[2.2.1]-hept-2-еne-6-carboxylic acid in a rate 65:35 are the products of [2+4] cycloaddition of trifluoroacrylonitrile to furan. After educing of the isomers (method of GLC) in individual condition by the RSA-method it was determined that the basic product is exо-izomer 1(Pic.1).

Pic. 1. The spatial location of atoms in the molecule of exo-izomer 1.

The length of the connections and valency angles have typical values for the bicyclic

systems. There are no short intermolecular contacts in the crystal, so, that explains high volatility of the compound. There were obtained the exo-izomers of derivatives on it’s basis: potassium salt 3, acid 4 and methyl ether 5.

O

CF2=CFCNO

FF

F

CNO

F

F

F

CN

O

FF

F

COOKO

FF

F

COOMeO

FF

F

COOH

+1 2

5 3 4

This investigation was made under financial support of ISTC (project No. 708).


Р-51

REARRANGEMENT OF 2-AMINO-1-ARYL-4-TRIFLUOROMETHYL-1,4-DIHYDROPYRIDINES

P. V. Pasternak, V. I. Dyachenko, Z. А. Starikova, А. S. Peregudov, M. Yu. Аntipin, N. D. Chkanikov

A.N. NesmeyanovInstitute of Organoelement Compounds, Russian Academy of Sciences,

Vavilov Str., 28, 119991, Moscow, Russia Е-mail: [email protected]

Methods for the synthesis of substituted polyfunctional pyridines are being intensively

developed nowadays9. The synthesis methods for various 2-amino-3-cyano-4-fluoroalkyl-1,4-dihydro heterocycles as potential insecticides have been developed10,11,12. In addition to creating new synthesis methods it is important to search for novel transformations of the above compounds and to study their reactivity.

We showed that 2-amino 1-aryl-4-trifluoromethyl-3-cyano-1,4-дигидропиридины2 (1) undergo earlier unknown rearrangement which gives 2-arylamino-1,4-dihydropyridines (2) in high yields. The rearrangement occurs in an ethanol solution in the presence of HCl.

N NH2

CF3 R

R'

CN

Ar

R''

NH

NH

CF3 R

R'

CN

Ar

R''

R' = Alkyl, R'' = Alkyl, H(1) (2)R = CO2Et, CF3

HCl

EtOH

The analogy for this reaction is Dimrot rearrangement in the pyridine series which is carried out in an alkaline medium and its moving force is the gain in energy as a result of aromatization of the end product. In our case migration of the aryl substituent from the endo-cyclic to exo-cyclic nitrogen atom with retaining the double bond distribution. The structure of compounds (2) was confirmed by NMR spectroscopy and X-ray diffraction analysis. The starting compounds (1) have been patented as insecticides13 and in association of this, the new transformation that we discovered has a additional importance.

This work was financially supported by E. I. DuPont de Nemours and Co., Inc. within the framework of the Agreement with the International Science and Technology Center(ISTC) (Project ISTC-1016).

9 Litvinov V. P. Usp. Khim. 2003, 72, 75. [Russ. Chem. Rev. 2003, 72, 69 (Engl. Transl)]. 10 Tyutin V.Yu. et al. Izv. AN SSSR, Ser. Khim. 1993, 552 [Russ. Chem. Bl. 1993, 42, 512 (Engl. Transl)]. 11 Golubev A. S. et al. J. Fluorine Chem. 2002, 114, 63. 12 Pasternak P. V. et al. J. Fluorine Chem. 2004, 125, 1853. 13 WO No. 9711057; Chem. Abstrs. 1997, 126, 305586f.


Р-52

WAYS OF RECEPTION OF LITHIUM HEXAFLUOROPHOSPHATE

N. G. Vasilev, B. A. Knyazev

The State Institute of Technology of Organic Synthesis (FSUE SITOS), 412950, Shihany, Saratov Region, Russia.

Fax: 8(84593)-5-16-79

Hexafluorophosphate of lithium LiPF6 - one of the basic salts applied in structure of electrolytes for lithium chemical electrical supplies. Compound very hygroscopic and decaying under action of heat, but for use should be received in highly purity and an anhydrous condition (≥99,9 % of weights) that creates weight of technological difficulties.

About 20 basic methods of reception of lithium hexafluorophosphate are known. The basic method of reception LiPF6 examined and developed in the world now - reaction

of pentafluoride phosphorus with chloride or fluoride of lithium in the environment of liquid

fluorine hydride at low temperatures (order a minus 80°C). It difficultly enough and dangerously

in execution. We offer a new way of reception LiPF6 convenient for technological use in the form of a

solution in propylencarbonate. At the first stage pentagalogenide phosphorus fluorinate the salt fluorinating agent in high-

boiling environment of solvent with reception of a mix of the salts containing hexafluorophosphate anion.

From the given technical mix take hexafluorophosphate - anion in the form of pyridinium hexafluorophosphate which refine recrystallization. This connection further enter into reaction with lithium hydroxide in propylencarbonate. After distillation light-fugitive products of reaction receive directly a solution of lithium hexafluorophosphate in propylencarbonate, applicable for manufacturing from it electrolyte by dilution by suitable solvents.

The given way is protected by patents of the Russian Federation. He is simple in execution, does not demand application of substances dangerous in circulation, at stages of process are absent extreme parameters.

Work is executed at financial support ISTC (the Project No. 2478).


Р-53

WAYS OF RECEPTION OF HEXAFLUOROARSENATE LITHIUM

V. F. Vaher, B. A. Knyazev

The State Institute of Technology of Organic Synthesis (FSUE SITOS), 412950, Shihany, Saratov Region, Russia.

Fax: 8(84593)-5-16-79

Hexafluoroarsenate of lithium LiAsF6 - one of the basic salts applied in structure of electrolytes for lithium chemical electrical supplies.

Hexafluoroarsenate of lithium – hygroscopic, ionic compound. For use in chemical electrical supplies it should be received in highly purity an anhydrous condition (≥99,9 % of weights).

In a world practice exists order of 20 basic ways of reception LiAsF6. As a rule, they are based on use of aggressive fluorine hydride in liquid or gaseous state as the fluorinating agent. It difficultly and dangerously enough.

We offer a new way of reception convenient in technological performance of lithium hexafluoroarsenate .

At the first stage receive an hexafluoroarsenics acid interaction of arsenic and fluoric acids at presence connecting water of a component - acetic anhydride. Received solution HAsF6 in an acetic acid further in the same reactor process a carbonate of lithium with formation of lithium hexafluoroarsenate with a yield close to theoretical. After distillation an acetic acid technical salt subject to two-stage purification; first will neutralize and delete sour impurities, and then recrystallization from solvent.

The given way is protected by patents of the Russian Federation. He is simple in performance, ecologically few dangerous.

Work is executed at financial support ISTC (the Project No. 2478).


Р-54

SYNTHESES OF CHLORO- AND BROMOPOLYFLUOROARENES BY COPYROLYSIS OF POLYFLUOROARENEMONO- AND -DITHIOLS

WITH CHLORINE AND BROMINE

P. V. Nikul’shin, A. M. Maksimov, V. E. Platonov

N.N.Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS 9, Academician Lavrentjev Ave., Novosibirsk, 630090 Russia


Method of synthesis of mono-, di-, trichloro- and mono-, dibromopolyfluoroarenes by copyrolysis of polyfluoroarenemono- and -dithiols with chlorine and bromine in a flow system has been elaborated. 4-Chlorobromotetrafluorobenzene has been obtained from 4-chlorotetrafluorobenzenethiol by this procedure with bromine at 350°C; analogous reaction of 4-bromotetrafluorobenzenethiol with bromine at 450°C gives 1,4-dibromotetrafluorobenzene.

X = Cl (47%), Br (69%)

Br2

∆F

SH

X

Br

X

F

Similar tranformation was realized for perfluoroindane derivatives. Thus copyrolysis of 6-

bromo-5-nonafluoroindanethiol with bromine leads to 5,6-dibromooctafluoroindane.

FFBr

SH

Br

BrF F

Br2

85% 500°C Examples of copyrolysis of mono- and dithiols derivatives of decafluorobiphenyl with

chlorine or bromine have shown that replacement one SH-group (in monothiols) as well as two SH-groups with formation the corresponding mono- and dihaloderivatives is possible.

Z = Hal = Cl, BrY = SHY = F Z = F, Hal = Cl, Br

FFHal2

SHY HalZ F F400-500°C

On the basis of technical mixture of dichlorotetrafluorobenzenes 1,2,4-trichlorotrifluoro-

benzene has been obtained.

400°C~80%~90%о-, м-, п-

Cl

Cl

ClF

SH

Cl

ClF

Cl2KSHF

Cl

Cl

Routes of these transformations will be discussed. The research was supported financially by the Presidium of the Russian Academy of

Sciences (IP №9.4).


Р-55

POLYFLUOROARENESULPHONYL BROMIDES. SYNTHESIS AND SOME REACTIONS

V. E. Platonov, V. V. Kireenkov, A. M. Maksimov, R. A. Bredikhin

N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS Acad. Lavrentjev Ave., 9,

Novosibirsk, 630090 Russia E-mail: [email protected]

Method of synthesis of practically unknown polyfluoroarenesulphonyl bromides by the

action of the mixture of hydrobromic, nitric and sulphuric acids on polyfluoroarenethiols has been developed. This has been used to prepare pentafluorobenzenesulphonyl bromide and its 4-substituted derivatives in good yields.

SH

X

SO2Br

X

F F

X = F, H, Cl, CF 3, C6F5

60 -100oC

HBr+HNO3 H2SO4

62-83%

Routes of formation of polyfluoroarenesulphonyl bromides will be discussed. Some chemical transformations of polyfluoroarenesulphonyl bromides in particular

reactions with KF, allyl bromide and chloride have been studied. Thus the corresponding polyfluoroarenesulphonyl fluorides were formed under the action of KF.

KF

H2O

SO2Br

F F

SO2F

As an example, reactions of pentafluorobenzenesulphonyl bromide with allyl bromide and chloride will be described.


Р-56

PREPARATION AND SKELETAL TRANSFORMATIONS OF PERFLUORO-1,2-DIETHYL-1-PHENYLBENZOCYCLOBUTENE UNDER

THE ACTION OF ANTIMONY PENTAFLUORIDE

V. R. Sinyakov, T. V. Mezhenkova, V. M. Karpov, V. E. Platonov

N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Lavrentiev Prosp. 9, 630090, Novosibirsk, Russia


Interaction of perfluoro-1,2-diethylbenzocyclobutene with pentafluorobenzene in an SbF5 medium and subsequent treatment of the reaction mixture with water, leads to the formation of perfluorinated 1,2-diethyl-1-phenylbenzocyclobutene (1) along with 7,8-diethyl-8-phenylbicyclo[4.2.0]octa-1,4,6-trien-3-one (2) and 2-(1-phenylpropen-1-yl)-(1-oxo-propyl)benzene (3). Under the action of excess of antimony pentafluoride during prolonged reaction time compound 1 undergoes cleavage of the four-membered cycle along with unusual rearrangement of the carbon frame, including expansion of the aromatic six-membered ring to the seven-membered one. As a result after hydrolysis of the reaction mixture perfluorinated 2-[1-(4-oxocyclohexa-2,5-dienylidene)propyl]-propylbenzene (4) and 4b,10-diethylcyclohept[a]inden-7(4bH)-one (5) were obtained.

Routes of the reactions are discussed.

CF2CF3

CF2CF3

F F1) C6F5H, SbF5

20°C

CF2CF3

CF2CF3

F FC6F5 +

CF2CF3

FC6F5

O

CF2CF3

C

C

CF2CF3

O

CFCF3

F

C6F5

+

1 2 3

1) SbF5

CF2CF3

CF2CF3

F FC6F5

1

C OCF3CF2

F

F

CF2CF2CF3

+

4 5

CF3CF2

CF2CF3

O

FF

2) H2O

20-50°C

2) H2O


Р-57

REACTIONS OF POLYFLUOROAROMATIC ORGANOZINC COMPOUNDS WITH ALLYL HALIDES AND CARBOXYLIC ACID

CHLORIDES

A. S. Vinogradov, V. I. Krasnov, V. E. Platonov

N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS Acad. Lavrentjev Ave.,9, Novosibirsk, 630090 Russia


We have found that polyfluoroaromatic organozinc compounds (1) can be used for the synthesis of allyl polyfluoroarenes (2), N,N-dimethylaminobis(perfluoroaryl)methanes (3) and polyfluoroaromatic ketones (4). Organozinc compounds 1 have been obtained from chloropolyfluoroarenes and Zn in DMF as well as from perfluoroarenes and Zn in DMF in the presence of SnCl2

1,2. Compounds 2 are formed from ArfZnX and allyl bromide. The difference in the reactivity

of ArfZnX relative to allyl bromide and allyl chloride was found. In the latter case the reactions proceed in the presence of copper(I) halides, which accelerate the formation of allyl derivatives 2.

Cl

F

ZnX

FCuCl (1 мол %)

R RДМФА

64-87%1 2

Reactions of ArfZnX with carboxylic acid chlorides in the absence or in the presence of

CuCl in DMF resulted in different type of reaction products. In the former case compounds 3 are formed whereas in the latter case ketones 4 are the reaction products.

F

ZnX

FCuCl

R RДМФА

R'O

R'COClR'COCl

ДМФАF

R

N

F

R3 1 4

The above compounds were obtained from polyfluorinated derivatives in benzene, indane

and pyridine series. For the synthesis ketones 4 aliphatic and aromatic carboxylic acid chlorides were used.

