Major Professor

Minor Professor1

rTrr: ector of til© Bopartoaat of Ch^olatry

Seen of tha Graduate *>chooI

SYNTHESIS OF BTELER-FREE ORGANOMAGNESIDK COMPOUNDS

THESIS

Presented to the Graduate Council of the

North Texas State University in Partial

Fulfillment of the Requirements

For the Degree of

MASTjER OF SCIMCE

By-

John B. Hanicak, B. A.

Denton, Texas

August, 1967

TABLi Of COSf^fS

J'age

L IS f OF 19

Chapter

i # HisfosiCAi, m m m o f o m & m i M m m m i ccmowm. i

XI. JSPEI I IK^m PROCEDURE . . 20

Mater ia ls Preparation and Analysis of Kther-froe

Organmagneaium Compounds Preparation and Analysis of Sthareal Grignard

Reagents Cryoscopic Molecular height Studios Inf rared Absorption studies

I I I , REijULIB M'J CGKCLU&I08&• 28

36

i l l

LISf OF TABtiSB

!• Conditions of sjathmm of Organo

* # # * *

11# Comparison of XIelds of Q gsaoamgussitiii. Cota-po-iiMs Praperod la iith r and Without joXv ©nt $ • • • • * • • • • « • • « • » • • •

IV

Pago

CHAPTSa 1

In 1890 f Phillippo Barbior attempted the synthesis of

2, 6~di»0thyl~2*-h9pten~6-ol from natural 2-©©thyl-2 hapten-

6-one via the •/agnsr-^aytzeff reaction (6k), which is the

action of zinc Ratal and mettiyl iodide on an athor solution

.. M s particular reaction did not work. Barbiar

decided to substitute magnesiun for sine, Tho desired re-

action procaoded nicelyf and Barbier reported his results

in X399 (7). In his article Barbiar stated that tho substitu-

tion of aagnasiuaa for zinc in the Mgn^r-Saytseff reaction

<ta$ new| that the modification of tha reaction enabled hia

to perform several new synthasest and that he raaorvad the

right to further develop his method* Barbiar, however, did

not publish further work in tha area#

.*hon Victor Grignard requested a thesis topic t Barbiar

suggested that he study the use of magnesium in tho synthesis

of a w organic compounds (^2). Bacause hs oncountared erratic

reactions and poor yields *#lth the Barbior aynthosis, Grignard

decided to attempt to isolate tho organomagne3ivac ccxapound,

which was the aaemetd reaction intermediate, and thon roact

it with scne substrata such as a katona# Grignard proved

with a asrioa of reactions that alfcyl halidas

readily react *!tii magnesium turnings in tho preoencs of dry

ether to form an organomagnesium compound, which, is ether

soluble and which reacts with carbonyl compounds to give

results, in most cases, than does the Barbier synthesis

OH). Grignard published his results in a paper entitled

"Sur quelques nouvelles comblnaisons organometalliques

du magnesium et leur application a des syntheses d' alcools

et hydrocarbures" in 1900 (29).

The Grignard reaction gained immediate acceptance. By

the end of 1905, the chemical literature contained 200 pub-

lications dealing with the Grignard reaction, and by the end

of 1912, more than 700 publications (U-2, pp. 1+8l-i+82).

Grignard proposed that the structure of his reagent in

ether solution is RMgX, where R is an alkyl or aryl group

and X is chloride, bromide, or iodide (27, 28, 29). Blaise

reported that ether is tightly held by the Grignard reagent

in spite of heating (10)• Baeyer and Vllllger proposed an

oxonium structure, where the oxygen of the ether is quadriva-

lent, for the Grignard reagent (6). Several authors (9, 25,

26, 51> 52, 53) accepted the oxonium theory until the report

by Thorp and Kamm ( 5 6 ) , which showed that the theory is un-

necessary for explaining the decomposition products of the

Grignard reagent in ethers.

Meisenheimer and Casper (37) viewed the Grignard reagent

in ether as a complex compound in which the magnesium atom

is central and has a coordination number of four. Two mole-

cules of ether are coordinated, through the oxygen, to the

Kagnesiura stem. According to this vie,/, when a carbanyl

compound reacts «*ith a Grignard mmgmt$ it mast first dis-

place one of the coordinated ether molecules on the magnesium

before reaction can occur, This vie* is essentially the

modem one of the structure of the Grignard reagent in

diethyl athar in concentrations bolov ®*h molar (62) and in

tetrahydrcfuran (3)»

Jclibols, based cn the fact that the compound Kgl2«2Et20,

where It is m ethyl group, is toioam, on the fact that

diethylmagnesium, although practically insoluble in ether,

readily dissolves in an ethor solution of Mglg* 28t20 to give

a solution which has many of the properties of the Grignard

reagent, on tho fact that both the ethyl Grignard reagent and

diothylmagnasiua decompose in tile absence of air at 1?5° C.

to form ethylene and magna siuaa hydride, proposed the structure

It2!'ig.MgX2 C32» 33).

Terentiev (55) reported that methyliaagnasima iodide in

diethyl other is a dimor based on the formula MgX« isalsen-

haimer and acblichenmaier (38) repeated and broadened Teren-

tiev'® rfork and found that the molecular weight of the species

in diethyl ether solution varioa with concentration.

In 1929» chlerik and ichlenk (^5) found that *rtien dioxane

is added to an ether solution of Grignard reagent, practically

all of the halogen is precipitated as the aagnoslua salt#

Thcgr int erpretad these data as meaning that toe Grignard

reagent in diethyl other solutions exists as an equilibrium

of «ithar

(a) + % % or

tw iwig.Mex^ty-ig -v MgXg,

kquillbriua Ca) should be independent of concentration, they

stated, rfhile equilibrium (b) should vary with concentration*

•jiaca they found no apparent chango in equilibrium for an

eightfold dilution of a Grignard solution, thoy concluded

th« structure is bast described by (a),

Recently| two groups of workers, caolik and 2©is#r (U6)

and Dossy and Johes (18), reported the results of electrical

methods of analysis. Both groups showed that tho conductiv-

ity of a mixture of diethyljaagnesium and jsagnesiuai bromide

is higher than vould be expacted, based on the conductivities

of each component alono. Thaso data v«r» interpreted to mean

that tha two co&ponents fora a complex v/hlch ionizes mom

readily than does either individual component* Both groups

reported that tho conductanco of a Grignard solution prepared

in th« ordinary fashion is lower than the conductance of an

squiciolar solution aado by mixing diethylmagnesium and

magnasiua bromide, although the disloctric constants of those

tm solutions ar® identical.

Iteasy and co-workers (li+, 15, 16, 17, 18, 19, 20, 21, 66)

have published a series of papors which triad to establish

that the Grignard reagent in diethyl ether axlsts as the

equilibria,

2MgX^=^a gMg + HgX2x s B2Mg#Mg3C,2

to which the species MgX makes a negligible contribution.