Mechanisms of reactions including organocopper intermediates formation with the use of additions of copper(I) halides to ArfZnX are discussed.

1 Miller A.O. et al. Tetrahedron Lett. 2000, 41, 3817. 2 Vinogradov A.S. et al. Zh. Org. Khim. in press.


Р-58

SKELETAL TRANSFORMATIONS OF PERFLUORO-3-ETHYLINDAN-1-ONE IN THE REACTION WITH SbF5 AND SiO2/SbF5

Ya. V. Zonov, V. M. Karpov, V. E. Platonov

N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Lavrentiev Prosp., 9, 630090, Novosibirsk, Russia


Perfluoro-3-ethylindan-1-one (1) heated with SbF5 at 70oC gives, after treatment of the reaction mixture with water, perfluoro-2-(but-2-en-2-yl)benzoic acid (2) as a mixture of E- and Z-isomers. When the reaction temperature is raised to 125 oC (7 h), a solution of salts of perfluoro-3,4-dimethyl-1H-isochromen-1-yl (3) and perfluoro-4-ethyl-1H-isochromen-1-yl cations (4) is obtained. Hydrolysis of the solution of the salts gives perfluoro-3,4-dimethyl-isochromen-1-one (5) and perfluoro-4-ethyl-isochromen-1-one (6), respectively. Increase in the reaction time (86 h) leads to the formation of a solution contained only a salt of cation 3. Reaction of ketone 1 as well as perfluoro-1-ethylindan with excess of SiO2 in an SbF5 medium at 75oC forms a solution of a salt of 4-fluorocarbonyl-perfluoro-3-methyl-1H-isochromen-1-yl cation (7). Hydrolysis of the latter gives acid 8. It has been shown by a separate experiment that a salt of cation 3 practically does not react with SiO2 even at 125 oC. Mechanisms of the reactions are discussed.

C2F5

F F

O

FO

F

CF3

CF3

FC=CFCF3

COF

1

3

F3C

FO

CF2CF3

F

4

+

F

++ 125oC

SbF5

FO

F

COF

CF3

7

+

SiO2/SbF5

FC=CFCF3

COOH2

F3C

FO

O

CF3

CF3

5

FO

CF2CF3

F

6 O

FO

O

COOH

CF3

8

H2O

75oC

H2O

H2O H2O

SbF5, 70oC


Р-59

THE MANUFACTURE OF EXTREMELY PURE POLYFLUOROCHEMICALS FOR MEDICAL APPLICATIONS

V. V. Kornilova, L. N. Kosarevaa, B. A. Melnichenkoa,

B. N. Maximov a, A.N. Kulikovb,

aFSUE «Russian Scientific Center ″Applied Chemistry″», Dobrolyubov Av., 14, 192198, St.Petersburg, Russia

E-mail: [email protected] bS. M. Kirov Military Medical Academy, Lebedev St. 6, 194044, St.Petersburg, Russia

Polyfluorinated chemicals have gained widespread acceptance in various fields of medicine

due to their unique physicochemical properties: chemical stability, high solubility of gases in them (that of О2 is up to 50% by vol.), high specific weight (~1.9), low surface tension, high transparency, sometimes high radiodensity, etc.

High solubility of gases (О2, СО2 , etc.) in perfluorocarbons predetermined those substances usage for efficient gas-carriers and gas-transport media.

Having in mind the specificity of those medical applications of polyfluorinated chemicals their purification to biologically inert state gains primary importance; so inert state requires both high content of the main substance (>99.9%) and very low content of impurities - no more than 10-5 mole/l as recalculated to the chemically bonded fluoride-ion.

The quantity of chemically bonded fluoride-ion characterizes that of reactive fluorinated impurities mixed with the main substance and measured with the help of a fluorine-selective electrode.

The authors investigated the possibility to produce extremely pure polyfluorinated chemicals using adsorption cleaning methods. Following rectification and preliminary cleaning from acid impurities the polyfluorinated substance is directed through columns filled with activated carbon and tripoli (kieselguhr) at 20÷100 оC, in so doing the fluoride-ion content reaches the value 1-2*10-5 mole/l.

The method was applied to achieve the said purity of perfluorodecalin, perfluoropolyesters RFO(CF(CF3)-CF2O)nRF, perfluorooctylbromide, perfluorinated tertiary amines. The cleaning procedure resulted also in the increase of those substances electrical resistance to as high as 1*1015 ohm*cm.

The polyfluorinated substances purified in this manner are applicable in ophthalmology, bronchoscopy and for gas-carriers in medical practice.


Р-60

REACTIONS OF 5,6-SUBSTITUTED URACYLS WITH ELEMENTAL FLUORINE AND PROPERTIES OF THUS PREPARED SUBSTANCES

S. G. Semenov, B. N. Maximov

aFSUE «Russian Scientific Center ″Applied Chemistry″»,

Dobrolyubov Av., 14, 192198, St.Petersburg, Russia E-mail: [email protected]

The methods of thin-layer chromatography, liquid high-resolution chromatography, IR-,

UV-, and NMR`Н and 19F spectroscopy were used to study the composition of the products resulting from the interaction between uracyl or 5,6-substituted uracyls (substituents were CH3, F, Cl, Br, or NO2) or 6-azauracyl and elemental fluorine in anhydrous hydrogen fluoride at variable reaction conditions and reagent concentrations.

It is shown that 5-fluorouracyl (uracyls) are not formed in the case of “6”-position of the substituent, when fluorine molecule is added to the double bond in positions 5, 6:

N

N R'

RH

OH

O

F2

HF

N

N R'

RH

O

FF

O

H The resulting 5,6-difluoroderivatives of substituted uracyls are quite stable (with the

exception of 6-azauracyl); their hydrolysis, alcoholysis and acydolysis results in 5-fluoro-6-substituted–5,6-dihydrouracyls, e.g.:

N

N H

CH3H

O

FF

O

H

CH3COOH

H

O

N

N OC-CH3

CH3H

O

FH

O The structures of those products are confirmed by their counter-synthesis through the

treatment of substituted uracyls with fluorine in appropriate solvents (water, alcohols, or carboxylic acids).

Those substances pyrolysis results in the formation of 5-fluorouracyl isomers, i.e.:

N

N OR''

RH

O

FH

O

H

O

H

N

N H

FH

O

N

N H

FH

O

F

O

R''= H , CH3C(O), CF3C(O), CH3, C2H5

R=H

R H

The fine structure of those substances is studied with the help of physico-chemical

methods, and it is shown that some products of fluorine addition contain the mixture of cis- and trans-isomers.


Р-61

SYNTHESIS AND CHARACTERIZATION OF SOME NEW FLUORNATED 1,3-DIXOLANE DERIVATIVES

L. M. Popova, S. V. Rusetskaya, S. E. Gonek, B. N. Maksimov

Federal State Unitary Enterprise «Russian Scientific Center ″Applied Chemistry″»,

Dobrolyubov Av., 14, 192198, St.Petersburg, Russia E-mail: [email protected]

The synthesis of 1,3-dioxolanes derivatives is well established [1-3]. Fluorinated 1,3-

dioxolanes are very interesting for study in their scientific as well as in practical aspects in connection with their various technical and biological properties. New derivatives of 2-trifluoromethyl-2-pentafluorophenyl-1,3-dioxolane (I-III) was synthesised according to the scheme as follows:

F5C6

C

C

O

F3

CH2Cl

CH2OH O O

CF3F5C6

O O

CF3

ClCl

F5C6

O O

F5C6 CF3

F

ClClF

ClCl

hexaneK2CO3

hvCCl4

SbF3/SbCl5

I II III

The reaction between octafluoroacetophenone and chloroethanol was carried out in hexane at minus 10oC, and the product of their interaction was then reacted with dry K2CO3 during 5-6 hours at 20oC. It resulted in the preparation of 2-trifluoromethyl-2-pentafluorophenyl-1,3-dioxolane (I) (the yield was 80%). The product (I) was colourless crystal matter with melt temperature 40-41oC (irritant). NMR 19F (CDCl3) δF m.g.: -162.3 (F2, 2F), -151.9 (F3, 2F), -137.7 (F1; 2F), -84.14 (CF3, 3F).

Chlorination of fluorine-containing dioxolane (I) was conducted in CCl4 at 80-90oC during 50-60 hours under irradiation. It resulted in of 2-trifluoromethyl-2-pentafluorophenyl-4,4,5,5-tetrachloro-1,3-dioxalane (II) (the yield of the main substance was 95%). The product (II) was colourless crystal matter with melting temperature 41-42oC, boiling temperature 140-141oC /40 mm Hg (irritant). NMR 19F (CH3Cl) δ m.g.: -160.2 (F2, 2F), -147.4 (F3, 2F), -136.2 (F1; 2F), -81.2 (CF3, 3F).

Fluorination of dioxolane (II) was conducted in SbF3/SbCl5 at 80oC during 3 hours. It resulted in of mixed fluorinesubstituted dioxolanes. Rectification of the mixture resulted in isolation (the main substance content was 96%) of 2-trifluoromethyl-2-pentafluorophenyl-4,5-dichloro-4,5-difluoro-1,3-dioxolane (III) (the yield of the main substance was 70%). The product (III) represents colourless liquid with pungent smell. The boiling temperature was 90oC /30 mm Hg (irritant). NMR 19F (CH3Cl) δ m.g.: -159.6, -159.3 (s) (F2, 2F), -146.73 (F3, 2F), -135.98(m) (F1; 2F), -84.61, -84.16 (t), -67.54 (m), -65.74 (s), -58.67, -54.01 (m).

All new fluorinated compounds have been characterized by elemental analyses as well as spectroscopy.

_________________________________ 1 US Pat. № 2,925,424 (1960). 2 US Pat. № 3978,030 (1976). 3 US Pat. № 4,431,786 (1984).


Р-62

ELABORATED METHODS FOR SYNTHESIS AND SPECTROSCOPIC IDENTIFICATION OF FLUORINECONTAINING D-GLUCOSE AND D-

MANNOSE USING IN POSITRON EMISSION TOMOGRAPHY

E. P. Studentsov, E. A. Klinduhova, M. B. Ganina

Saint Petersburg State Institute of Technology (Technical University) 198013, Saint Petersburg, Moscow Pr., 26

E-mail: [email protected] Positron emission tomography (PET) is a unique noninvasive method of radionuclid

diagnostics of various human pathologies induced by the most socially important diseases (oncology, cardiology, psychoneurology). PET demonstrates physiological and biochemical processes in the organism on the subcellular and molecular levels using mostly [2-18F]-2-deoxyglucose (18FDG).

In this paper we report on the modified preparative method for synthesis of 1,3,4,6-tetra-O-acetyl-2-O-trifluorometanesulfonyl-β-D-mannopyranose (Mannose triflate TATM), key precursor in 18FDG synthesis, in which the high degree of D-mannose conversion into 1,3,4,6-tetra-O-acetyl-β-D-mannopyranose (TAM) (70 %) and selective introduction of triflate group into TATM at C-2 hydroxylic group were achieved, provided a high quality desired product (TATM), stable and suitable for long-term use. The reported method for TATM synthesis is economically more efficient which is very important as the requirements in Mannose triflate have increased a lot recently.

Mannose triflate clinical application in several PET centers in Russia demonstrated that the radiochemical results and 18FDG purity are well reproducible, providing reliable diagnostic information. FDG epimerization into 2-fluoro-2-deoxymannose (FDM) in FDG tetraacetate basic deacetylation under different conditions was investigated by HPLC and NMR 19F methods and the yield and quality of either labelled or unlabelled FDG were optimized. Large scaled FDG syntheses were fulfilled by two methods: 1. Mannose triflate was treated by fluorides in the presence of interphase catalyst (cryptands, quaternary ammonium bases) or 2. nucleophylic substitution of 2-OH group in TATM diethylaminosulfurtrifluoride in dioxane accompanied by inversion of configuration at C-2 following by intermediates deacetylation. Electrophylic fluorination of 3,4,6-tri-O-acetyl-glucal by Selectfluor-F-TEDA-BF4 in aqueous dimethylformamide is an effective stereospecific method of FDM and FDG syntheses. Detailed spectroscopic (high resolution NMR 1H and 19F) and chromatographic identification of fluorine-containing D-glucose and D-mannose derivatives. All these data were used in elaboration and confirmation of pharmacopoeia article of industries for quantitative determination of possible mixtures in radiopharmaceutical Fluorodeoxyglucose 18F.

____________________________ Korsakov M.V. et al. RF Pat. № 2165266.


Р-63

REACTIONS OF CAMPHENE AND α-PINENE WITH TRIFLUOROACETIC ACID

Yu. G. Trishin, L. A. Tamm, M. A. Yazvenko

St. Petersburg State Technological University of Plant Polymers Ivan Chernykh Str. 4, St. Petersburg 198095, Russia


The esters of perfluorocarboxylic acids, RFC(O)OR, where R are the residues of terpenic alcohol, have not been enough investigated. At the same time these esters are of great interest as potential physiologically active compounds. One of the ways for obtaining these compounds can be addition of perfluorocarboxylic acids to terpenes. In this association we studied reactions of camphene and α-pinene with trifluoroacetic acid.

It has been found that reaction of camphene with trifluoroacetic acid is a chemo- and stereoselective process. When the reagents ratio is 1:1, isobornyltrifluoroacetate is virtually the only product which is isolated in 90% yield.

CF3COOH

OCOCF3

The stereoselectivity of this reaction decreased if the ratio of the initial reagents was increase to 10:1.

The structure of isobornyltrifluoroacetate was identified by GLC and 1H and 19F NMR spectroscopy by comparing the corresponding data with those of the known isobornyltrifluoroacetate prepared by the reaction of isoborneol with trifluoroacetic anhydride.

(CF3CO)2O

OCOCF3OH

- CF3COOH

The studies of thermostability of isobornyltrifluoroacetate showed that it is stable for 1.5 hours at 100oC, but at it decomposes 150oC and 180oC (17% and 73%, respectively).

Unlike camphene, α-pinene reacts with trifluoroacetic acid to form a complex mixture of the final products including isobornyltrifluoroacetate (5%) and bornyltrifluoroacetate (7%).


Р-64

A METHOD FOR THE SINTHESIS OF α-H-CONTAINING POLYFLUOROALKANETHIOLS

А. N. Кovregin, R. N. Serdyuk, А. А. Tsvetkov, А. Yu. Sizov, А. F. Еrmolov

Military Academy of Radiation, Chemical and Biological Defence,

Brigadirskii per., 13 , 105005, Moscow, Russia Е-mail: [email protected]

Evident about α-H-polyfluoroalkanethiols is restrict, because their synthesis1-3 was based

on use a little accessible reagents, difficult and dangerous processes. We developed a new method for the synthesis this compounds by thermal cleavage benzyl-

1,1-dihydropolyfluoroalkylsulfides in the presence 2-3 fold excess P2O5. Thus was obtained thiols (1-3) in a yield 80 – 95 %.

Rf = CF3 (1), HCF2CF2 (2), HCF2CF2CF2CF2 (3).

RfCH2SBnP2O5, t oC

RfCH2SH

(1-3)

The reaction was carried out by heating reagents and the distilled product were collected. Thiols were obtained of over 95 % purity.

Under these conditions secondary polyfluoroalkylsulfides giving thiols (5, 7). Sulfide (4) was synthesis by addition benzylsulfenylchloride with bis(trifluoromethyl)ketene, following hydrolysis and decarboxylation.

BnSCl + (CF3)2C=C=O1. CH2Cl2

2. H2O(CF3)2CHSBn

P2O5(CF3)2CHSH

1.

2.

MeOH/KOH

H2SO4

MeOOC CHSBn

CF3

P2O5 MeOOC CHSH

CF3

(4) (5)

(6) (7) We consider, that the process thermal cleavage with P2O5 analogous cleavage

benzylsulfides undergo Lewis acids4. The reactions of thiols (1-3, 5,7) with chlorine, fluoroolefins, perfluoroiodides were studied. _________________ 1 Middleton W.J. et al. J. Org. Chem. 1965, 30, 1384. 2 Harris J.F. et al. J. Chem. Soc. 1963, 85, 749. 3 Harris J.F. et al. J. Org. Chem. 1961, 26, 354. 4 Nguyen T. et al. J. Fluorine Chem. 1987, 35, 523.


Р-65

SYNTHESIS OF POLYFLUOROALKYLTHIOACYLHALIDES

А.N. Кovregin, V.A. Porosyatnikov, А.А. Tsvetkov, D.O.Korneev, А.Yu. Sizov, А.F. Еrmolov

Military Academy of Radiation, Chemical and Biological Defence,

Brigadirskii per., 13 , 105005, Moscow, Russia Е-mail: [email protected]

Usualy, polyfluoroalkylthioacylhalydes is obtain high temperature reaction (450-550 оС)

from polyfluoroalkanes, polyfluoroalkenes and their Hg-derivatives with boiling sulfur. Another way – cleavage α-chloropolyfluoroethylbenzylsulfides undergo Lewis acids (TiF4, TiCl4)

1. Thermal decomposition benzylperhalogenalkenylsulfides, containing F-atom in α-location, in presence fluorohydrosulfonic acid2 or phosphorpentoxid3 lead to α-hydropolyfluoroalkylthioacyl fluoride.

We found that reaction of benzylpolyfluoroalkylsulfides, which containing α,α-difluoromethylene group, with P2O5 at 180 оС afforded a mixture of thiols and thiocarbonyl fluoride.

P2O5, toCCHFXCF2SBn CHFXCF2SH + CHFX C

S

F

NaF(1, 2)

X = F (1), Cl (2). Apparently, the first stage to form thiols that follow partially dehydrofluorination under

this condition. Polyfluoroacetylfluorides (1, 2) was isolated in the individual form after crossed volatile mixture over NaF.

Under analogous condition benzyl-1,1-dichloropolyfluoroalkylsulfides generated exclusively thioacylchlorides (3-5) in yields 90%.

(3-5)

RfCCl2SBn RfCCl

SP2O5

180 oC

Rf = CF3 (3), HCF2CF2 (4), HCF2CF2CF2CF2 (5). Возможно, механизм реакции включает первоначальное протонирование атома

серы и промежуточное образование тиолов. При этом процесс может промотироваться примесями полифосфорных кислот и далее развиваться автокаталитически. Отсутствие в данном случае в продуктах реакции даже следов тиола свидетельствует о меньшей стабильности 1,1-дихлорсодержащих тиолов, по сравнению с 1,1-дифторированными тиолами. Не исключена также вероятность, что первичным актом реакции может являться внедрение фосфорного ангидрида по связи S-Bn.

Thioacylhalides (1-5) was studied in reaction with nucleophiles and [4+2]-cycloaddition with 1,3-dienes.

_________________ 1 Nguyen T. et al. J. Fluorine Chem. 1987, 35, 523. 2 Bekker R.A. et al .Bull. Acad. Sci. USSR, Div. Chem. Sci., 1990, 39, 1725. 3 Kovregin A.N. et al. Russ. Chem. Bull., Int. Ed. 2003, 52, 1198.


Р-66

NEW FLUORINATED HETEROCYCLIC CHELATES FOR IMMUNOFLUORESCENCE ASSAY

D. V. Romanova, S. V. Moiseevа, A. I. Lyamina, N. P. Ivanovskayab, N. S. Osinb,

A. V. Semochkina, N. V. Vasil'eva

а Military University of Radiation, Chemical, and Biological Protection,

per. Brigadirskii 13, Moscow, 105005 Russia; bState Research Institute of Biological Instrument Design, Volokolamskoe Sh. 75/1, Moscow, 125424 Russia


Fluorine-containing benzo heterocyclic β-diketones 1 and dibenzo cyclic tetraketones 2-4 were prepared by the Claisen condensation of corresponding acetyl-containing aromatic compounds with the esters of fluorinated carboxylic acids in order to study them as ligands in immunofluorescence assay. The resulting compounds occur in solutions only in an enol form.

n = 1 6X = O, S, NH, NEt

Rf = (CF2)nY1

X: O, S, NH

X

OHO

Rf

3

Y = H, F, Cl, CO2Alk, OR

OHO

Rf

OH O

Rf

X

HOOH O O

Rf Rf

2

n=1, 2, 4, 64

O

(CF2)n

OH OHO

These reagents are radically different in terms of luminescence spectral properties and the stability constants of their complexes with Eu3+. Thus, the complexation of β-diketones 1 from the benzothiophene, benzofuran, and indole series differs only slightly from the complexation of currently used analytical reagents, such as naphthoyltrifluoroacetone (Kb ∼ 1 × 10-7 mol/l). The binding constants of compounds 2-4 differ from that of compound 1 by several orders of magnitude (≤ 1 × 10−11 mol/l). Moreover, compounds from the fluorene and, particularly, carbazole series are characterized by a long-wavelength shift of the excitation frequencies of the resulting complexes to ∼360 and ∼390 nm, respectively. Because of this, more efficient energy pumping sources can be used.


Р-67

SYNTHESIS AND CYCLOADDITION REACTIONS OF POLYFLUORINATED KETONE IMINES

S. V. Moiseeva, V. M. Goncharova, G. V. Zatonskiib, V. F. Cherstkovc, N. V. Vasil'eva

аMilitary University of Radiation, Chemical, and Biological Protection,

per. Brigadirskii, 13, Moscow, 105005 Russia; b N. D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences, Leninskii Pr. 47, Moscow, 117913 Russia; cA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 117813 Russia

E-mail: [email protected]с.ac.ru

It is well known that methods for the preparation of polyfluorinated ketone imines containing fluorinated substituents at nitrogen are difficult to perform in many cases.1,2 The highly electrophilic perfluoro N-sulfonyl imines of fluorinated ketones were prepared previously by the deoxygenation of corresponding oxaziridines, which is a labor-intensive procedure.3 We found that the reactions of trifluoromethylsulfonylsulfinylamine with polyfluoroketones can be conveniently used for the preparation of fluorinated ketone N-trifluoromethylsulfonylimines 1,2. Thus, the reactions of this reagent, as well as pentafluorophenylsulfinylamine, with ethyl trifluoropyruvate unambiguously occurred at 110°С with the elimination of SO2 and the formation of corresponding imines 1,3 in satisfactory yields. Analogous reactions with hexafluoroacetone occurred only with cesium fluoride as a catalyst.

4. R=CF3 Rf=C6F5 (11 %)3. R=CO2Et Rf=C6F5 (61 %)2. R=CF3 Rf=SO2CF3 (69 %)1. R=CO2Et Rf=SO2CF3 (35 %)

1-4

C

N

CF3R

Rf

C

O

CF3R

1100C

RfN SOSO2

The method developed for the synthesis of polyfluoroketone trifluoromethylsulfonylimines 1,2 is

responsible for the preparative accessibility of these compounds, and it allowed us to study their reactivity in cycloaddition reactions. These compounds exothermally react with cyclopentadiene, 2,3-dimethylbutadiene, furan, and other dienes. Only in the case of cyclopentadiene, the reactions occur unambiguously with the formation of expected [4+2]-cycloaddition products. In the reaction of hexafluoroacetone imine 2 with 2,3-dimethylbutadiene, an ene reaction by-product is formed along with the [4+2]-cycloaddition product, whereas the reaction with furan occurs with the formation of an insertion product. The reactions of imino trifluoropyruvate 1 with these reagents and norbornadiene occur ambiguously; this is likely due to its extremely high electrophilicity: E (LUMO) -0.067 eV (calculated at the 3-21G ab initio level)..

NCF3

CF3

SO CF3

O

NS

CF3

CF3

O CF3

O

9

H

O CF3

CF3

N S CF3

O

O8

65H

O

CF3

CF3

N S CF3

O

O

2

___________________ 1 Fokin A.V. et al. Usp. Khim, 1984, 53, 398 (Rus. Chem. Rev., 1984, 53, 238). 2 Osipov S.N. et al. Usp. Khim., 1992, 61, 1457 (Rus. Chem. Rev., 1992, 61, 798). 3 Petrov V.A. et al. J. Fluorine. Chem. 1994, 68, p.277-286.


Р-68

SULFOTRIOXIDATION OF FLUOROHYDROOLEFINS

D. M. Stepashkov, V. F. Cherstkov

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 117813 Russia


Reactions of fluorohydroolefins C3-С4 with SO3. have been studied. It was shown that unsaturated polyfluorinated esters of fluorosulfonic acid or sultones are formed depending on the number and position of hydrogen atoms in a substrate.

CF3CF CH2SO3

1

O

O2S O

SO2

CF3

F

2

C2F5CH CF2 C2F5CH CF2

OS

SO3

5

O2

6

CF3CH CHCF3SO3/[B(OMe)3] CF3CH CHCF2OSO2F

3 4

(66%)

(65%)

(90%)

The reactivity of the sulfoderivatives was investigated.

6

2 CF3CCH3

O

H2SO3,H3BO3

7 (67%)

4LiBr

diglymeCF3CH CHCF2Br

8 (60%)

C2F5CHCOF

SO2F

NEt3

9 (95%)


Р-69

REACTIVITY OF PERFLUOROALKYLAZAANIONS OF VARIOUS STRUCTURE

V. K. Grinevskaja, L. L. Gervits

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,

Vavilova Str., 28, Moscow, 117813 Russia E-mail: [email protected]

Earlier it was shown that internal perfluoroazaalkenes react with fluorides of alkali metals

to form stable perfluoroalkylazaanions. Reaction of perfluoroalkylamination of various compounds such as (CH3)2SO4, (C2H5)2SO4, ClСН2OСH3, BrCH2COCH3, ethylene oxide, etc. was studied. It was shown that the reactivity of perfluoroalkylazaanions depends on the chain length of perfluoroalkyl substituents. The following order of activity for perfluoroalkylazaanions can be proposed:

(CF3CF2)2N > (CF3CF2CF2)2N > (CF3CF2CF2CF2)2N Moreover, it has been found, that the cyclic perfluoromorpholylazaanion obtained by reaction of perfluoromorpholinoimine with cesium fluoride is highly reactive in perfluoroalkylamination reactions.

O NF O NF CsCsF

O N CH3F

O N CH2COOCH3

F

O NF

ClCH2OCH3 (CH3)2SO4

N

O

BrCH2CH=CH2

O N CH2SCH3F

CH2OCH3

SO

O

O

CH2CH2CH2SO3Cs

CH2CH=CH2

ClCH2SCH3

F

O N

F

ClCH2COOCH3

We showed by the example of the reaction with ethylene oxide that if a new nucleophilic

reactive center (A) is formed as a result of nucleophilic substitution, it is capable of replacing the fluorine atom in the starting azaalkene:

FO N + CsF O N CH 2CH2OF CsO

CH 2CH 2

O N F Cs

A

O NF

O N CH 2CH2OF

O

N

F

B

CsFO N

O

F

Cs

+O N CH CH2F

The formation of vinyloctafluormorpholine can be explain by ability of the intermediate azaalkenyl ether (B) to alkylate F-ion1 like perfluoroisoalkenyl ethers.2 This work was financially supported by 3М Company. ______________________ 1.Gontar’ А.F. et al. Izv. Akad. Nauk SSSR, Ser. Khim. 1976, (10), 2381-2383. 2 Gervits L.L. et al. Izv. Akad. Nauk SSSR, Ser. Khim. 1981 (5), 1085.