The basis for all of Des&y*s work on th© structure of Grignard

reagents is th© assumption that the Grignard r#ag#»t made by

the reaction of an alley! or aryl halide with aagasslim in

dry diethyl ether la exactly equivalent to an eqitnolar mixture

of dialkyl- or diarylaagne sius and mgyieslua halide la diethyl

ether. If £&9ay*s assumption be true and if the equilibrium

stated above actually describes the sp©ei#s in solution, then

th© existence of th© entity EEgX offers a pathway for th©

exchange of a groups or a pathway for the exchange of magnes-

ium. If BMgX is not present in the solution, two chemically

different kinds of magnesium are present, one bound to halo-

gen and one bound to allsyl or aryl groups. In this discussion

th© molecules of ether coordinated to th© magnesium atoms

have been oraittod for clarity# Dosay <21, 66) established

that equiiaolar mixtures of diethylnagnesiura and magnesium

bromide result in a solution whose kinetics and relative rate

of reaction with 1-hexyn© are the s»i as those of th© normal

othyloagneslura bronide. Dessy and co—rorkars then triad to

prove by dioxana precipitation (16, 17) and electrical studios

(18) that there were two chemically different kinds of tarni-

m&Xvm which hav» no pathway for exchange. Using Mg28sr^t

Deeey (17) found 6 to 10 par cent ejsclmngs. iitti

hoover, Bessy and Handler (16) noted complete exchange, a

situation they attributed to an impurity in the magnesium,

an iapurity which acts am a catalyst for the exchange. Here

the sard "catalyst" Is not used la tho normal mmm but Is

us ad to mean a substance >/hich alters the actual course or

jsechanlsaa of tho reaction* Jinco he did not find exchange

./ith Grignard grade magnasiiaa, Dossy concluded that the ex-

change found with Sg2? is not important to the structure of

an ethereal Grignard reagent, He stated that tho Grignard

reagent is best described by tho following equilibrium*

K2Kg f UgX2^=^i li lg MgX2

Dessy*3 formulation was widely accepted (5)» Recently

Vreugdenhil and Blomberg (60, 61, 62, 63)» Ashby and co-

workers (1, 2, 3, J?)f find Rundle and co-workers (30,

have x?ublish0d papers about tha atructura of the ethereal

Grignard reagent which refute Bessy's conclusions, Ashby

and Becker (3) reported that for concentration up to W o

molar, ©thylmagnesiust broe&do and chloride are inonomeric in

te trahydrofuran and have the structure IHgX* Ashby also

presented positive evidence for alkyl exchange in tetra-

hydrofuran and possible evidence for exchange in diethyl

ether. Ho pointa out that on® should expect differences bet~

¥@@a tetrahydrofuraa and diethyl ether to bo of degree rather

than kind (2, 5) J thus one should eiqxact the ©xistaaee of

HfcgX in diethyl ether, Hundle m d eo«uo*k»rs (30, 5*0 reported

that is the solid state, X-ray diffraction aho./s that both

phenyl-and ettiylmagaeslM bromide diotherate have tho struc-

ture &MgX#22toQ, One cannot say that structure in the solid

state is the structure of a species in solution. Vreugdenhil

and Blomberg (62), working in an oxygen- and moisture-free,

sealed glass system which has no ground joints or stopcocks,

conclusively proved, that for concentrations below O A molar,

a diethyl ether solution of ethylmagnesium bromide is not

equivalent to a solution of a mixture of diethylmagnesium

and magnesium bromide \ above concentrations of 0„}+ molar, the

two solutions are essentially identical. Dessy, Green, and

Salinger (155 repeated their work with Mg2® (17) and found

that there is statistical exchange with some but not all

grades of magnesium. Ashby (1) has shown that the initial

species formed in the reaction of ethyl bromide and magnes-

ium is ethylmagnesium bromide, RMgX, Further, when a diethyl

ether solution of ethylmagnesium bromide is added to a large

excess of trlethylamine, KtMg3r.K(Et)^ is Isolated in 90 per

cent yield* Ashby concludes that this is proof for the

existence of the species BMgX in diethyl ether solution, as

probably the symetrical dimer

Xv

R " M S r g~R*

In summary, most chemists now believe that the Grignard

reagent in diethyl ether solution exists as either the monomer

or symetrical dimer of BMgX, The unsymetrlcal dimer proposed

by Dessy,

Kg Kg, R ^X

8

*/hich is the logical species fori&ad by the mixing of H2;lg

and MgXgi isay be a fairly stable species *hich is slo«r to

convert to tho MgX spocios or its aynetrical dicer in the

absence of a catalyst. Aohby (1) proposes the following

as a pathway for exchange»

.X s

h«I% ^ 2ai<igx^=*n-Kg^ H g - x

H X ^ v / x

— ' RJig + KgXg^—* Kg Kg. / \ /

R X

Kocently ^eiss (6?) reports that X-ray diffraction studies

of the solid remaining after diethyl other is roaoved undor

vacuus at 100 to 120 degrees centigrade from mathylaag-

nesium chloride and bromide and othylx&agnesium chloride

and broraide indicate that tho solid is a niacture of RgHg

and KgXj. Under thoso conditions, Kharasch and Heinmuth

state thoro is still socio coordinated other. Apparently

the major factors are kno^nj however, thero ara still sous#

a3i>*jrinental details to bo resolvad in the study of tha

structure of the Grignard.

when an alkyl or aryl halide reacts with magnesium

eithor in th» absence of a solvent or in the presence of a

hydrocarbon solvent, the organomagnssiwa product is not

identical to tha corresponding Qrignard reagent (11, 2k)*

9

virignard (28) raportod that there is no reaction bet-

m m alkyl telMas and B&goesitai in beaag&ft or ligroin.

}-ialiig»a C35) found m reaction bet*/eoa aIgfofr»c«iiphogyl

broolde and magnesias in boiling bdasaaa, but reaction

occurred ia boiling toluane or xylono. Taohalinsoff <53)

found no reaction of sogftaslisn i&th an unspeoifloft sarins

of iodidea in boiling benseru* aftar V8 hours, Aoehalinseff

used both tMopli»®»fra© aai thJk)ph0n««-oontaisinated teasame*

ia -tylom3t tewtfj ho found that ethyl* JDrP*opylt fi-butylt

a»c! i atsyl ioiisfes- roactod with m&gmBtm *&thout a eatalyst*

The reaction of alkyl and aryl halidea and aagnasium

dltbaut a aolvant was raf/ortad by Spencer and <50)

and later aptftte&r and Crawdson (*»9)* They found that aryl

chloridoa and the lo^wr alkyl halldas, up to &-butyl# form

organooagnasiUB products only in sealed tubes heated to

2?0 degrees oentigrade. Aryl brotsides and iodides and tUo

liigtor alkyl halites form organooagnasium produots in yields

of ka to SO por cent*.

wovaral groups of workers <6, 31, kl9 5l» 52f 571 59)

havs studied the fomatlon of orsazH&agBaaim easpouads in

hydrocarbon solvents in reactions initiated by the addition

of a snail osount of a basic "catalyst" such as an other or

a tertiary aeaine. K&cently Ashby <**) showed that ^»a a

tertiary «i»©f auch as triethylamino, is preaant in mi

atsount 3<iui»olar to the alkyl or aryl halide in a iiydro-

% rbon solvent) tfi# resulting organonagnasium compound is complotoly soluble and lias the structure MgX«

10

Gddo (39) demonstrated that ©agnaeiura does not form

organaciatallic oooLpounds la banson© vmicbi is froe of all

tr«tcas of athars# amines, and thiophon«» Itowevor, he

aho.*sd that 3arbier-typ» syntheses could m a in bansoao

with eaffeonji eoaoipounds*

tills® «ad Bro' n. (22) found that phenyl <&lorldo ra~

actod In $*+ per cont yield with mga@siim is, th« absence

of aolvants in &a evacuated, s wiled glass tubo haatod to 150

to 160 dograes centigrade for thraa .tenra« ^ohorigla and

co-workars (V/) obtained a Enziai® yield of 70 par cent

phanylxaagnesiuE chloride in a stirred, iron autoclave heated

to 160 to 165 degress contigrado for thraa hours with a

pressure of t*o and one half atmcsphara3# Nanske and

leuinghara (36) uasd axceaa phanyl chloride aa the aolv^nt

for the synthoaio of phenylmagnasiua chloride olah (Ho)

vas isouad a patent -hich describes the synthesis of aryl-*

sagnosima halidss in an exoass of aryl tialMs# la oas

axamplo, Olah dascribes tha ua« of ligroin m a solvant for

the synthesis of an alkylraagna aium broaide by uaing a cisc-

tura of a E-otal hydride and a friedel-Crofts metal halide

catalyst to initiate the reaction, aichards and Eolt (l*3)

describe tha synthesis of Grign&rd-typo compounds in hydro-

carbons yfeieh era solide at ordinary mm teaperatures»

;Jchl«nlt (*tW) reported the reaction of aagneatti® with a

series of al'Kqrl iodides in 3©aled tubes which aere mechanically

11

shaken for two months. Benzene is the solvent that ochlenk

used. Although some of the yields were high, they were

rather erratic#

Schorl gin, Issaguljanz, and Gussewa (U-6) reported

failure in the attempt to react magnesium with n-butyl, i-

amyl, or n-octyl chloride at the temperature of the refluxlng

alkyl halide.

Bryce-Smith and co-workers (11, 12, 13), while studying

Friedel-Crafts alkylation with alkyl halides in the presence

of small amounts of magnesium, discovered that some organo-

magnesium compounds can be easily made in hydrocarbon sol-

vents, that in some cases the compounds are made in yields

approaching those in ether, that the organomagnesium com-

pounds resulting from the lower alkyl halides, from secondary

and tertiary alkyl halides or from benzyl halides, are pro-

duced in low yields, and that the solubilities of the com-

pounds in hydrocarbon solvents vary but are usually appreciable,

They stated that for high yields in hydrocarbon solvents,

extreme attention to experimental conditions, which vary from

compound to compound, is required.

Zakharkin and co-workers (67, 68) reported the synthesis

of a series of organomagnesium compounds without solvents and

in various hydrocarbon solvents. Their reported yields in

most cases were almost equivalent to the optimum yields in

diethyl ether. Their work is in contrast with the work of

12

Gilaari and KcCraeksn (23), which states that in ether-hydro-

carbon mixtures, the yields are about ten per cant lower

than the corresponding synthesis in ether,

Recently Glaze and Solnan (2*+) reported that when a-

amyl chloride reacts with magnesium in benzene solvent,

di-^-amylisagne siura is the species in solution.

At the tine this work was begun, there was some confus-

ion about the technique necessary for the successful synthe-

sis of organoiaagnesiuci compounds in hydrocarbon solvents

and without solvents. It was decided to repeat the work of

Bryce-aaith and Zakharkin, Thus began the study of the

synthesis of organoiaagnesium compounds without solvents; the

study of* the reaction products of these organosxagnesiina com-

pounds in hydrocarbons plus 2-butanone compared to the reaction

products of the corresponding etheral Grignard reagent plus

2-butanone5 and a prelianinary study of the nature of these

organomagnesium compounds in hydrocarbon solvents.

011&&T£M BIBLIOGRAPHY

Ashby, C, . "Proof f o r the M4gX Composition of Grignard Compounds i n Diethyl Bther# BMgX, the I n i t i a l Species Formed 111 the Reaction of EX and M*«,r Journal of tfra

2510 Cfaamieal t m v ] rime, 1955), 2<09«

"The Signif icance of Grignard Heagent Composition to the Kechanism of Addition to Ketones m ic t iona g£ Jh® l e g Aea&aamr of »>cienca«

[October, 1 W , 29-33.

3* Ashbey, B» C, and .v» ii, Becker, "Concerning the St ructure

Ashby, E, 0# end K» Head, "A Method f o r the Preparat ion of Grignard Compounds i n Hydrocarbon Solution

2JL iOJSjEflflikS. P y • XXXI (x4arch, 19t>o), 971-972*

5# Ashby, S. C» and H. B. Smith, "Concerning the -Jtructure of the Grignard Hsagent, I I , In Diethyl lit her . Halevance of Grignard Composition to the Mechanism

•370t

6* Baeyer, A, and V» V i l l i g e r , "Uebor die basischen Eigenschafton des u a u e r s t o f f s , "

, XOv(Hareh» 1 9 0 2 1 7 x ^ 1 - 1 2 ^

itilH das

?* Barbior , P . , "oynthes© du Dimethylhoptonol," *" Vdoaiagjlgfia .Maneaa do l ' i c

iaSlSttfifla, CXX\?xIlQJanuary, 1399 ; , 110^11*

6* Barre, P# and J . Hep e n t i t y , "Synthese des Derives Organoaagnesians Sans Bthsr ," Canadian Jrmrnai of Hosaarchf XX7II(August, 19*$) , 7l6«720.

9» Bla i se , E , , "Nouvelles .Reactions des Derives Or ganoraet a l i i« " " atea gftndtta SaMoaad.mi.res des Jeancas cte

iai l 3QlanceaT C3&ftfr (£iaroht 19G2), 5*1-553. ques,"

13

V*

10,

IX,

12 <

13-

/

I "vsur l©s i&rlvs* St^^««o,fgMSosia|B#si<»S|H

ft. sad u* Cox. "urgaacoa tal l ie Compound# of Group XI. Part III. tlnsolvated urganoaaagnesiua Ualidaa," JflUiaafftJL s£, .C^eisifial. MQilXICltajretii 1961) i iTWlaa. '

Brycd- oKiitJa, B# ami J* Cox, "Formation of Pre® Radicals during the Preparation of Grganoffiagnasiuja Compounds in a Hydrocarbon oolvent," Igpimi jj£ J&ft ~

• :t MCiaflilCMaroii, 19^; , io^o-io?3.

Bryes-drnitiu £• and J* O ren, "organoraotallic Compounds of Group 111 Fart XX, Alleviation of Aromatic Ilydro-carbons "by us# of I&gnaalm sad Alkyl BaXMeSf

nal of tha ^32~.

r, naiLX<August| I960):

i»©ssff &• J#f "The Constitution of tha Origmrd Edag«ntf" Joamal of fcjgganla. filMBdLalaag* XXtridaeeB!fe*r» I960) * 2260.

15# £»ss?f li» S # i B. ar*on, sacl E* &« tfftXlng«rt Constitution of th« Grignard ftoagant," tmt&mmAmn,. hsmsSLt aiCE&j, 196**), 1369-1373.

16# D#ssyf 3, and S* Handler, "The Constitution of tha Grignard Raagant." Jpttgflqfr o£ tha jfaaajglmtti doajUtyf i m C l o v e a l e r T ^ w

17# i)©3syt E*, G, iiandlar, 5# «>tiz, and C, Holllnga »ror th, I 4i# * M # amw.^4| W * * W Constitution of tha Sri,

3W-W?«

€ Itsagant*1' feari :f iJSXXCJtily# 19!

18* y©ssyf B* ii* and S» K. «5ones, wftis Conductivity, idelactric Constant, aM £#a«f»*3 of ilos© Sitjyi, jaagnesiuci Compounds," mv<Hov®nfrer# 19593.

191 i>es«y, H# .&* and K» M» Ua3,lagarf "The il-®ehanissi of the abaction of Qrignard Reagents with i-ohiff Basest*

ugust, >30-3531. i x m l x

t "Sis Sato of Beaction of Sub3titutmrhexw2m^&%mim Bromides."

* , ~ fitrwrtfl Sto&tteEt -dfxc6©pt«fe#rf 19&1J» 3^19*3^0*

15

21* das*?* iii,f <oti», issul Cf .lolliags^orttij "The E©« action of 1-AXkyaoE with ur ganoiaotallic Compounds, VI, The Kochani an of reactions of Grgaacmagn^siisa Cofiapouadsy

M Jcauaial a£. tlic XJOOXUaoaary, 1957)» 3 5 8 - 3 ^

22# G i l « a t 14# aacl It* Brown, "The Preparation of Phenyl* m&gmsXm Chlorids in the Absoaee of a i*>lv«ntf" Journal a t torn, Mariean ChflBjeal SafitefcZ* iUC4isgmstf i P T 3 3 3 0 - 3 3 3 2 *

23, Oilman, II# and a# hcCracken, "A tu<5y of th© Effect of Jesse 'MlmsAs on th© fieXcb of Orignard Jieagants,"

Xravaux & Hiw www $ XLVKJuly,

2*+» Glass, «• a . and C, k. Jelaaa, "The Preparation and Properties of Orgaro&ag&esiuxB Compounds in Benzane solvent f

n iM ¥(3«pt0Sfe#jp#

25* 0j*ign&#dt V., "Jur Is Hods *1© -Seissioa de® Combinations Organoiaagnasiennas Kixtes* Action d* l'Gxyde d*Kthyleoa9

n Biillatia de l a J a d e t a CtdBlfltta. de .Earl^u KIXCMay, 1903), 5l

25# .. t "Jur 1© Mode do Scission das Cotabinaiaorui Cfrgsa«api©si©iii»s Mixtas , CXXvrCKay, 1903)»

27,

2S.

291

30,

y, "our las Ck}i3tdn^30^ Organoma^esionnes

i»arch» 1901

Kixtas et d*AXcools ©t d*Hydrocarbur©s," Amialas de

m rnmskmt, x o t u b u , w x l , S 3 3 - W .

a leg &yttth&s$s d ^ c o o l a »t dfHyd»<»rbaf®a

&Lf 1900if 1322-132V.

auggimbaj»g«r» L. and B« Snails t "Ths 4t#uetura of Ethyl-mpi t s l t i s Sronide i)i«th«rate. to X-ray Diffract ion itudyj" ilanaaJ, fi£ "

a v u LOTWifceafflSer, 1 9 W , :

16

31. li<3S5t !#• as4 11« llhotaboldt> '"J ©bar di® roduziorend© ..Irkung des Orignard-iieagens und usbor dis iSxlsitstts von H«log#n«-ii:agas3liBi--'.*assar3toff," BarteMe? d«r

"i t Viwv&eptmbo?»

3E» Jol lbois , £•» | "uir l a jfoxsula do iteriv© 0*gflftonagn»8lum at sur l*Hyairuff» de J-agn£aiusa,:t

ISH JsSMgp M OTHiayr^lfiTr353-355*

33< , "^ur l ' lodur* de lisgTOslt® ftothylei1

liabdomadElPaa das "i1 < ,» ClYICKarch, 193.3), 712<?I»«

3**» KJmrasch, • and 0* Roirsauth, _ £yd$aiaMaa§ S#w forte, Prehtice-Hall , Inc. t

35* feaXg3*©nf <>• , "synthase*! l a dor Cajapbargrupp© n l t t a l * R a g a s a i S a g ^ e M | a | | | ^gtlefa^p^Ctoaisalian

36# Msnuk#* Ii» and 1* Ladingham, "Jom© Aaosialous Enactions of PhaagftnagnaslUB Chloride." Canadian J a m a l of. Basaarah. XXVII(March, 19W» 158-060.