Р-70

REACTIONS OF PERFLUORINATED O-AND N-ANIONS WITH ACTIVATED AROMATIC COMPOUNDS

D. P. Deltsova, V. K. Grinevskaja, L. L. Gervits


Vavilova Str., 28, Moscow, 117813 Russia E-mail: [email protected]

Previously it has been shown that heptafluoroisopropoxy-anion does not give any products

of nucleophilic substitution with such activated aromatic compound as perfluorotoluene.1 We showed that perfluorobuthoxy-anion also does not give products of nucleophilic substitution with perfluorotoluene, 2,4-dinitrobenzene, cyanuric chloride and –fluoride. We assumed that more probably this is explained by instability of the resulting aromatic ether, not only by insufficient activity of the aromatic ring. To check this assumption it was necessary to exclude fluoride-ion from the reaction mixture. For this purpose we used perfluoro-tert-buthoxide as O-centered anion.

CF3CCF3

O

CsF(CF3)2CFO Cs

CF3Si(CH3)3

-Me3SiF (CF3)3CO Cs

CF3F

CF3F(CF3)3CO

(ClCN)3-CsCl

N

N

N

(CF3)3CO

(CF3)3CO OC(CF3)3 Traces Cesium perfluoro-tert-butoxide readily reacts with cyanuric chloride to form trisubstituted

product in 40% yield. Reaction of cesium perfluoro-tert-butoxide with perfluorotoluene gives only trace amounts (1 %) of the target product.

It was shown, that when CsF react with a solution of tris(perfluoro-tert-butoxy)-1,3,5-triazine, the ether bond is cleaved to form the starting perfluoro-tert-butoxide and cyanuric fluoride.

N

N

N

(CF3)3CO

(CF3)3CO OC(CF3)3

+CsFdiglyme

(CF3)3CoCs (FCN)3+

Perfluorinated N-anions rather easily substitute the fluorine in perfluorotoluene and the

chlorine in cyanuric chloride to give tertiary amines.

FO N + CsF F CsO N

CF3F O NF CF3F

(ClCN)3

N

N

N

O NF ON

F

O

N

F

This work was financially supported by 3М Company. __________________

1 German L.S. et al. Izv. Akad. Nauk SSSR, Ser. Khim. 1989, 188-9.


Р-71

1-HYDROHEXAFLUOROISOBUTENYLOXYTRIMETHYLSILANE - A PROMISING STARTING SUBSTANCE

FOR THE SYNTHESIS OF VARIETY FLUOROORGANIC COMPOUNDS

A. Yu. Volkonskii, E. M. Kagramanova, N. E. Mysova

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Str., 28 , 119991 Moscow, Russian Federation.


CFH=C COF

CF3

CF2=C CHO

CF3

[C4HF5O]nO

O

CF3F F

CF2=C

CF3

(CF3)2C=CHOSiRMe2 (CF3)2C=CHOCH=C(CF3)2O

O CH(CF3)2

CH3 CH3

(CF3)2CH

>550 oC,

1 Torr,

quartz

300 oC,

1 Torr,

KF

CsFdiglym

Me2RSiCl CHFXCF2NR2

[BF3 . OEt2]

20 oC

+

[BF3 . OEt2],

o20 oC

(CF3)2C=CHOSiMe3(CF3)2C=CHO- Cs+

20 oC

Et2O/hн

(CF3)2C=CHOCH=CCF3

COF

This study was in part financially supported by the Russian Scientific Center (Applied Chemistry), St.-Petersburg (Contract No. 17/01).

Volkonsky A.Yu. et al. Izv. Akad. Nauk, Ser.Khim. 1994, (1), 85-88 [Russ.Chem.Bull., 1994, 43(1), 80-83 (Engl. Transl.)]. Volkonskii A.Yu. et al. Izv. Akad. Nauk, Ser.Khim. 2004, (8), 1629-1635 [Russ.Chem.Bull., Int. Ed., 2004, 53(8), 1693-1699 (Engl. Transl.)]. Volkonskii A.Yu. et al, Izv. Akad. Nauk, Ser. Khim. 2004, (12), 2663-2669 [Russ. Chem. Bull., Int. Ed., 2004, 53(12), 2774-2781 (Engl. Transl.)].


Р-72

POLYFLUORINATED β-DIIMINES AS NEW LIGANDS

M. A. Kurykin, О. Е. Petrova, Е. Е. Nikolaeva, V. N. Khrustalev, M. I. Buzin

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Str., 28 , 119991 Moscow, Russian Federation.


Chelating ability of the polyfluorinated β-diimines synthesized by the methods developed in the Laboratory of Organofluorine Compounds of INEOS.1,2

Diimines were shown to form easily intrachelating complexes (I) with a number of metal cations.

NH

CF3

F

NH

Rn

-

F

Mn+

I M = Mn(II), Fe(III), Co(II, III), Ni(II), Cu(II), Zn(II), Pd(II); RF = CF3, C2F5, C3F7, C4F9.

Complexes (I) were obtained from metal acetates by exchange of ligands. The chelate structure of the obtained compounds was confirmed by X-ray diffraction analysis. The structure of the β-diiminates was also confirmed by GC-MS, IR-spectroscopy, and element analysis data.

The complexes synthesized are air stable, solid, crystalline compounds. They have high volatilities and are soluble in most of organic solvents. The thermal properties of β-diiminates (I) were also studied.

___________________ 1 Kurykin М.А. et al. Izv. AN SSSR. Ser. Khim. 1980, (12), 2827. 2 Petrova О.Е. et al. Izv. AN, Ser. Khim. 1999, (9), 1710.


Р-73

SYNTHESIS AND PROPERTIES OF THE TRIFLUOROMETHYL CONTAINING TRIBUTYLTIN PHENOXIDES

V. M. Pachevskaya, V. I. Dyachenko, A. S. Peregudov



An intense development of fluorine chemistry in the latter half of twentieth century has led

to the appearance of biologically active compounds having fluorine atoms or polyfloralkyl groups. It has been shown that a replacement of OH-protons by organotin groups in certain

biologically active phenol compounds having either α-hydroxyhexafluoroisopropyl substituent or β,β,β-trifluorolactic acid moiety results in some cases in a considerable increase of their antibacterial and fungicide activity.1,2

Thus, the interaction of substituted phenols and 8-oxychinolines with di(tri)butyltin

methoxides in absolute ethanol gives rise to the corresponding trifluoromethyl containing di(tri)butyltin methoxides 1-5 in high or quantitative yields.

Some of compounds 1,2 have a combined activity and exceed up to now in the most active to Phytophthora investans and Peronospa cubensis then ridomil and karathane fungicides using in agriculture. According to preliminary data the cyclic tin derivatives 3-5 have a pronounced antineoplastic activity and, therefore, may be subject to a further study. ---------------------------------- 1 Dyachenko V.I. et al. Inventor certificate № 4878694/04. 2 Kravtsov D.N. et al. Invertor certificate № 48998993/04.

CF3

OHR1 OSnBu3

R2

N

OSnBu3

CF3 CO2OMeOH

R2

R1 = CF3, CO2Me R2 = H, F, Cl, Me, tert-Bu, -C(CF3)2OH

OSnBu2

OO

O

CF3 R1CF3 R1

O

OSnBu2

O

OSnBu2

CF3

NHN

R2

R2

1

4

2

35

ArOH Bu3SnOMe ArOSnBu3- MeOH+


Р-74

BIOLOGICALLY ACTIVE FLUORINE-CONTAINING FERROCENE–MODIFIED HETEROCYCLES

A. A. Simenel, E. A. Akulinina, L.V. Snegur, T. V. Efanova, Yu.V. Kuzmenko

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str, 28, 119991 Moscow, Russia; Fax: (495)135-5085,

E-mail:[email protected]

Within the past years the belief in unique properties of fluorine compounds has been growing. The substitution of a hydrogen atom in heterocyclic systems by a fluoroalkyl group pronouncedly affects the lipophility of molecules. This favors assimilation of biologically active species by organisms and accelerates their migration through biomembranes. Introduction of ferrocene moiety into a molecule of organic compound often provides the latter with biological activity. Thus, compounds of a ferrocenylalkyl azole series exhibit marked antitumor activity while being low toxic.

Acid catalyzed ferrocenylalkylation of nitrogen-containing heterocycles with ferrocenyl carbinols proved to be a convenient method for the synthesis of a variety of ferrocene compounds. By application of it, we have prepared ferrocenylalkyl derivatives of a number of fluorine-containing diazoles – 3,5-ditrifluoromethylpyrazole, 5-trifluoromethyl-3-methylpyrazole, 2-(α-hydroxytetrafluoroethyl)benz-imidazole, and 5-trifluoromethyl-3-(2-thienyl)pyrazole in high yields (up to 95%). By application of 2D NMR spectroscopy, the alkylation of trifluoromethylmethylpyrazole was shown to proceed into the N-1 position of the heterocycle.

.

Fe

OH NHN

S

CF3

+

HBF4

CH2Cl2 / H2O

NN

S

CF3

Fe

Fig.1 Molecular structure of 1-N-ferrocenylbenzyl-3-trifluoromethyl-5-(2-

thienyl)pyrazole

Compounds with chiral centers were analytically resolved to enantiomers with the use HPLC on chiral columns. For 1-ferrocenylethyl-2-(α-hydroxytetrafluoroethyl)benzimidazole, all four isomers were separated employing the column with γ-cyclodextrin. The structure of ferrocenylbenzyl-3-trifluoromethyl-5-(2-thienyl)pyrazole was supported by X-ray analysis. Some of compounds synthesized were tested on acute toxicity and antitumor activity in experiments with animals.


Р-75

COORDINATION CHEMISTRY OF ANTICROWNS. UNUSUAL COMPLEXES OF CYCLIC PENTAMERIC

PERFLUOROISOPROPYLIDENEMERCURY WITH TETRAFLUOROBORATE AND HEXAFLUOROSILICATE ANIONS

K. I. Tugashov, I. A. Tikhonova, F. M. Dolgushin, A. Yu. Volkonsky,

I. G. Barakovskaya, A. G. Buyanovskaya, V. B. Shur

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street 28, Moscow 119991, Russia

[email protected]

The synthesis and structure of an unusual complex of cyclic pentameric perfluoroisopro-pylidenemercury [(CF3)2CHg]5 (1) with tetrafluoroborate anion is reported. The complex was prepared by the interaction of {[(CF3)2CHg]5Br2}

2– (2) with two equivalents of AgBF4 in THF at 20ºC followed by the recrystallization of the resulting product from CH2Cl2 and has composition {[(CF3)2CHg]5(BF4)(CH2Cl2)}

– (3), i.e., contains one [BF4]– anion and one CH2Cl2 molecule per

molecule of the anticrown. An X-ray diffraction study of the complex has shown that the BF4–

ion and the dichloromethane ligand in 3 are located on different sides of the metallacycle plane. Interestingly, the anionic guest in 3 is bonded to 1 by its all fluorine atoms, one of them being symmetrically coordinated to all five mercury centres of the anticrown, i.e., the coordination number of this fluorine atom is equal to six. The CH2Cl2 molecule in 3 is bound to 1 through the chlorine atom which also interacts with all five Lewis acidic Hg sites of the macrocycle.

With the aim of the synthesis of a fluoride complex of macrocycle 1, the reaction of 2 with

an excess of AgF in acetonitrile at room temperature has been studied. However, it turned out unexpectedly that under such conditions a hexafluorosilicate complex of 1, viz. [{[(CF3)2CHg]5}2(SiF6)]

2– (4), is produced. According to the X-ray diffraction data, the complex has a double-decker sandwich structure wherein the anionic species is disposed between the two anticrown molecules and is bonded to them by its all six fluorine atoms, two of which are again symmetrically coordinated to all five mercury centres of the neighbouring macrocycle. The complexation with [SiF6]

2– leads to a noticeable distortion of the geometry of the starting macrocycle.

The synthesized adducts 3 and 4 are the first examples of complexes of an anticrown with tetrafluoroborate and hexafluorosilicate anions.

This work was supported by the Russian Foundation for Basic Research (The Project code 05-03-32891) and the Russian Science Support Foundation (K.I.T.).

Hg

HgHg

Hg

Hg

F3C

F3C

F3C

F3C

F3C CF3

CF3

CF3

CF3

CF3

(1)


Р-76

REGIOSELECTIVE N-ARYLATION OF AZOLES UNDER THE ACTION OF FLUOROAROMATIC COMPOUNDS IN THE MICROWAVE

IRRADIATION CONDITIONS.