37* Kois©nlioi©«irf J* and J# Caspar, "Uobar die Konatltution

1 § a^I?

38. hoi83tthdl»«i», J» and ^chlioh#msai«r, "u'eber das ^lekuItrge'iJioht und die Konstitution der Grieaardaohen. kagimsiunnrarbindungett." Bajglahta dsr _ __ fihaiBiflabftft . f i^al l ,s^a£.^yTgClp?ily 1^2H)t"720-?29»

39# Oddo, B#f "Otenarallzs&siona della fomteioa© doi Cospcsti Cj anoHQUtygaaalacl Kist l con 1® ^oatauss Osstgamt©," Sasnt ta , i M A s m * xLiOamwupy, i m i l t 2 7 3 - ^ *

l*0# Olah, G*| Halted utates Patent 3*O95t**60# 1963#

Vl# Pikard, B» ami J« Kenyan, *'Contributions to tns Otieuistry of Oxygen Compounds# I . Th© Compounds of Tertiary Fhoajpb&na Cxldes with 4cid$ sust ^alts.*1 Journal of JHut M s a l iiofilaiact upaax(x906>, 262-273 »

t-SU aiieinboldt, H. t «i-" f i f t y Years of the Grignard Heaction«"

- - IQT/IIC September, 1950),

1?

Richards, D. and K. UoXt, United atntes Patent 3,080,32*+, liarch ?, I9&3*

ochlonk, W«, "Die DarsteXXung Aethor-froier Organo-mgnesiumbaloganidc," garlfiMa. & £ &9UtSSfrgn

XXXVyApyilt X931/J 73w»i;

i+5, acWLenk, <i. and 4. SohXoakj "Uebar di« Konotitution dar Grignardschon Kagncsiumvorbindiingen," a & £ X&KftB&fia 1.XEI(April, 1929; t 920-

i*6» ^chorigin. P., <• Isaaguljanz, and A. Guseova, "Ueber Darstellung und Vorarbsitung von crganonagnesiu»-verbindungen ohne Anv/endung von Aether. II. llittoilt U«ber die Einvirkung von Hagnosiuo auf verachiadsne

Arylchloridofjga^dbta. gar^ggi^ai^n^

^/# aeborlgia. ?», ><• Isaaguljanz, A. 0u88o«/&, ¥* Oefliposra. and C* Poljakorfa? "Uaber dio DarstoIIung und Vorarbai-tung von OrganoJ^gnesiuavarbindungan ohne Anwendung von Aether. 1# Hitteili Ueber die DarstoIIung von beta-Fhenyl-aathylalkohol,"

%S4

HQ* J» and U# Crotfdson, "Th« Direct Interaction

50.

51.

52#

Gctober

-taalik, J. and 0. 2ois*r, "Beitrag zur Keontnla der organiachen Kagnaaiumvorbindungen,M qaatahaftg. fuar Ghfijgtie und fSHRrtitec.

of Kagnesiura and AlkyI , # 3 ,

a.oaiety» XCIXK1908), X82X-of tha

J# and jS» 3tokes« "Tha Diract Interaction of Ajnrl HaXidos and Magnesium," Jflmaaal .pit £&& "**

" * XCIIKI903), 6S-?2.

;>tadnikcff. G., "Ueber dsn HeaktionacKichaniaxaua boi dor &itstehung von aagnosium-organischan Verbind ungen,

XLX? [ w T W i T , nw-xie

1 9 x 3 ) ,

"Uobor die Grignardscho Beaktion,rt Praktischo Cheraie, LX3QT/III (January,

18

53 < rtZw* Prage dsr Ossatia-fsrblMms^B ;schaa Cheaiselisai ftaaallsel

Hept*Ser$ 1913>• 2W-2503* Jtf 3GLVX

5**. atueley, 5. aad a# iiundla, "strueture of jft&aoylaagpaalUBi Brooido Oiathor&te and th© *1atur# of Gj?igaard Eaagants,"

fitoaUsA LXXXV (April, 19®,1002-1003•

55» 1'eratiav. A, f # s "Debar dio Lonatitution dar garnischtea !^agnasli«aorganischan Verbindungen," ZiAi^ahsltt fnar Aap^gaaiacltg mid Mle#aaiaia. Ghogii6T afICtosptwb«rf 19aJ5»773;

56. Thorp9 !•# and 0* Lam, "4 atudy cf fcha Keehanioa of tha iirigimrd ivmction," Jotraafll of. tba. .MeiAeaa Cft«aifial Jofliety. 3Emi<*Iay# 19WV 1022-1028.

57* Tingle. J# and S* Oorsllno, "Influence of siolvanta ia to® uiaison Condensation. Catalytic Action of Sther and of Tertiary Bmm ia tills Reaction and also in the Fom&tim of t&# Orignard ftaagent."

nuarxz<Mareh« l$07),

58. Tochalinzaff, • i "Die Thaoria dor $rignard,sc&©n

m*

Roaktion und elae neua DarstsllungsEathode dar Magna siutiorganisolien Verbindungen," Hsglehta 4ef

x3aynili©v«in»*t

"Uaber dia Umwaniloluns individuailar n oi ffi&gfe®si»lf,fMase^lsl, Varbindungan in ClrigimM'

Sasyeracho OaconiiMbasan und die tharmochaniache Unterauohung disser E^rnktiofi." Berlohta dar f

3e&allachaftT XXTVIlTtUotober. 19^/ , 366¥-W3. •

60. Vreugdanbil, A. aad C. Biotabare, MTha Constitution of tt» §fiiaaM ftac$entv" gam#il dog XMraam Ci <&a* wa6o»v, ASMsSKfa& ap,

LXXXXX (Kay, 1953)7*5 61,

o «i

Mf!is Constitution of the Grigoard Reagent, Part Ia," B®eaitli den fmvmx ChiaiQiifta. doa UafiaSASL*

. .. t "file Constitution of the Grigaard ftoacant III , Conductlvity cf mm iSthylsuBgnasim:} Compounds," Xlgeiifil ftci .^ggm:

" " des Fays-Baa. , »iim.

19

63.

<$ejg

"Constitution of the W Itecuall daa

f M^w^T^aouajpyi X955}f 39«

6**. 4«gn«*. Or# and A* asytssf f , u£»ynth*se dee X&aot&yl* carbinols, dins n«u«n Igoaeren das Aayl&lkohols," Mtmiafi d i r Jliffifcaa Laibiga f CLXXVC October, 1S75), 351-371^

65» <«eisa, iS«t u'J«ber &i© Konsti tut ion niahtsoXvatisiertar

apignara»Vt3r*jindune®n»rt ^bemiaohe Berichte. XCVIIX (i£®pt&Bber> 1965) i 28o5-tE2I7 " —

66* <oti2« J . , C# Holl ings^orth, and 1. Dsssy, "The Is** action of l~Alkyn«s v i t h Organoaetallic Compounds. V. Xha Hsaction of Diathylmgnasiuiei «Ath Haxyne~l i n th« Prossnc# of Jt&ga#sii» Broe&de.* lotamai of M l l M l l l l t XXX(October, 1956), 106>106SV

67* iaktoarkin, l . , , o, Okiilobystin. aM B» Jtrunin, "Appl i -cations of 0rg®aosa|n#sl'ti8i Compounds fo r tha dyntheses of Grganie itorivatives of Group II~V Slomants i n a 3o&Mfrth*ittl Akadamila ilank tfStM. a£ & &

sagaeaima (iompounds from Kagnesiuu i n Hydrocarbon Kedia»n ^ 1962), 631-633.

"Or,

L, XXVUuly,

CHAPItfii 21

acraiiiiviiifAL vmcmm

Materials?

Three kinda of magnesium are used in tills study* an

unspecified lot of coarse mapi#si» turnings described m

Grignard-grad© from Fisher scientific Company, an unspeci-

fied lot of ?0 to 80 meah sAga#sia» ponder from *lsh»r

Scientific Coiapany, « M an unspecified lot of purified 150

neeh magnesium powder from Baker and Company*

She benzene and hexana solvents are Phillips Pure Grade

hydrocarbons* Beth hydrocarbons vare dried by distillation

froa lithium altatiim hydride onto &ol«eular sieve* The

diethyl ether purchased froia ilsher scientific Coapany, is

refluxed for twenty-four hours in contact with lithium

aluaimaa hydride and then distilled into a dry flask pro-

tected from moisture by calcium hydride*

The alkyl and aryl halides are purchased fmm gaatsan.

Chemical Coapany* The organic halides are analysed by gas

chromatography and used without further purification if they

are found to be at least 99 per cent pure. Those halides

of lower purity are distilled $mt prior to uae.

20

21

r repara t ion and Analysis of u ther- f raa Organaoagnasium Goa&omds

fha solvantless erganemagnasiua compounds are prepared

in e i ther one quarter or one half xaole quanti ty, A tfir#$

nack, on© 11 to, round-bottom f l a sk equipped with 2M*Q

standard tapor ground Joints i s us©d. The f lask i s equipped

tflth a Hirschbarg nichrome wirs s t i r r o r i n m Asco t e f lon

s t i r eland with a ll#opr#ae o-r ing s ea l , with a 150 m i l l i t a r

dropping funnal with a pressure equalizing l i n e , and with a

condenser connectad to a nitrogen manifold rfhich maintains

about two eantimatcrs of mercury pressure on the system,

f.t» Condensar wmt«? i s chi l led with cruahdd ioe* A Glascol

heating uiantlo controlled by a rheostat i s uaad to hsat th«

flask*

The glassware i s cashed, dried ovornight a t 125 d#gr«es

centigrade, assembled while hot , and cooled under a atreaza

of dry nitrogen* m amount of ©agneslue equ&aolar to the

organic halide plus a tsn weight pm cent excess i s placed

in the f l a s k . The f l a sk Is heated to about 150 dogrs»a

cantigrade. aomotixaea a t t h i s point a small c rys ta l of

iodina i s added, She organic halide 1© added dropwise to

tH© f l a sk in such a way that i t f a l l s onto the aagneftiua

ra ther than the hot *a l l s of the f l a s k . For tha higher

&Xkyl halidoa the reaction i s vary sxothymic t and soii«tiffl#g

the f l a sk must be cool ad with an a i r Jet* >*hen most of the

organic halid* has b#an added, tho contanta of tha f laak

22

fons a thick mud-lika mixture, fh# stirring rata is in-

eveasod from the initial 30 revolutions par raiaute. The

dropping funnel which contained tho organic halide is re-

sieved a&3, quickly r«plac®d *dth another *hich ©omtaiias

tba Hydrocarbon solvent* a tiigh nitrogen flov is s&alntain*d

during tfo» switch to prevent air fron cooing into contact

with, the orgai»afi»sii«i coi&pound# fiis hydrocarbon is

s M to tho flasfc wA allowed to reflux for about two hours*

fbaa tiis dropping funnel </hich contained th* hydrocarbon is

quiclcly replaced with & m «hich contains a quantity of 2-

tetsBoa©t squimolar to th© organic halido, dissolved in

talcs its volura# of hydrocarbon* The 2-butanon* solution is

addad droprfiae tc the flask at such a rat# so m to maintain

a g«ntle reflux, Usually th« ilmk is cooled vith an air jot*

After all th# solution lias baan addod, the flask la heatad

to maintain geatlo reflux for two tours* The reaction ctoa-

plm is hydrolyssad by ©itb&r pouring th« contents of the

flask ovor acidified crushed ice or by carefully adding to

tha tlmk of 2.5 nomal hydrogen chloride in anhydrous athanol

equimolar to th© nagneaium proaent.

Ihe hydrolyzad product is colls»ct#d and analyzed by gas

chromatography. "III© g&s chroraatograph is on Aerograph

A-350B. t m packed cclissns are mod for analysis t Apieaon

L and #L(ii Carbovfax* The conditions for analysis vary for tts©

different confounds, Authentic «ajaplas of tho tertiary alco-

hols oxp^ctod as products are made from the corrasponding

23

ethereal Grignard reagent and 2-butanon©. standard solu-

tions of the purified alchols a m made ia hydrocarbon

solvents* A series of standard dilutions is used to con-

struct graphs shoeing the concentration of the alcohol

versus the response of the gas chroiaatograph, i-rhich are used

to detenaine tho molarity of the alcohol in the reaction

product. Fro® the iaolarity and tho total volume, the moles

of alcohol are calculated* From the moles of the alcohol

and the Doles of al&yl halide used* the yield ia calculated*

In trfo cases datermination of the yield of ether-free

organoiaagnesium compounds is made by means other than re-

action *rlth 2-butanone« "n-nexylaa^tteaium bromide" and

" phenylsaagnesium bromide" wore analyzed by hy&rolyzing the

organometallic compound a&th acidified ice and determining

by gas chromatography the aaount of hexane and benaene

liberated. Here the quotation marks are used to designate

the reaction product of the corresponding organic halide and

magnosiun in the absence of a solvent | the t&m inside the

quotation marks does not indicate the actual structure of the

species*

Preparation and Analysis of Ethoreal Grignard Reagents

The am® equipment as described in Preparation and

Analysis of i£ther«froe Organoaagnesium Compounds is used for

the preparation of ethereal Grignard reagents* A quantity of

coarse nagneslun turnings, equimolar with respect to the

organic halide plus ten weight per cent excess , is placed in

2%

the flask and covered with $00 milliters ,cf diethyl ether

freshly distilled fro© litliiua alisalnun bydrlda* without

stirring^ a small crystal of iodine and ten to twenty drops

of the organic halide ore added to tha ether in the flask.

Reaction usually begins within a f m ainutas. In some oases

the fla$k is heated so that th* ather gently refluxes until

the reaction basins* The stirrer is turned on, and tho

solution of organic h&lido in twic* its voltaae of athar is

addod |mst fast enough to maintain gentle reflux of th»

®thsr. After all th$ organic haUde is addod, th® reaction

sslxture is refluxed for tm hours. The dropping funnol is

replaced with a m which contains 2«butanona dissolved in

twice its volume of «thsr. The solution is added to the

flask drop>«i30. The flask is cooled with an air j@t* Tim

laixturo Is r«flux*d for tm hours after the addition of all

the k-butaoono solution*

flis reaction mixture is hydrolyzed by the addition of

2.5 normal hydrogon chloride in anhydrous ethanol* A saapl«

of the. hydrolysed product is analysed by gas chromatography,

Th© bulk of the athsr solvent la reeovad froa tha product

mixtura under vaouunk. Tha product is slowly diatilled through

a six inch colussn packed with glass helices* The fraction

within two d&gtms centigrade of the boiling point of tha

tertiary alcohol is redistilled through a spinning band

coluan with a tan to ono reflux to takeoff ratio. Tha purity

of the distilled product is greatsr than 96*5 cent.

25

Tho tertiary alcohols are identified by their boiling points,

indices of refraction, sad infrared spectra. (1, 5, 6)

Cryoscopic Molccular height studies

A theraoplle is made according to the specifications

of Glover and Stanley (2, 3 ) . A telegraph key, a 15*000

volt noon transformer, and two load pencils are used to

m M the junctions. A water and ice aixture is used as the

reference point. The sample half of the theraopile is passed

through, a rubber stopper into a benzene solution of "ethyl-

j agnosiun bromide" or "ethylsagnesiuBi iodide" contained in

a twelve inch test tube. The o3p$mmmgnm%vm product formed

by the reaction of methyl iodide, ethyl bromide or iodid© and

m&gnesiun, which has been in contact ith refluxing benzene

for at least two hours, is taken into a dry box and filtered

through a medivsa porosity sintered glass frit. The filtrate

is placed in a twelve inch test tube with the sample side of

the ther&opile submerged in the liquid. The test tube is

removed from the dry box and placed into a Dewar flask con-

taining crushed ica and tfater. The reference side of the

thermopile is placed into a water and ice slxtur®. The test

tube is shaken by hand. The voltage output of the thernopile

is recorded on a 10 millivolt recorder. The test tube is

cleaned, filled «ith pure, dry benaene, and the procedure is

repeated. By knowing the concentration of the organoaagne slum

compound in solution, tho difference between the freezing

point of the pure solvont and the freezing point of the 3olu-

'6

tion, tli© jnolal freezing point constant of the solvent,

and by assuming that the densities of the pure solvent

and the solution are the sane, on© can calculate the

apparent Kolecular weight of the species in solution.