D. V. Davydov, I. P. Beletskaya, Yu. F. Oprunenko

Chemical Departament of MSU, 119992, , GSP-2 ,Leninskie Gor, Moscow, Russia E-mail: [email protected]

N-Arylated pyrazoles, imidazoles and triazoles, including those of high NH-acidity, are known to exhibit a wide spectrum of biological activity1. The most useful route to these compounds is the direct regioselective N-arylation of the corresponding azoles. However this approach is rarely effective, for example to 3-nitro-1,2,4-triazole, 3-nitropyrazole, 2-methyl-5-nitroimidazole, due to low reactivity similar azoles and their ambident character . We have observed that in the presence of low valent copper the arylation of such azoles by either perfluoroarenes (scheme 1) or fluorosubstituted diaryliodonium salts (scheme 2) is highly regioselective. The reaction can be further accelerated and reaction time shortened by roughly an order of magnitude by microwave irradiation:

NH

Y

N

R

+

N

Y

N

R

ArR = NO2, CF3. Y = CH. R = NO2. Y = N.

70 W, 100 C, 0,5 h.o

or

ArF

ArF = C6F5N, C6F5CF3, C6F5Cl, C6F5CO2Et, C6F5CN, C6F5Br.

Toluene,CuIEt3N,

75 - 90%

Scheme 1. Regioselective arylation pyrazoles and triazoles by perfluoroarenes.

NH

Y

N

R

+N

Y

N

R

ArR = NO2, CF3. Y = CH. R = NO2. Y = N.

70 W, 100 C, 0,5 h.o

or

Et3N, Cu, ROH

Ar2IX

Ar2IX = (p-FC6H4)2ISO3H, (m-CF3C6H4)2BF4, (C6F5)2IO2CCF3.

60 - 80%

Scheme 2. Regioselective arylation pyrazoles and triazoles by Ar2IX.

2-Methyl-5-nitroimidazole reacts regioselectivly with both types of the arylation agents also producing the products of arylation at the less hindered nitrogen atom. The isomeric substitution products are observed in trace amounts and are readily removed from the target products during isolation. Fluorosubstituted aryliodides were shown to be unreactive in both Cu and Pd-catalysed protocols. Comprehensive Heterocyclic Chemistry, Elsevier , Editors: A. R. Katritzky and C.W. Rees, 1997, Volumes 1-7.


Р-77

NEW APPROACH TO THE SYNTHESIS OF TRIFRUOROMETHYL SUBSTITUTED AMINO PHOSPHONATES

D. V. Vorob’evaa, I. D. Titanyukb, I. P. Beletskayab, S. N. Osipovа

aA. N. Nesmeyanov Institute of Organoelement Compounds,

Vavilov Str., 28, 119991,Moscow, Russia bDepartment of Chemistry, Moscow State University Leniskie Gory 1,build. 3, 119992, Moscow, Russia


In context with our constant interest in new fluorinated building blocks1 we have developed an effective method for the preparation of new fluorinated synthon – diethyl-1-diazo-2,2,2-trifluoroethylphosphonate and have investigated its reactivity with respect to different hydroxyl- and amino compounds under rhodium(II)- and cupper-catalyzed conditions. For instance, the following chemical transformations have been studied: • Insertion reactions of the corresponding fluorine-phosphorus carbene into ОН- and NH-

bonds of carbamates and amino acids; • [2,3]-Sigmatropic rearrangements as well as 1,2-Stevens shift of in situ generated ammonium

ylides formed from the corresponding metallocarbenoids and tertiary amines.

N P

CF3

OEt

OEtOH

O

RO POEt

OOEt

O

CF3O

N

H

PG

F3C POEtOEt

N2

O

N P

CF3

OEt

OEtOMe

MeN P

CF3

OEt

OEtOMe

Me

O

NH2RO

[Rh]

O

HO

Ph

N

H

PG

[Rh]

PhCH2NMe2NMe2

[Cu] [Cu]

Fig. 1. Synthesis of trifluoromethyl substituted amino phosphonates.

This work was supported by Russian Foundation of Basic Research (RFBR № 04-03-32644).

___________________________________ 1 a) Osipov S.N. et al. Tetrahedron Lett. 1996, 37, 615;

b) Osipov S.N. et al. Synlett, 1995, 1269;

c) Titanyuk I.D. et al. Synlett, 2006, accepted.


Р-78

EFFECTIVE PATHWAY TO THE α-CF3-SUBSTITUTED HISTIDINE AZA-ANALOGS

G. Т. Shchetnikov, S. N. Osipov



Synthetic non-proteinogenic α-amino acids play an important role in modern drug discovery

process. Incorporation of such amino acids (especially α,α-disubstituted) into key positions of biologically active peptides, as a rule, leads to significant enhancement of conformational and proteolytic stability, increases selectivity and improves of pharmaco-kinetic properties of the potential drugs as well14.

We have developed a convenient method for the preparation of α-CF3-substitute aza-histidines based on Cu(I)-mediated 1,3-dipolar cycloaddition of different organic azides to propargyl-containing α-CF3-α-amino acid derivatives.

HN

CF3

PG O

O+

CuI (5 mol%)

R-N3

H2O/BuOH

NN

N

CF3

NHPG

CO2Me

R

NN

N

CF3

CO2Me

O

O

HN

O

O Ph NN

N

CF3

CO2H

HN

O

O PhH

NN

N

CF3

CO2H

HNH2

5 % KOH

MeOH

H2, Pd/C

MeOH

98 %

100 %

85 - 97 %

PG = Boc, Cbz, CO2Et, SO2Ph

O

N3

AcO

AcOAcO

OAc

RN3 = N3

O

OH

N3

O

O

N3; ; ;

Method A: CuSO4/ascorbateNa

DIPEA, THF

Method B:

Fig. 1. Synthesis of trifluoromethylsubstituted azahystidines

This work was supported by Russian Foundation of Basic Research (RFBR № 04-03-32644). _______________________ 1 Hruby V.J. Nature Rev. Drug Dis. 2002, 1, 847.


Р-79

SYNTHESIS AND REACTIVITY OF 2-(α-HYDROPOLYFLUOROALKYL)BENZIMIDAZOLES

Т. P. Vasil’eva, А. F. Kolomiets, D. V. Vorob’eva, S. N. Osipov



Benzimidazoles (BI) form an important class of organic compounds, because many of them

are used as pharmaceutical preparations, especially 2-substituted BI. Among them, it should be noted 2-benzyl-BI (dibazol) used as hypotensive drug and and as prophylactic agent against grippe. The compounds exhibiting high anti-HIV activity have been found among N-alkylated 2-substituted BI.1 It is well known that modification of biologically active compounds by introducing fluoroalkyl substituents often leads to increasing the efficacy. That is why the studies of the synthesis and properties of 2-fluoroalkyl-BI are topical. Previously we have synthesized the first representstive of this class of compounds (I, Х=Н, R=CF3)

2. In a continuation of the studies in this field we have developed a general preparative method for obtaining new 2-(α-hydropolyfluoroalkyl)-BI (I) by reactions of о-phenylenediamines with perfluoroolefins.

NH2

NH2X

+ F2C=CF-RN

N

H

R

FX

I[X=H, Cl, Me; R=F, CF3, OCF3]

(67-85%)

The influence of solvents and catalysts on the yields and purity of the products (I). We

parformed silylation of compounds (I) using N-trimethylsilyldiethylamine, This opens new opportunities for modifying fluorinated BI at nitrogen atom.

N

N

H

RF

X N

N

R

RF

X

R-Cl

[RF=CH(F)CF3, R=MeCO, SR']

N

N

SiMe3

RF

X

Ar present the the studies on the further functionalization are carried out. (I). _________________________ 1 Roth T. et al. J. Med. Chem. 1997, 40 (26), 4199-4207. 2 Fokin F.V. et al. DAN SSSR, 1985, 284 (6), 1492-1494.


Р-80

FLUOROALKENYL DERIVATIVES OF INDOLE-, QUINOZOLONE- ALKALOIDS AND 1-METHYL-2-AMINOBENZIMIDASOLE.

A. A. Kadyrova, N. D. Chkanikova, K. V.Gordeeva, G.-V. Roschenthalerb,

Z. Ch. Kadyrovac, T.-P. Tulyaganovc.

aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova St. 28, Moscow, Russia;

bInstitute of Inorganic & Physical Chemistry, University of Bremen, Leobener Strasse, 28334 Bremen, Germany;

cS.Yu.Yunusov Institute of the chemistry of plant substances of AcSci Republic Uzbekistan, H. Abdullaev St., 77, 700170, Tashkent, Uzbekistan


Perfluoromethacrylic acid diethylamide Et2N(O)C-C(CF3)=CF2, perfluoroisopropenyl-

phosphonic acid diethyl ester (EtO)2(O)P-C(CF3)=CF2 and 2-monohydroperfluoro butene-1 C2F5CH=CF2 easily react with natural alkaloids “Harmine” (7-methioxy-1-methyl-9H-pirido (3,4-b) indole) and “Vazicinone” (hydroxy-1,2,3,9-tetrahydropyrrolo- quinozolone-9) which are available from the plant “Peganum harmala” and 1-Methyl-2-aminobenzimidasole to form corresponding enamines (I-III).

N

N

CH3

NH CF C Rf

X(III) (E:Z)

Rf = CF3; X = C(O)NEt2 (a), P(O)(OEt)2 (b). Rf = C2F5; X = H (c)

NN

CFCH3

CH3O

C

F3C X

N

N

O

O CF C X

CF3

X = C(O)NEt2 (a), P(O)(OEt)2 (b)

(I) (E:Z) (II) (E:Z)

Hydrolytically stability and other chemical and biological properties of those fluorinated derivatives of known biologically active compounds will be discuss.


Р-81

NEW MONOFLUORINATED ISOSTEROIDAL ALKALOID

A. A. Kadyrova, N. D. Chkanikova, R. Sh. Shakirovb, T.-P. Tulyaganovb

aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova St. 28, Moscow, Russia

cS. Yu. Yunusov Institute of Chemistry of Plant Substances of AcSci Republic Uzbekistan, H. Abdullaev St., 77, 700170, Tashkent, Uzbekistan


New fluorinated analog of isosteroidal alkaloid "Imperialine" was synthesize by fluorination. Attempts of fluorination of "Imperialine" by (2-Chloro-1.1,2-trifluoro) diethylamine (Yarovenko reagent) or N-(1,1,2,3,3,3-hexafluoropropyl) pypyridine (Ishikava reagent) does not lead to the result expected. There are no reaction at low temperature and if reaction mixture was heated up to ~50-60 oC it was explosive reaction to escape of hydrogen fluoride form of a tar, and unidentified mixture of volatile and solid compounds.

NOH

CH3

O

F

We have found mild conditions of substitute fluorination of hydroxyl in the position 17 of the isosteroidal ring to form monofluoride (46%). Structure, methods of isolation, biological activity and fluorination of some other structural analogues of "Imperialine" will be discuss.


Р-82

REACTIONS OF PENTAFLUOROBENZALDEHYDE PROMOTED BY METALLOCOMPLEX SYSTEMS BASED ON

IRON PENTACARBONYL

A. B. Terentiev, T. T. Vasilieva, O. V. Chakhovskaja, N. E. Mysova, K. A. Kochetkov

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova St., 28, 119991, Moscow, Russia


We have created recently that metallocomplex systems based on iron pentacarbonyl may be used as an effective promoter to introduce fluoroorganic compounds in different types of reactions: Zaitsev-Barbier, Reformatsky, reductive dimerization of aldehydes to produce polyfunctional fluoroorganic compounds, in particular with potential biological active groups. Reactions, promoted by metallocomplex systems based on iron pentacarbonyl may be carried out in benzene solution at 80oC (2-4 hours) or room temperature (3-4 days). The method is free from usual limitations (heterogenic reaction mixture, water-free solvents, inert atmosphere and effective stirring) for such type of reactions. The use of pentafluorobenzaldehyde, that contains strong electron withdrawing pentafluorophenyl group, allowed us on the one hand to study the influence of polar substituents on the character of reaction products and on the other to elaborate the effective preparative method for the synthesis of different polyfunctional compounds with pentafluorophenyl group in molecule. In all above mentioned types of reactions (Zaitsev-Barbier, Reformatsky, and reductive dimerization of aldehydes) namely pentafluorobenzaldehyde demonstrates the best yields and selectivity.

Pentafluorobenzaldehyde’s reactions with mono- and polyhalogensubstituted esters and nitryles result in corresponding β-hydroxyesters, β-hydroxynitryles, acrylates:

CH3CHBrCO2Me + C6F5CHO C6F5CH(OH)CH(CH3)CO2MeFe(CO)5

ICH2CN + C6F5CHO C6F5CH(OH)CH2CN CHBr2CO2Me + C6F5CHO C6F5CH=CHCO2Me

The results of Zaitsev-Barbier reactions are very sensitive to polar characteristics of reagents: allyl iodide reacts with pentafluorobenzaldehyde to form the corresponding carbinol with quantitative yield, in the same time n-perfluorobuthyliodide and benzylbromide form adducts with yield 10-15%:

Fe(CO)5C6H5CH2Br + C6F5CHO C6F5CH(OH)CH2C6H5

C6F5CHO + CH2=CHCH2I CH2=CHCH2CH(OH)C6F5Fe(CO)5

Reductive dimerization of pentafluorebenzaldehyde results in formation of (dl)-1,2-

bis(pentafluorophenyl)-ethanediol-1,2 with quantitative yield and de=100%:

2C6F5CHOFe(CO)5 C6F5CH(OH)CH(OH)C6F5HMPA

][ HCl aqC6F5CH-CHC6F5

Fe(CO)xO O

In water-free conditions this reaction results in corresponding stilbene

C6F5CH=CHC6F5. We believe that a metallocarbene is an intermediate in the process. This work was financial supported by RFBR (project 06-03-3282).