Infrared Absorption utudiea

Infrared absorption mmm mm obtained on filtered ben-

zene solutions of tha organomagno siura compounds made from

©ethyl iodide, ethyl iodide, and ethyl bromide# The spectra

froia t*o to sixteen raicrons are obtained on a Perkin-Elrser

©od*I 237 infrared spectrophotometer, and the spectra from

fifteen to thirty-five aicrona are obtained on a Parkin-

Slxaer aodel 21 infrared spectrophotometer equipped with

cesium bromide optics. The aolutions are loaded inside a

dry box into a one millimeter path length cell *ith cesium

brooide v.rindov/s» oamplea of each solution are checked for

the presence of the Grignard-type compound by the raethod of

Oilman (**)•

CHAPIiuR BIBLIOGRAPHY

2,

6,

Church, J., f* Vhitmore, and H. McGrev/, "The 0aonoly3i3 of Purely Aliphatic Olefins. The Behavior of the Five Simplest Normal Alkyl Radicals in the Dehydration of Tertiary Alcohols," Journal of the Amsrlean Chemi-cal jocletyf LVI(January, 193*+)» 17o-18m^

Glover, C. and H» Stanley, "Construction of Thermopiles from fine ^ire," Analytical Cheaistry, XXX(March, 1961), *•77-W*

"Ebulliometric Apparatus for ar-Average Molecular Weights of Polymers

, XXX(Karch, 1961), W/-%50*

Gilman, H. and ?• achultz, "A Qualitative Color Test for the Grignard Reagent," Journal of the American Chemical Society, JLVIXtftOy, 1 9 2 5 7 7 ^ - ^ ^ ^ ^ ^ »

Howard, F», T* Kears, A. Fookson, P» Poaerantz, and D. Brooks* "Preparation and Physical Properties of Several Aliphatic Hydrocarbons and Intermediates," Journal j

(March,IwTT36?-39r

*hitoore. E«, and 0# Badertscher, "The yields of some Aliphatic Tertiary Grignard Keagants aad the Limits of their Usefulness as Synthetic Koagants," Journal ~ ^aacisfla m m M A m m x » mApril, 1933),

'V7

CKilPT^ 111

RESULTS M'Q CGHGLUBIGHS

As mentioned in Chapter I, in spit© of a largo number

of reports in the area of the synthesis of organomagnesium

compounds in the absence of solvents and in hydrocarbon

solvents, there is much conflicting and ambiguous data in

the literature. The problem »rt.th which this investigation

is concerned Is the synthesis of organomagnesium compounds

without solvents, the study of the reaction products of

these organomagnesium compounds in hydrocarbons plus 2-

butanone compared to the reaction products of the correspond-

ing ethereal drignsrd reagent plus 2-butanone, and a pre-

liminary study of the nature of these organomagnesium compounds

in hydrocarbon solvents.

Tab]e 1 contains a summary of the data from the syntheses

of several organomagnesium compounds in the absence of sol-

vents and the yield of their addition product rfith 2-butanone.

Organomagnesium compounds can be made in the absence of sol-

vents and in some cases can be made in high yields. Bryce-

amith's comment (1) that good yields require extreme attention

to experimental details, vrtiich vary from compound to compound,

is true. There is considerable scatter with the data of the

iodomethane, iodoethane, and bromosthane. Apparently the

more volatile organic halides are easily lost.

o.Q

29

X

cmmtimu of u? mm-tmm ommtMAmmiw amvwm ma mam OF timn wtmm

pmmm 'dim 2-MTmmu •

ffpe of Iodine

lime tm PeiTtSsSF Addition I'taM of of HaliS© Addition

Iodoethazxo f

l-Broaopropane 2*Brooopropane 1-Iodobutaria l-2o4oltttistt® I-»Iodobtttaus l~Br©»obtttane l~Chlorobutane 1-Bro3op©ntan<a l'BrcasojpeataiM 1-Brwaohexwus

b b c b JL

yc

yes y«s yes no

1.0

o.?5 .75 1.5 2.G 2,0 1.5 i *? A* 7 2.0 2*0 1.5 1*5 1.5

itstor i»ci@atifio Company ?0-b0 mosk B&gMsltta powder* 3aker purified 150 mash rsagnsaluia po«?d#r. Mistier Jeieatifie Company urign&rd tirade taagtwaluft Xao flask tout oool to touch during th« haliiSa addition, 'flmk lieateii to dryness aftsr halida addition befor®

•#m add&d. OrgonoBagaoslUB product is spontaneously flan&ac&le in air. *lask oooldd and baasene added as soon as last of fcalide

# «

1# 0 1.0 1.0 1.0 .75

JLhU.

c i

&

t g

fat 30-50$ of alkyl halida found aa tlM coupling product b w i t t

i JSmtteimle reaction* 4 Vary exothermic reaction. k Xleld detanained by hydrolysis and analysis of liberated

hydrocarbon*

30

Koglecting the two rims dlth iadooothane In which the

halida 4as added to a cool flask and tho t*o runs ./ith

iodoethane in ./hioh the flask -4m baked to dryness bafor*

tho addition of the hydrocarbon solvent, the yields of the

addition production of 2-butanone *ith tho tm halides arc

65 and 79 per cent, respectively, Tho yields of th» 1-

bromopropane derivative are unique* The presence of largo

amounts of coupling product in this particular reaction and

not in the reaction products of the other alkyl halides ha3

no ready explanation. The only secondary alkyl halide used

in this study, 2-bromoiropane, fonaed a product */hose yield

is much lower than that of the corresponding 1-broinopropane

product, a result supported by tho data of Bryce-Sn&th and

Cos (1), For tho only data reported by Sakh&rkin and co-

workers (5) which is directly comparable to data from this

study, the data describing the yields of the crgaaoaag-

aaslun compounds derived from the 1-iodo-, 1-broao-, and

l-chlorobutanea, the Russian tfork reports yields j/hich

average 6»5 per cent higher than the yields found in this

work. The paper by £akharkin audi co-workers does not state

how the yields of the organomagnesium coapounds ware deter-

mined.

Data in Table I demonstrate that for the l-haloalkanes

above C3, the yield becomes higher as tho organic group be-

becomas larger. The addition of iodine to the magnesium matal

before the addition of the organic halide has a snail but

31

positive effect upon the yield of til© organometallic com-

pound. la the only case whaa an aryl halide was used,

brojaobafissn©, the reaction conditions wer© more sever©

than those used for the alkyl halidea.

In soma cases soma of the or ganomagnesium compounds

splashed high on the walls of the flask where it was un-

available for reaction with the 2-butanone. Higher yields

could be gotten if a hydrocarbon solvent is added early in

the reaction or if xaost of the organic halide is added as

a hydrocarbon solution.

In most case3 the reaction product of the organo-

magnesiusa expound and 2-butanone was liberated with 2.5

normal hydrogen chloride in anhydrous ethanol. The reasons

for using this rather exotic method are, one, the product,

a tertiary alcohol, is fairly soluble in water; two, a gel

or two liquid phases result vihsn aqueous hydrochloric acid

is used.

Table II contains a comparison of yields of organo-

magnesium • compounds prepared in ether andprepared without

solvents. The yields of the organomagnesium compounds pre-

pared in ether in this study compare favorably with the

corresponding yields reported in the literature {3 ) . The

yields in the literature were determined by acid titration,

a method which always gives high results, according to

Oilman (2). The solventless or ganomagnesiuci compounds can

32

only "be directly compared to tho literature report In the

cases of til© 1-iodo-, l-bromo-f and tho 1-chlorebutane

derivatives as mentioned earlier#

Tho preparation of the Grignard reagants in other is

straightforward. No problems mr& encountered oxcopt for

two unreported roactions in Jhlch tho contents of the flask

boiled out through tha condenser because too much organic

halide had boon added to the flask in attanptlng to start

the reaction#

The molecular weight determinations of three different

preparations of each of the organomagnesiura derivatives of

icdomethano, lodoethane, and broraoathane m m all inconclusive.

In each case although the bonseno solution of tho organomag-

nesiuia compound gave a positive color test for tha presence

of a Grignard-typ« compound, only a single drop of 0.35 nor-

mal hydrochloric acid ./as necessary to titrate five alllitors

of the bonsens solution to a phenolphthaloin Indicator and

point, indicating that tho concentration of the orgataossg-

nesium coQpotmd in the bonaene was less than 0,006 ncraal.

Cryoscopically, no differences could be discerned bot«/ean tho

benaan® solutions and the puro bsnsono within experimental

error. In oach case the precipitate regaining froia the

filtration of tho bensono solution of the or ganomgns slun

m s stirred with frashly distilled diothyl other for two hours

and then tested for tho prosonce of Grlgnard-typo compounds*

33

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3V

In aach case the Qilman color test *ras positive; hovover»

two drops or less of 0.35 normal hydrochloric acid was re-

quired to titrate five milliters of the othar solution to a

phenolphthalQin and point#

Infrared spactra m m obtained on portions of each of

the solutions uaad for the cryo3copic nolecular weight stud-

ies in an attempt to find the characteristic C-Mg~C absorp-

tion. iicans vera got on both tho other and the benzene

solutions. The solutions ./ore so dilute that no meaningful

conclusions could be drawn about the species in solution.

To recapitulate, organomagneaiuni compounds can ba made

in tho absoncs of solvents in yiolds v/hich, in ths case3 of

tho higher alkyl primary halidss, approach tho yiolds of the

corresponding Grignard raagenta. Tho crganoaagnosiun com-

pounds isada froffi alkyl halides higher than propyl and oryl

halides show appreciable solubility in hydrocarbons. The

methyl and ethyl halide derivatives are practically insol-

uble. Thaso organonagnesiuia compounds hav® chonical properties

siiailer to thosa of the corresponding Grignard reagents.

CHJUPTIFIR BIBLIOGRAPHY

Bryce-*$mith, D. and G, Cox, "Or ganome tallic Compounds of Group II, i art III, Imsolvatad 0rganomagneslum Halides," isaml fi£ MGHXJOt (Karch, 1961)7^1175-1182.

2. Gilman. H« and F. chultz. "A Qualitative Color feat for the Grlgnard Reagent," Journal at MM Chemical society. XIVII(July, 192?), 2002-200!

3* Kharasch. M* 3. and 0. Beinmuth, Or!guard Raaatioag. Si Monmetallic oubstances. Hew York, Prentice-Hall Inc., 1951**

iest, E. and Glaze, "The Infrared Spectra of Alkyl-lithium Compounds." foiiroal., oL tM. imxiMtL Ghaalfial

IXXXIICSeptember| 1961), 3560-

5* 2akharkin, L., 0# Olshlobystin, and B, Jtrunin, "Grgano-magna sluia Compounds from Kagnesium and Alkyi Bolides in Hydrocarbon Media," tetrahedron. L,ett.#i?.s« XIV(July, 1962), 631-633•

35

Bimioamm

Books

Kharasch, K* and 0, Koinrauth, fix,lfl,nfl,r.3 Haaotioaa ina-—'~-\f Uev York, Prentic^-nall, Inc*,

Articles

Ashby, B. C, uompoua' Foraad ia the Reaction of HX and Kg,"

,1 LXXXHXCJune

w * # *

, fiL >, 2 W «

,, "Tha .Significance* of Orignard Roagont osition to the M&chanism of Addition to Ketonea,"

of the Sew York Ae^dQav of etofeern 196M-) , 29-33*

Aslifey* S* C» aod K# Becker, "Concerning tte ^>tructur« of tM^Qrigasg^Beageat$" Jogga^!

Aahby, &* C, and E, lleadf "A Kathod for th« Preparation of Grii of.

i v# •**# *** x v* w ? & wj/iau »nard Compounds In Hydrocarbon solution,n

xxXE<Ha*eht 1966), 9?I< .972*

A3hby, E. C# tad M# B. Srnitii, "Concerning the Structure of tlm Grlgnard Haagent XX, la Methyl Sthar. RoXcrvanc® of Grlgnard Composition to the Mechanism of Addition to Ketones*" Joiieaal of .tha. AaagJ UOOff I(October,

Bs®y©rf A# and. V, Vllliger* "Uebar die basiscUen Kigeaschaftcn das aaueratoff8," Barlohta der Beataetea Chi

xfe (Harch, 1902} , 1201-12i;C

B&rbier P

HciyntU«j3c d . dimthylhaptonol." tl&a gaaaeaf. c|a. l,.f.^cM%lQ.

anuary, 1899)» XXO-111»

Barro, P# and J* Itapontlgny, "tfyntheaa das Peri-Yes Organo-m m m s U m Mns Zth&rt

tt Q m e M m I W w 44WMW| yjjftaL X5C/XX (August, 19^9)9 71^720,

36

3?

Blaisa, S* , liouvalloa H«actiona des derives Grgaaamotalli-quaat," Coastes gaqdas. &L 1*

das MglgfifiM* CXXXIV(March, 1902), 55X-f?3• 'Tiwfliip riT«nVti.WPre WO WBP( rJW.'i 'I W!Jp W T

, M*5ttr las Dorivea £theroM3rganomagn«sians vn

3ryc«j~Jinith, &» and C-» Cox, ,fi;rganoaataXlic Compounds of Group XX | . art 1X1, Uasolmt^d orgaaor4sgaositsi

tharch, 19 175-US2 KC&LXI

Bryce-uir&th, •£* and J» Cox, "Fomation of Fre© iiadicala during th# Preparation of Organojaagnosiiua Compounds la a Hydrocarbon iJolvent," Jammal s£ tha Chanleal .'joel ia liaiLfXXXCHarc s 1958) i 1G 50-1053.

Brycs#-4iEith, D« and J# Qmn,f "OrganoaotaXlic Compound® of Urou|/ AXf Part IX, Alkyl&tlon of Aromatic Hydrocarbon

tli® by Use of Magnaslum and Alkyl Halidaa," _ _ _ _ a«Mfia.iSS4ste» mmmmt, 19m, 35I$=553».

Church, J«| F. dhXi&om* and ft* &«Cfara»f "Th« Gsonolysls of Puraly Aliphatic Cu«fina. The S trnfioi? of th« Iflve iilsplsat fiformal Alkyl Radicals la the Rehydration of tertiary Alcohols,

1VX(January

GXo¥«rf C# and II# Stanley, "Construction of rharsiopilos fmm fins 'iirf,ft Aiaaatlcal Chm±stmt ZX&CHaroti, 1961), U77" 76«

t niibulllc*aetric Apparatus for

studying tfuabor-Average Molecular heights of Poly&ers," .^mlg^eal g.heMstryt "?XiCK&rchy 1961), '&7->+50.

Sassy| 2U S*9 "file Constitution of the Grignard iteafcent," *£ iTyqnln SbaalfiJLcXf s?Ci>#c»b©rf i960), 226a,

i^say* ii« E#i a» E, Qraan, and &» id. ialingsr, »the Constltu-tioa of the Grignard Zioagont," ffatoflfraflrgR teMiffii XXX (Kay, 196»f) s 1369-1373.

Qm&jm !• I*. and G. ;>* Handler, "The Constitution of tha Orls£iArd Heagaat*" Journal of the itesriean Chaalaal

fcC'lOTosIm?,

3&

-Pisasfi 1* j>». S» Handler, J* .©tia, and €# Hollioga* worth, "Thft Constitution of the Srignard Heagorit,"

tha .Aaaegieaa Chemical , 3 W ^ ? .

IJXSX '

Jtessy* lt» E* and li* E* Jones, "Tha Conductivity. Llslactrlc woiistaatf • &M S*st•f«,s of i«ae lithyteaga^siiia C^sanouniis," &&&3$Lnfi£ £teiai£tCK* ^a¥CloWi»fers 1959) t

U* E* and H# K» ^oling9?v wTh® ic#eiaai$s of the &©•

action of tiripmrd Ikmgmts with ichlff Bases," •fomTifil ja£ j&fi ._ .. (August| 1961), 3&0-3&1.

Jtvf ^ «$». -a®*

'The Sate of Reaction of

£ 3

itessy, H» E«, J* ^otia, aa3 C, HolJ&igstfc>jrth» "The MmtUm of l-AXKynes vith Organom<atallic Cocpounda, VI. The li©eliaui« of Eaa&ticns of" Orfaaomagnesit® CoEfoyaisf

tt

January t i1 **3

Oilman, II* and E« Brovnx, r,Tho Preparation of Phonylzaagneaium Chloride in tba Ato&nea of -&3Xif#iits;,n Jaiignal of the J n u f t u u £fegala& m m s : * m u x m l t r w W ; 3330-3332*

v i tam, H« and EcCr&eb&n, "A iStu&y of tfoa &fT»ot of ^eee •solvents 011 the tl&Ms of arignard lieagents," Ileeaall Mm $gasum SMMsmm i s a ftnHBftftt ^ v i u m y , 1927) ,

Olliaan, II. ami l?» >chults, "A Qualitative Color Test for thv Grignard ll@flg©&tt

B Journal of tha Asiarteafi Chez * " - rf XLVII<July# 1925), 2002^2005.