Р-83

FLUOROAZOMETHINES IN CYCLOADDITION REACTIONS

А. F. Gontar’


Vavilova St., 28, 119991, Moscow, Russia E-mail: [email protected]

Previously it has been shown that fluoroazomethynes do not enter thermal pericyclic

reactions. For example, CF3N=CF2; CF3N=C=O and CF3N=C=N-RF do not react with phenylazide,

isobutene, and butyl vinyl ether even under severe conditions.1 Nevertheless perfluoro-2-azapropenes were shown to be involved in reaction with

cyclopentadiene to form the corresponding 2-bicycloheptenes (1).

CF3N CF

R+ N

R

CF3

F R = F, CF3, C≡N (1)

The rearrangement of fluoroalkylazides (2) to carbodiimides (3) earlier discovered

(Knunyants-Gontar’ rearrangement)2

CF3N CF

RF

+Me3SiN3

CF3N CN3

RF

tCF3N=C=N RF

(2) (3)

and a new method for obtaining perfluoroalkylisocyanates (4)1

RFNHCO

FRFN=C=O

(4)

RFN=CF2

RCOOH KF

-HF

make it possible to increase a number of 2-azabicycloheptenes, for instance,

CF3N CNRF +N

N

CF3

RF

N

N

CF3

RF

X

X

X2

(6)(5) The 2-azabicycloheptenes obtained (1, 5) can be easily halogenated at the double bond to

give the corresponding 2-azabicycloheptanes (6). ____________________________ 1 Gontar A.F. Diss. (1989). 2 Gontar A.F. J. Fluorine Chem., 15, 1980,169-172.


Р-84

ADDITION OF PERFLUOROALKYLHALOGENIDES TO ETHYLENE INITIATED BY SYSTEM CUPRIC ACETATE – HYDRAZINE HYDRATE

К. Е. Narinyan, V. L. Don, V. А. Vyazkov, S. М. Igumnov

Joint Stock Company «Scientific Industrial Association “P&M-Invest”»

Vavilova St., 28, Moscow, 11999, Russia E-mail: [email protected]

Previously, we described addition of perfluoroalkyl iodides to allyl alcohol, octene-1

and hexene-11 in the presence of the system of reagents cupper acetate – hydrazine hydrate. We have established that the above system cupper acetate – hydrazine hydrate can be successfully used for addition of not only perfluoroalkyl iodides, but also for addition of perfluoroalkyl bromides to ethylene. The yields of the products of addition were 40 to 80%.

Cu(OAc)2/N2H4

RfX+CH2=CH2 RfCH2CH2X

Rf =C2F5, C3F7, BrCF2CF2, BrCF2Cl, BrCF2, i-C4F9, n-C8F17 X=I, Br

_____________________ 1 2-d International Conference “SNAF’97”, St.Peterburg, Russia, 1997, 2-35.


Р-85

SYNTHESIS F PERFLUOROCYCLOHEXENE-1 CARBOXYLIC ACID FLUORIDE

S. M. Igumnov, G. I. Lekontseva, V. А. Soshin, G. Yu. Natsibullina

Joint Stock Company «Scientific Industrial Association “P&M-Invest”»

Vavilova St., 28, Moscow, 11999, Russia E-mail: [email protected]

Federal State Unitary Enterprisу «Russian Scientific Center “Applied Chemistry”», Perm Branch, Voronezhskaya St., 41, Perm, 614034, Russia


Perfluorocyclohexene-1 carboxylic acid fluoride (PFCH-1-CAF) is of interest as a starting product for the preparation of its derivatives, as well as fluoromonomers for the preparation of polymeric materials with improved properties (thermal stability, freeze resistance). We have studied a process for the preparation of PFCH-1-CAF by catalytic decarboxylation of 1,2-difluoride of perfluorocyclohexanedicarboxylic acid (1,2-DFPFCHDCA), which is obtained by electrochemical fluorination of phthalic acid derivatives in an anhydrous hydrogen fluoride medium. The reaction is described by the following scheme:

F

COF

COF

T, katF

COF

The reaction products have been identified by IR and NMR spectroscopy and gas-liquid chromatography. The decarboxylation is carried out in a flow tubular reactor of stainless steel at a temperature of 350-450oC. Aluminium trifluoride supported on aluminium oxide (I) and activated carbon promoted by potassium fluoride (II) were used as catalysts. It has been found that the catalyst II has much more activity in comparison with I and permits to obtain PFCH-1-CAF in an yield of more 90%. As a result of the study of the catalytic decarboxilation reaction of 1,2-DFPFCHDCA a novel technologically feasible method of the synthesis of PFCH-1-CAF has been developed.


Р-86

SYNTHESIS OF OCTAFLUORONAPHTHALENE

S. M. Igumnov, G. I. Lekontseva, I. V. Markin

Joint Stock Company «Scientific Industrial Association “P&M-Invest”» Vavilova St., 28, Moscow, 11999, Russia

E-mail: [email protected] Federal State Unitary Enterprisу «Russian Scientific Center “Applied Chemistry”»,

Perm Branch, Voronezhskaya St., 41, Perm, 614034, Russia E-mail: [email protected]

Octafluoronaphthalene is of interest as a starting material for the synthesis of a variety of

new compounds. At present the need for this product is growing and so the development of new effective methods for its preparation is a high-priority task.

The known methods for the preparation of octafluoronaphthalene, which are defluorination of perfluorodecalin over an iron gauze at a temperature of 460-500oC and fluorination of octachloronaphthalene with BrF3 and SbF3 followed by dehalogenation with zinc and also by the action of potassium fluoride in sulfolane, have substantial drawbacks: high temperature, high pressure, resinification and carbonization of the reaction mass and as a consequence low yields of 24-60% /1/.

We have carried out a process for the fluorination of octachloronaphthalene with potassium fluoride in the presence of catalyst in a standard reactor of stainless steel. Hexaethylguanidinium chloride was used as a catalyst which permitted to lower a temperature down to 180oC and run the process without pressure.

Cl Cl F FKF, kat180o

C

Octafluoronaphthalene was separated from the reaction mass by distillation under vacuum with a purity up to 93-97%. As a result an effective industrial technology for the preparation of octafluoronaphthalene in an yield up to 92% with a 100% conversion of starting material has been developed. The technology has passed an evaluation test at the pilot plant of «Russian Scientific Center “Applied chemistry”» Perm Branch.

1 Syntheses of Organofluoric Compounds. Edited by I.L.Knunyants. M.: Khimiya, 1973.


Р-87

ELECTROCHEMICAL SYNTHESIS OF FLUOROANHYDRATES OF PERFLUOROCARBONIC ACIDS

V. A. Matalin, G. I. Kaurova, D. D. Moldavsky,

N. B. Lisnevskaya, A. A. Ludikainen

FSUE «RSC “Applied Chemistry”», Dobrolubov Ave;14, St.Petersburg, 14, Russia E-mail: [email protected]

Of obvious industrial interest are perfluorocarboxylic or sulfonic acid fluorides (С7 or more)

produced through electrochemical fluorination (ECF). These substances are used as raw materials in the synthesis of high-performance fluorinated surfactants applied to metallurgy, transport, manufacture of fluoropolymers, etc. However, their synthesis is limited by low yields due to destruction and gumming of the initial substrate in the course of electrolysis.

We conducted comparison studies of the synthesis of acid fluorides through ECF of H(CF2-CF2)4CH2OH with the addition of H(С2F4)CH2OH (according to1) and with the addition of tertiary amines. The amines provide HF solubility of the substrate and electroconductivity of the electrolyte, their ECF results in perfluorinated amines that are commercial products. Besides of that ECF of C8H17SO2F and с-C6F11СОF was conducted with the addition of tertiary amines and the results were compared with the data on ECF with the addition of NaF and C4H9SH. The results of the study are shown in the table below.

Electrolytic additive

Anode current density, A/cm2

Passed electricity, Ah (Ah/l)

Yield by current of

crude product, %

Main components of crude product, % mass

ECF H(С2F4)4CH2OH F(С2F4)4COF C8F18 (RF)3N* H(С2F4)CH2OH 0.02 4371 (2186) 21 35 27 -

C5H5N 0.03 1062 (1610) 21 22 23 28* (C2H5)3N 0.03 963 (2139) 34 47 28 5 (C3H5)3N 0.03 2640 (4000) 40 39 15 25

ECF C6H5СОCl C6F11СОF (RF)3N* NaF 0.03 611 (1222) 46 55 -

C5H5N 0.03 246 (546) 57 53 14 (C2H5)3N 0.03 231 (462) 70 - -

(C3H5)3N pulsation:

30″-0.03A/cm2 5″-0.001A/cm2

2708 (5417) 67 50 25

ECF C8H17SO2F C8F17SO2F C8F18 (RF)3N* NaF,C4H9SH 2 ≤0.002 − up to 40 - - -

(C3H7)3N 0.03 1133 (1718) 46 57 20 12 (C3H5)3N 0.03 1584 (2400) 52 50 14 24

* The percentage of the main product of amine fluorination that is perfluorinated analogue; in the case of C5H5N it was perfluoropentane C5F12.

From the above data one may see that the proposed method allows one to improve the electrochemical synthesis of perfluorinated organics. The attendant products are perfluorinated tertiary amines that distinguished for their unique thermophysical and dielectric properties and find wide range of applications in various industrial sectors. _______________________________________________________________ 1 Maximov B.N. et al. RF Patent №2107751 (1998). 2 Cauquis G. et al. J. Electroanal. Chem., 100 (1979), 205–215.


Р-88

ELECTROCHEMICAL FLUORINATION (ECF) OF TOLUENE AND BENZOTRIFLUORIDE IN THE PRESENCE OF TRIALLYL AMINE

V. A. Matalina, G. I. Kaurovaa, V. V. Berenblitb, V. I. Gribela

аFSUE «RSC “Applied Chemistry”», Dobrolubov Ave;14, St.Petersburg, 14, Russia

bFSUE “S. V. Lebedev VNIISK” Gapsalskay str., 1, St.Petersburg, Russia E-mail: [email protected]

The synthesis of perfluoromethylcyclohexane (PFMCH) through ECF is limited by the low

yields as the initial substrate is insoluble in HF, and its destruction and gumming in the course of electrosynthesis embarrass considerably arrangement of continuous electrolysis.

Those effects can be diminished by adding some depolarizer that would fix the stationary electrolysis regime1, providing electroconductivity and solubility of the initial substrate in electrolyte.

Both destruction and isomerization of the substrate may be decreased through the usage of partly fluorinated initial structures.

It was important to find such electrolytic additives that would suppress the electrolyte gumming, increase its lifetime and favor formation of merchantable products.

In this connection we carried out comparison studies of PFMCH yield in the course of ECF of toluene and benzotrifluoride with the addition of triallylamine (TAA). At the conditions of non-interrupted electrolysis ECF of TAA is a stationary process that results in the high yield of a blend that consists of perfluorotripropylamine, perfluoro-N-propyl-5- and -6-merous heterocycles2.

ECF was conducted in a laboratory direct-current Simons electrolyzer, in anhydrous HF, the electrolyte concentration was 10% by mass, and the ratio “substrate: TAA“ was 1:1.

In ECF of benzotrifluoride the yield-by-current of the crude product within the bottom layer reached rather high value 0.53g/A⋅h. The results of the ECF process study are shown in the table below.

Test conditions Yield # Charge, g (mole) Produced, g(mole) %mole g/A⋅h

ECF of toluene and triallylamine (DA=0.03A/dm2,Q=440A⋅h) СН3С6Н5, 62.0(0.68) СF3-c-C6F11, 5.0(0.021)+c-С6F12, 2.5(0.013) 5.1 0.017

1

(СН2=СНСН2)3N, 75.0(0.55) 0.2(C3F7)3N+0.8C3F7N<cC6F12,32.2(0.081) 8.1 0.073 ECF of benzotrifluoride and triallylamine (DA=0.03A/dm2,Q=440 A⋅h)

СF3С6Н5, 127.4(0.87) СF3-c-С6F11, 236(0.67)+c-C 6F12, 41.4(0.14) 93 0.35 2

(СН2=СНСН2)3N,121.0(0.89) 0.2(C3F7)3N+0.8C3F7N<cC6F12,82.2(0.21) 24 0.105 The crude product was GLC-analyzed and rectified. We isolated three fractions as follows: head fraction (b.p.=52-54oC); target fraction (b.p.=76-78oC); heavy fraction (b.p.=129-131oC). The head fraction contained the isomers of c-С6F12. The target fraction contained СF3-c-С6F11 (80%) and the isomers resulting from narrowing of the hexamerous cycle: perfluoro-1,1-dimethyl- and perfluoro-1,3-dimethyl-cyclopentanes, and C2F5-c-C5F9, all identified by their NMR19F spectra. The heavy fraction contained [%mass]: (n-С3F7)3N [20.3%]; n-С3F7-N<cyclo-С4F6(-3,4-СF3)2 (both cis-[41.2%] and trans- [18.7%]); n-С3F7-N<cyclo-С5F9-3-СF3 [19.3%]. Our study opens the way to provide high yields-by-current of some organofluoric substances for medical and technical applications through ECF of benzotrifluoride and triallylamine.

1 Berenblit V.V.et al. J. Applied Chemistry (Russ.), 1974, 47, 591 2 Inventor Certificate USSR №1094287 (1984).


Р-89

SULFURTRIOXIDATION OF HEXAFLUOROBUTADIENE, NOVEL DATA

N. V. Lebedeva, G. A. Emelianova, F. A. Mahmutovb, D. D. Moldavskiyc, V. V. Berenblita

aS. V. Lebedev Institute of Synthetic Rubber, Gapsalskaya st., 1, St.Petersburg, 198035, Russia bSRC Medical and Ecological Chemistry, Tula, Russia

cFSUE «RSC “Applied Chemistry”», Dobrolubov Ave;14, St.Petersburg, 14, Russia E-mail: [email protected]

The products of interaction of hexafluorobutadiene (HFBD) with sulfur trioxide depending

on conditions and medium were investigated. Using NMR 19F spectra it was found that during sulfurtrioxidation the formation of hexafluorobuten-1-sulton-3,4 take place:

1-cisF\ /F2-vinyl

/F4-ax

C = C –/C3F – C ↕127.5Hz

1-transF/ SO2 – O/ \F4-eq The chemical shifts of magnetically non-equivalent nucleuses in sultonic cycle show that

sulfur in it is oriented to iternal C-atom of HFBD, but not to terminal one as I.L.Knunyants et al. suggested1. The value of heminal spin-spin coupling constants (SSCC) is in accordance with four-chain cycle �-sulton-3,4. The content of above mentioned product varies from 30 to 70%mol depending on temperature and medium.

In a case of low conversion of HFBD (by excess of sulfur trioxide) the signals of hexafluorobutene-1-pyrosulton-3,4 appear in spectra. Chemical shifts and SSCC of vinyl group of fluorine nucleuses differs little from ones of �-sulton. In the same time, heminal SSCC at 163.5Hz is close1 to the structure –C3F-/CF2

4, what can be the evidence of six-chain sulton cycle. \O-SO2

Yield of such pyrosulton is about 5%mol. In investigated mixtures the product of addition of sulfur trioxide and HFBD with

formation of hexafluorobutene-2-sulton-1,4 was identified. Its content was in a range of 15-25%mol depending on conditions.

At -68 and -140 ppm there are two signals at spectra, with ratio intensities equal 1:2. Their SSCC is close to the SSCC of –OC1F2-C

2F= in hexafluorobuten-2-sulton-1,4. These signal correspond to 7-chain cycle of hexafluorobuten-2-sulphate-1,4 of structure:

C3F - C4F2OSO2 \\C2F-C1F2O

/

The content of this cycle in mixture was varied in a range of 1-15%mol. It is formed1 while heating hexafluorobutene-2-sulton-1,4. But the mechanism of such transformation is not clear. This sulphate should be formed under elimination of sulfur trioxide with hexafluorobutene-2-pyrosulton-1,4, which (unlike to sulton 3,4), could be distinguished using NMR-spectroscopy from sulton 1,4. Among the products of mixture the perfluoro-4-fluorosulphatebutene-2-oil-1-fluorides FSO2OC4F2C

3F=C2F1COF were identified which are formed while uncovering described cycle. These fluorides have differences in chemical shifts and SSCC values of fluorine nucleases in cis- and trans- positions. As a result of elimination of sulfur trioxide while heating mixtures cis- and trans- isomers of perfluorocrotonoilfluorides were identified.

______________________________________________

1Kazmina N.B. et al. Izv. AN. SSSR, Ser. Khim., 1979 (1), 118.


Р-90

THE INTERACTION OF 1,4-CUBANE DERIVATIVES WITH ELEMENTAL FLUORINE. NMR STUDY

L. T. Eremenko, G. V. Oreshko, G. V. Lagodzinskaya

Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432, Chernogolovka, Moscow Region, Russia


Elemental fluorine can be successfully used for fluorination of cubane derivatives.1 The nature of the products depends on the fluorination conditions: in CH3CN at –20 to –30°C, dimethyl 2-fluorocubane-1,4-dicarboxylate was obtained from dimethyl ester of 1,4-cubanedicarboxylic acid; in CF3COOH at –12 to –15°C in the presence of alkali metal acetates, 1,4-cubanedicarboxylic acid and its dimethyl and diethyl esters gave complex mixtures of fluorinated cubane products. Our investigation by 1H and 19F NMR spectroscopy and spectra computer simulation revealed production of mono- and difluorinated cubanes. Fluorine-containing cubane derivatives were also found with extra substituents in other than 1 and 4 positions (see following Scheme).

R

R

FI

F2

R

R

F

F

IIa

HF-

R

R

FR

R IIIa

R

R

FF

IIс

R

R F

R

R IIIс

R

R

F

F

R

R

FR

R IIIbIIb

HF

HF-

-

-

R

R

R

R

R

R

R

R

Products of polycondensationand destruction

F2

COOC2H5COOCH3 ,(2) (3),(1)R=COOH

(1-3)

(1-3)

(1-3) (1-3)

(1-3) (1-3)

(1-3) The work has been performed with financial support from DSWA, USA (Contract DNA

001-95-C-0021). _____________________________ 1 Eremenko L.T. et al. Spectrochimica Acta Part A, 2001, 57, 1663–1672.


Р-91

STERICALLY HINDERED FLUORINATED AND BROMINATED TRÖGER BASES: SYNTHESIS AND X-RAY CRYSTAL STRUCTURE

INVESTIGATION

D. A. Lenev,a K. A. Lyssenko,b R. G. Kostyanovskya

aSemenov Institute of Chemical Physics, Russian Academy of Sciences,

119991, Kosygina 4, Moscow, Russia bNesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Vavilova

28, Moscow, Russia Е-mail: [email protected]

Tröger bases (TBs) are readily available prime stereochemistry objects with chirality solely

due to bridgehead nitrogen atoms. Variety of TBs have been synthesized, and the procedure for the synthesis was optimised and reoptimised and now libraries of the TBs are available.1 One of their interesting applications is the use of TBs as DNA drugs.2

A complication in the enantioselective chemistry of TBs is the easy racemization in acidic media via iminium intermediate. It was shown that for the interconversion to occur, a transition state has to be passed which is sensitive to steric effects.3 Thus, bis-ortho-substitution by methyl groups increases the barrier of racemization by ~ 30 kJ mole-1.3 Bulky substitution at ortho-positions may further increase this barrier. For instance, CF3 groups with high steric volume also could provide interesting electronic properties to TB core. We have synthesized two bis-ortho-substituted TBs: bis-(ortho-,para-trifluoromethyl) 1 and bis-(ortho-tert-butyl, para-bromo) 2. The crystal structure investigation of 1 is presented.

N

NR2

R2

NH2

R2

R1 1.5/n(CH2O)n

CF3COOH 5-30%

R1

R1

2, R1=R2=CF3

3, R1=Bu-t, R2=Br

Fig. 1 The general view of 1.

This work was supported by the Russian Foundation for Basic Research (grant Nos. 03-03-32019 and 03-03-04010), the Russian Academy of Sciences (Nefedov-Tartakovsky programmes) and INTAS (grant No. YS 04-83-3442).

___________________________ 1. Demeunynck M. et al. ‘‘Recent developments in Tröger’s base chemistry’’, in: Progress in heterocyclic

chemistry, vol. 11 (Eds.: G. W. Gribble, T. L. Gilchrist), Pergamon, Oxford, 1999, pp. 1-21. 2. (a) Yashima E. et al. Chem. Lett. 1991, 1017-1020, (b) Tatibouët А. et al. Chem. Commun. 1999, 161–162; (c)

Baldeyrou B. et al. Eur. J. Med. Chem. 2002, 37, 315-322. 3. Lenev D.A. et al. Chem. Eur. J. 2006, http://dx.doi.org/10.1002/chem.200501532


Р-92

ELECTROCHEMICAL PROTODEMERCURATION OF INTERMEDIATES OF PENTAFLUOROPHENYLMERCURY BROMIDE

REDUCTION IN LOW-ACIDIC MEDIA

V. А. Kurmazа, А. B. Ershlerb†

aInstitute of Problems of Chemical Physics RAS,Chernogolovka, Moscow Region 142432, Russia bA. N. Frumkin Institute of Electrochemistry RAS, Leninsky Prospect 31, Moscow, 117071, Russia


It was studied by current reversal pulse galvanostatic method, and conventional linear sweep voltammetry and chronovoltammetry the electrochemical behaviour of symmetrical organomercury compounds contained aromatic and perfluoroaromatic groups: perfluorodiphenylmercury (C6F5)2Hg, synthesed via one-electron reduction of pentafluorophenylmercury bromide C6F5HgBr, and bis(phenylacetylenyl)mercury (C6H5C≡C)2Hg. It was demonstrated that a condensed phase of (C6F5)2Hg is formed near Hg-electrode surface during controlled potential electrolysis of C6F5HgBr in basic and neutral aqueous-alcohol solutions (10% vol. of EtOH or МеОН) of inorganic salts and buffers, whereas a structure of monolayer and suspension and their chemical nature are different. Perfluorodiphenylmercury was established to form complexes with anions1 of a background electrolyte or a solvent behind the monolayer that are able to reduce, depending on experimental conditions, separately2 or with antecedent dissociation together with this monolayer. Some important properties of complexes have been determined (the charges and the dissociation kinetic currents).

A destruction of (C6F5)2Hg condensed phase was revealed in low-acidic media (3 < рН < 6), and acids addition did not affect the monolayer properties. In the case of (C6H5C≡C)2Hg that is able to reduce either directly or with antecedent quasi-reversible surface transition into a metastable “organic calomel” [RHgads] (scheme 1) such additions of acids lead to disappearance of the “calomel” reduction wave. It was supposed that observed effects were caused by “electrochemical” protodemercuration (or protodemetallation, if to take into account the data for other systems3) of [RHgads] intermediates near electrode surface. Apparently, such reactions can play significant role in chemistry of organometallic compounds.

R 1H g++e

[R 1H g]

[R 2H g]

+2e

+2BH +

+H 3O +

2R 1(R 2)H + 2B + H g

R 12H g

decay productsR 1: C 6F5; R 2: C 6H 5C C

+ H g+ H g

+2BH +

+2eR 2

2Hg

+2e

+2BH +

Scheme 1

1 Saitkulova L.N. et al. J. Organometal. Chem. 1999, 585(2), 201-210. 2 Ershler A.B. et al. Sov. Electrochem. 1980, 16(7), 817-825. 3 Butler A.L. et al. J. Electrochem. Soc. 1997, 144(12), 4212-4217.


Р-93

NOVEL REACTIONS OF α,β-UNSATURATED TRIFLUOROMETHYL KETONES

V. G. Nenajdenko, S. V. Druzhinin, E. S. Balenkova

Moscow State University, Department of Chemistry, Leninskie Gory, Moscow 119992, Russia

Fax: +7-(495)-932-88-46, E-mail: [email protected]

Due to its unique stereoelectronic properties trifluoromethyl group nowadays is a very

important substituent in organic chemistry, because of principal differences existing between methyl and triflouromethyl groups in physical, chemical and physiological properties. Compounds containing trifluoromethyl group, particularly heterocyclic, are of intense interest. α,β-Unsaturated trifluoromethylketones, readily obtained from various organolithium or organomagnesium reagents and CF3-enaminoketones, are perspective building blocks for synthesis of alicyclic and heterocyclic compounds containing trifluoromethyl group. We have shown the efficient application of α,β-unsaturated trifluoromethylketones in synthesis of CF3-containing pyranes, derivatives of pyridine, nitro- and cyanoketones, pyrolines and pyrollidones, bicyclic carbo- and heterocyclic systems.

R

CF3

O

O

OH

CF3R

N

O

OH

CF3RO

OH

CF3R

NH

R

OH

CF3

O

NH

R

CF3O

R

O

CF3

CN

O

EtO

R

O

CF3

NO2

O

EtO

R

O

CF3

NO2

O

R

NC

R1CF3

OH

NH

R

NC

R1CF3

OH

NH

R

NC

R1 CF3

N

R

NC

R1 CF3

Figure 1


Р-94

SYNTHESIS OF FLUORINE CONTAINING HETEROCYCLES USING FLUORO AND CF3-SUBSTITUTED STYRENES

V. G. Nenajdenkoa, V. M. Muzalevskya, A. V. Shastinb, E. S. Balenkovaa

aMoscow State University, Department of Chemistry, Leninskie Gory, Moscow 119992, Russia

bInstitute of Problems of Chemical Physics, Chernogolovka, Moscow Region 142432, Russia E-mail: [email protected]

Organofluorine compounds are an object of increasing interest due to their biological

activity. Earlier using catalytic olefination reaction we elaborated a novel method for synthesis of fluorine containing styrenes ArCR=CXCF3(F), X=Cl, Br. These compounds contains sufficiently active halogen atom and hidden carbonyl function. Combination of both functions allows to utilize these styrenes for the synthesis of wide variety alkenes containing cyano-, sulfonyl-, thioalkyl-, dialkylamino- and alkoxy-groups. Heterocycles of indole, isoquinoline, pyrrolopiperazine and imidazopyridine series were also obtained.

R1

R2

X

CF3(F)

R1

R2

CN

CF3(F)R1

R2

SO2R

CF3(F)

R1

R2

SR

CF3

R1

R2

OR

CF3

R1

R2

NR2

CF3

NH

RF3C

N

NCF3

R1

NCF3

X=Cl,Br

ArHet

R1


Р-95

ALLYLBORATION OF FLUORINE-CONTAINING CARBONYL COMPOUNDS, CARBOXYLIC ACIDS AND DINITRILES

N. Yu. Kuznetsova, M. E. Gurskiib, G. D. Kolomnikovaa, S. Yu. Erdyakovb,

Yu. N. Bubnova

aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Science, 119991, GSP-1, Vavilova str., 28, Moscow, Russia

bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991, GSP-1, Leninsky pr., 47, Moscow, Russia

E-mail: [email protected] In 1962, Knunyants and Dyatkin1 have prepared fluorinated tert-homoallylic alcohols by

thermal (20-200 °С) and catalytic (AlCl3, −10 °С) ene-reaction of hexafluoroacetone (HFA) with propene, isobutene and cyclohexene. Such alcohols are also readily available via allyl- and methallylboration of fluorinated aldehydes and HFA; crotylboration of the latter proceeds with allylic rearrangement2,3.

Here we report the allylboration of perfluorinated carboxylic acids, three isomeric fluorobenzaldehydes and a series of dinitriles, leading to unsaturated carbinols and diamines in good yields:

)3B

1.O

F

2. H2O, OH_

N C X CN

1. RCOOH

81-93%

R

OH

_2. H2O, OH

OH

F

X NH2H2N

87-96%

R = CF3, C6F13, CF3OCF2CF2, C6F5

N

X = (CH2)6, (CF2)6, ,

The reactions proceed stepwise in the common organometallic manner with the transfer of the allylic group to the carbon atom of the C=O or C≡N bonds and the boron atom to the oxygen or the nitrogen atom, respectively.

Compounds thus obtained are excellent precursors for the fluorinated dienes, cyclopentadienes, and macromolecular compounds.

We are grateful to the President of the Russian Federation (grant № 2878.2006.03), Presidium of the RAS (Programme № 8), Division of Chemistry and Material Sciences RAS (Programme № 1) and Russian Foundation for Basic Research (grants № 05-03-33268 and 05-03-32953) for financial support .

________________________________________

1 Knunyants I.L.et al. Izv. AN USSR. Ser. Khim. 1962, 355. 2 Mikhailov B.M. et al. J. Organometal. Chem. 1978, 154, 131. 3 Ramachandran P.V. et al. Tetrahedron Lett. 2004, 45, 1015.


Р-96

BORON TRIFLUORIDE REACTION WITH ALLYLIC BORANES AND 1-BORAADAMANTANE

S. Yu. Erdyakova, M. E. Gurskiia, A. V. Ignatenkoa, V. P. Ananikova, V. V. Kachalaa,

Yu. N. Bubnovb

aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,

119991, GSP-1, Leninsky pr., 47, Moscow, Russia bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Science,

119991, GSP-1, Vavilova str., 28, Moscow, Russia E-mail: [email protected]

Diorganyl(fluoro)boranes are available by the redistribution reaction of trialkylboranes

with boron trifluoride in the presence of catalytic amounts of boron hydrides1. We have found that triallyl- and allyldialkylboranes readily react with BF3 at -120 − -100

ºC without a B-H catalyst, giving rise to the corresponding allyl(difluoro)boranes.

BF2- Pr2BF

BPr21 eq. BF3

)3B + 2 BF3 BF23F2B

FB

All

All

BF2

-120 0 єC

quant.δ NMR 11B 28.0 , t J = 70 Hzδ NMR 19F -73.2, q J = 70 Hz

Reaction proceeds as the intermolecular allylic rearrangement, that we detected with the

faze-sensitive 11B-11B NOESY NMR spectroscopy. Note, that the methodology proposed, can not be applied for the preparation of

diallyl(fluoro)borane: even with a triple excess of triallylborane equilibrium can not be moved to monofluoro derivative.

)3B + BF3 BF2 BF2 )3B+ +

δ NMR 11B 81.456.8, d J = 114 Hz 28.0 , t J = 70 Hz Reaction of boron trifluoride with 1-boraadamantane proceeds under mild conditions

(0 ºC) leading to 3-fluoro-7-difluoroborylmethyl-3-borabicyclo[3.3.1]nonane derivative as a result of 1-boraadamantane core rupture.

δ NMR 11B 27.1 , t J = 79 Hz 59.6, d J= 119 Hz

B

Et3N

B BF2

F

- Et3N·BF3

δ NMR 19F -72.3, q J = 79 Hz -32.6, q J = 119 Hz

BF3

0 єC, pentane

We are grateful to the President of the Russian Federation (grant № 2878.2006.03),

Presidium of the RAS (Programme № 8), Division of Chemistry and Material Sciences RAS (Programme № 1) and Russian Foundation for Basic Research (grants № 05-03-33268 and 05-03-32953). __________________________________ 1 Koster R. Organobor-Verbindungen I, In Houben-Weyl Methoden der organishen Chemie, (Ed. H. Kropf), Georg

Thieme Verlag, 1982, Stuttgart, New York, Band 13/ 3a, 910 p.


Р-97

α-FLUORONITRO COMPOUNDS IN THE SYNTHESIS OF ISOXAZOLINE-N-OXIDES.

R. A. Kunetsky, A. D. Dilman, S. L. Ioffe, M. I. Struchkova, V. A. Tartakovsky

N. D. Zelinsky Institute of Organic Chemistry, Leninsky prosp. 47, 119991 Moscow, Russia


Isoxazoline-N-oxides (1) constitute an important class of cyclic nitronates. These compounds can be straightforwardly accessed from α-bromonitro alkanes and olefins1; however, the long reaction times represent the major limitation of this methodology.

We found that employment of α-fluoronitro compounds, obtained by fluorination of nitronate anions with selectfluor,2 significantly affected the mechanistic picture of the process and afforded noticeable rate enhancement. Thus, the α-fluoronitro compounds are silylated with Me3SiCl/NEt3 to give unstable α-fluorosilyl nitronates, which rapidly undergo 1,3-dipolar cycloaddition with the alkene furnishing 3-fluoro-N-silyloxyisoxazolidines. The fragmentation of the latter species with the loss of Me3SiF can be effected in refluxing acetonitrile furnishing target isoxazoline-N-oxides in good yields.

R1

NO2

R1

NO2

F

N

N

Cl

F 2BF4–

R1

N

F

O OSiMe3R4

R2

R3

NO OSiMe3

R2

R3

R4R1

F

Me3SiCl/NEt3

NO O

R2

R3

R4 R1

MeCN, ∆–Me3SiF

2. Selectfluor

Selectfluor

1. KOH

1

The peculiarities of every elementary step of this method are mainly determined by the

fluorine atom. The comparison of fluorine with other halogens in their ability to influence the stability and reactivity of intermediate silyl nitronates and isoxazolidines will be presented.

This work was supported by Russian Foundation for Basic Research (grant 05-03-32733 and 05-03-08175 afi).

___________________ 1. Kunetsky R.A. et al. Org. Lett. 2003, 5, 4907. 2. Peng W. et al. Tetrahedron Lett. 2005, 46, 4905.


Р-98

EMPLOYMENT OF TPIS(PENTAFLUOROPHENYL)SILYL DERIVATIVES IN SYNTHESYS OF C6F5-SUBSTITUTED AMINES

V. V. Levina, A. D. Dilmana, P. A. Belyakova, A. A. Korlyukovb, M. I. Struchkovaa,

V. A Tartakovskya

aN. D. Zelinsky Institute of Organic Chemistry RAS, Leninsky Prosp. 47, 119991, Moscow, Russia.

bA. N. Nesmeyanov Institute of Organoelement Compounds RAS, Vavilova St. 28, 119991, Moscow, Russia.


In recent years there has been a notable growth of interest towards amines bearing fluorinated substituents, that is associated with their diverse biological activity. Many of synthetic methods towards such compounds require the employment of highly reactive organometallic reagents that narrow the scope of the suitable substrates. We exploit another approach based on the ability of fluorinated silanes to serve as nucleophilic reagents under mild conditions.

We found that the propensity of silicon atom to expand its valence shell may be significantly increased by the introduction of several pentafluorophenyl groups16. Importantly, the hypercoordinate siliconate species, resulting from the interaction of C6F5-substituted silane with a Lewis base, behaves as a source of nucleophilic C6F5-group.

As an example of this methodology we performed the synthesis of C6F5-substituted aminoethanols17. Thus, the alkylation of imines with 2-tris(pentafluorophenyl)silyloxyethyl triflate affords silyloxyethylimium salts. Their treatment with sodium acetate induces C-C-bond formation proceeding as transfer of the C6F5-group from the five-coordinate silicate intermediate to the iminium center.

O+(C6F5)3SiOTf OTf

R1

NR2

(C6F5)3SiO NR2

R1

(C6F5)3SiO

NaOAc

NR2

R1

OSi(C6F5)2

AcO

C6F5

NR2

R1

HO

C6F5

NR2

R1

OSi

AcO

C6F5

C6F5C6F5

aq. Na2CO3

OTf

This work was supported by the Ministry of Science (MK-2235.2005.3) and INTAS (2003-

55-1185).

__________________ 1 Dilman A.D. et al. Org. Lett. 2005, 7, 2913. 2 Levin V.V. et al. Synthesis. 2006, 489.


Р-99

REACTIONS OF NITROFLUOROBENZENES WITH CARBANIONS LEADING TO THE ANIONIC HEPTATRIENIDE MOIETIES

Y. G. Gololobov, O. A. Linchenko

A. N. Nesmeyanov Institute of Organoelement Compounds RAS,

Vavilova St. 28, 119991, Moscow, Russia Е-mail: [email protected].

We have established that reactions of NCCH2COOMe (1a) and CH2(CN)2 (1b) with 2,4-

dinitrofluorobenzene (2) at the presence of Et3N result in deeply-colored crystalline stable salts (4a, 4b) with anions that contain a system of conjugated bonds.1

Et3N

F

NO2

NO2CH

CN

XEt3NH

NO2

NO2

Hβ '

Hα Hβ

C

CN

X

Et3NH

Et3N

Et3N.HF

3 4

-+ 2

X = C(O)OMe (a), CN (b)

H2CCN

X

1

Carbanion 4a reacts with isocyanates unusually. The transiently formed intermediates 5

undergo migration of alkoxycarbonyl group from carbon to nitrogen to form the corresponding carbamates 6.

Ph N C O

Et3NH Et3NH

C(O)OMe

NO2

O2N CCN

CO

NPh

Ph

NO2

O2N C

CN

CO

C(O)OMe

N

NO2

O2N CCN

C(O)OMe

Et3NH4a 5 6 FC6H3(NO2)2-2,4 reacts with zwitter-ion 7 giving in the first stage obviously σ-complex 8,

stabilisation of which leads to the stable hexadienic stracture 9. The formation of the zwitter ion 9 is, apparently, the result of disintegration of 8, which one includes attack by fluorine of C(O)OEt group. The disruption of C-C bond is due to it weakness. FC(O)OEt was identified by NMR(1H,19F) and IR spectroscopy.2

i-Pr3PCH2CCN

C(O)OEti-Pr3PCH2C

C

O=COEt

N

F

NO2

NO2 i-Pr3PCH2C

C

NO2

N NO2

-FC(O)OEt7 9

2

8 The success of above-mentioned transformations is conditioned by presence of the

electronegative substituents at the carbanionic center. The driving force of the reactions is probably influenced by an energetic gain from the more effective delocalization of anionic charge in the product being formed. Structures of the 4a and 9 were conformed by x-ray investigations. The given reactions bring about new types of carbamates and high-conjugated hexadienes, bearing an anionic and cationic charges in one molecule.

The research was supported financially by Russian Foundation for Basic Research (Project No. 04-03-32489). _____________________________ 1 Gololobov Yu.G. et al. Heteroatom Chem. 2006 (in press) 2 Gololobov Yu.G. et al. Izv. AN, Ser. Khim. 2005, 54(10), 2323-30.


Р-100

METHYL TRIFLUOROPYRUVATE IN CYCLOCONDENSATIO WITH 1,3-BINUCLEOPHYLES

A. Yu. Aksinenko, V. B. Sokolov

Institute of Physiologically Active Compounds, Severnyi proezd 1, 142432, Chernogolovka, Russia E-mail: [email protected]

Methyl trifluoropyruvate was studied in cyclocondensation with various 1,3-C,N- and N,N-binucleophyles (methyl 3-aminocrotonate 2, 6-aminouracyls 3, 6-aminothiouracyls 4, N-substituted 3-aminocyclohexenones 5, N-substituted benzamidines 6, and ureas 7). This reactions results in 5-member fluoro-containing heterocycles of various types 8-13.

1312

2

11

1098

7

6

5

43

1

NHCHC

O O

OHCF3

CH3O

N

NH

O

CF3

OH

R

ON

N

R

O

CF3

OH

N

O

R

CF3

OH

O

HN

N NH

O

S

R

O

CF3

OHHN

N NH

O

O

R

O

CF3

OH

CF3 C

O

C

O

O(O)CH3

All these conversions are realize according to scheme cyclocondensation – addition of methyl trifluoropyruvates to 1,3-binucleophle followed by cyclization with an elimination of methanol. In the case of 6-aminouracyls and ureas the products of addition 14 and 15 were isolated and characterized.

15

14

1R NH C

O

NH2

HN

N NH2

O

O

R

R NH C

O

NH

CF3

C(O)OCH3

OH

HN

N NH2

O

O

R

C(O)OCH3

CF3 OH

CF3 C

O

C

O

O(O)CH3

Structures of compounds synthesized were proved by mass- and NMR-data. The research was supported financially by Branch of General and Technical Chemistry of

Russian Academy of Sciences (Program N 10 “Biomolecular and medicinal chemistry”).

notes.fluorine1.runotes.fluorine1.ru/fluor_conf_06/pdf/posters1_100_en.pdf · 2012-06-18 · 7th...

Documents