.** and C. a#Jsaas, "f!i^ Preparation sod ^fop^rtiss of orgaoat^naslutt Compounds in Seasons ^elvont," Jougai" pr •y.ggam.ag.taHle.. V(&»pte&ft9r, 19&6)7wf-400,

Gyignardi^V*! Is isod* 4$ --ciosion do 3 Cambism!sons Organo-aamesi annas Mixtes* Action de loxy d© g'&thylanftt'1

. da 1& a a s i a ^ £bteism to '-aria, XXIXtMay, 1903}, |jp 4- n

39

i f H;>ur Is Koda do aeistioa dos Cosbinaisons

14i t©sfM Co no tea fffidM il

Msmm M * ****&<*«*•* ** mwTim)i >-1262,

Xlrte'iL^ foflantas ur les Comblnaisons orga»\ossagnaaioaaoa

1901)7 » ndm 1m Ccaabinaisona o gai»magB®si#aa«@

Kixtas at leur Application a des 3y&tSb*9* decides, d^Alcool-s et d*Kydrocarburas," .Q&ftJU &1 &£.

XXIV (July, 1901), ^33-W.

,i "aur quelaues nouvallas Conbinaisons 'ues du I'iagaasiHB et l©ur Application a

das Jynth^soa d'Aleools ot^Kyarocarburtts," " ISS <&*/ i s#sTr^^«i3£C'

anggeab^fgafi L« and a# Hmto, Mtha atructurd of thyXoagnofiiuiB BrostM© jatstiisrat©* An &»ray DlffmetioB. atiidy,' Jmirp"1

. aoftjaty. LlSCflCOaeeeMi?^ 19fc*<v,

II@s® $ I» and H* lii®iiiboMt, "Uober die r*du2ier<mdtf *irkung S@s Gpiipaiufd-lleageas und ueber die &x±st&nz von Halogaa-Kagaasitaa-Jjasaarstoff," JBagiflhta. 1 J „;l ftaaallaahaft* llVCSeptasbor, 1921)7 26%3»20*

Howard. F»; f* I-lears* A, Sfcokaoa, P. F©te@raatsf and !>• Brooks, "Preparation and Physical Proportiea of «>©voral Alipfcatic M^droeafbeiis and Interra«diat«s~ " " *

Hmsm sL LXTtfarch» 19W

Jolibois, ? # l "our la fonsnla du. itorlva organoHcmgnssiuts ©t sur l*Hydure de UagnasiuR." jfraaafcafi randaa HghflamadfliJEi daa -^ajiftea M IMyMdftil* dag » 353-35%

our I'lodure de Magaesiasi Kstfcsylej *4 msmr Aam A**£un{*<a$t Hla 1 t AtiAAftr

-Tl'CIIai S, 1913)7 f das

Halmgfes, .*•, -tf "uynthos<m in dor Caiaphor grappa gdttails tiam^pimpalvei?®," fltorlflhta jBeixtaafoaa 0 aaaallaehaft, JvXIiYIC July, 1903), ? ^ b - 2 f c .

MiiiisSlMt a# and A* L^di8gha»t sik»8 ^noisalous Be&etio&fs of

Pharfflsagfiosios Chlorida," £y xml&areh, 19^) 1 15*3-160.

heisenhsimer* a M J# Caspar. "Uebap die HonstltutIon dor - • • * - - - - i»« 3 m m m m

ilVuSe. 1923 ? #iu!& i62p«»JU&02#

R®ls«aheia«jp| J* and ^ehXloheimetie^* ''Uebor 4ms tioXslculaegs* *rt.cht uad die Konstitutlon d«r Orignardachon Kagnaalust*

garlgkla Aac. iteataftfrsa SmsHS,-U2( April, 1$2S), 7£0~729»

wddo, S#s "Gcjiioralizaazlona della Foraaslon® dal Coapoeti 0ri«»-«&fri©8i&ai Kistl con lo So stanza &ssig@i»ta

gotta Cblalo Italians, 3U.I(«Taauary, 19115* 273-29*+!

Plkard, lit, and J* F.onyon, "Contributions to tli« Chemistry of Oxygen Compounds, 1# Tho C&&$ouftda of tartlary phosc*' oxides with Acids sad ^aXts«tt

~~4 ~**rf LXXXIX(1906)| 262-273".

the ttrti. ,1 30Sf"flC- pti>Bb®ll,|

t

•, Dia ©arat^Xlmg asttisr-ffsisr OrgaHo^agnasiuEa* Uil>id9 * '* w _____ \t iWi(April* 1931)7 739-7^

ll # w? c'olonk* "Labor &I® Constitution ds»r B@rie&t$ dor ifcttits*

Je!»rlgiS| F., .»• Xssagttljfins* and A« Gi»sr«rs# "Uaber • 9 SI ^ ««£&& | id Y&ra?b$lti

duogaa olms Anvenduag von Aether, II# Kitteili Uatakr die Blwrfirkung von Mapiaslw auf Alicyl-

^ Bagit^ta^dgg Daut^hgy-h *

f ?*i *. Isis,guljaiigf A« Guasawtt, V# 08slpoway and €• i oljekowa, °U«ber die itors tel lung undi Vai

A»th«rt 1* Mittailt Uabor dia Daratellung von

2p>"#*2- 590 LOT (October, 193'X

,«tlAi£f J# and C* "Beitrag Kur lleaatais der ojrganlsehea

'DecsBbar,

h i

%«aeerf *?• and M* Uro^dsan, rt£h« Direct Interaction of Kagnosiun «sA M$KY%- Halides/' SMMMA fi£ iilM

r, ACIIX(190e), 1821-1826#

wpeneaffj J . and &» £tolsfts, "Tho Direct Interaction of " las told Kagmsltfou II

JDDIlia90S)f 6B*

"Uebor die Gringnardscho ftaaktion." tibMii LaXSVXXX(January, 1933)* l-«20«

"Uobar a©n Iteaktion^ochiuaisBms Mi dor

^tadnlteofXt 0# Xtt£& &E&

11-Stir Fmge ier i>»riit®.-faj,biMima'aa

f «M SXVI C&sp teiaber»

istuekf. «. and S. Handle, "iitructura of plwayliaafaesiwi mM@ jJiath&rate and to Katoro of SrlgaaM a e s | « i t 3 | ' t

I s p M i J&& a i2fi£lsS2f IJDSt {April* I963)t 1002-1003.

1'orantisv, A» } *Ueb©r ilia Ilesstitutioa dsr gealsohton isagass-| m * * W f P w %&**»<'$ v* vU

i\aoorganiseh®n Ycrbiixdungon." und CLVX<&Qpt«c&be*, 1926

fliorpi !•* ibk! o» E«®if "A £tu£y of the Keobanisa of the Gri gourd f a c t i o n , " j £ ^ p l a£ JM i f i l l i s t e sxmimm* I91mTT1022-1028,

Tingle, #* aad JS* Ocrsliny. "Xnfluatice of Solvents in Claiaen Condensation, Catalytic Action of Ethar and of 'Jtertiary Bases X n this Ba«ctlonf and Also in the formation of the Grignard ftaageat (Kwoh. 1907)* **

m f l l

Tschalinz*ff, •4*, ni>i© Thaoria der a^ipiai»dtsolieii Heaction xmd oia# n«tio jJarGtallungsnetUoda dor sagaasimorgaaisetea Vd*M2i$ fthaf't;. f i l c i ovenber.

., "Ueber di« "UGwandolung individueller aagaaa** Verbindung in Grignard-Baeyerscho Oxcnium-

baaan~und uia thewcoeharaisch© tmt©rsuc&ung diosor llaaciioa," dor

sb©rt i905)V 36< m v x x x

f ftfef

Vraugdenhll| A* sac! €« Biomborg, "itie Coaatltutloa of Urlgnard l®ag#sts

tt fiamatl dag Tr-— '*»-*-* LJC^I 1%3 )7M3-

&*a$en€f . « ntlm Cagatltut&oa of tie

ST, ParTflT1 ^ (i LJijCxi X ( ayJ X§o3/ > *+0x +63•

^ .. ^ « "Xho Constitution a£ tha C»rigiMur& Seagont, XIX* cShductlvity of ttthyl* nagttesiia CoaponiadSj|tt *'" " — -

* Hfiis Ceastittttloii of tti© WT« Kseuall das Iravaux

S?>pTf 39"^ •

*agnerf 0» «n& A* i&yt&Bff* "iiyntiwao des t eios neu«a Iaoiaeren dee A&ylalkohola ," "" "

«#•>£# "Uebor die Konstltution nicbtsolvatiaioptor ti r

( eptt&ibur, if65) t 2805~VJ13<

K« aad 4* Gla£o» "fli© Infrared upectra of Alkyllithiua

i ^ 3 ^ f ! . a s B i s a l i ^ £ l

Wbitaor * A aad B» ftadartsahor, ttTim Xi«ids of ass© J4if>tmtie Tertiary Qrignard Beagests mi. tho .Limits of thair lis®-

. * 1 *« . »» * » « » ' O ^ «,. . A * - t »ft f _. J* A- f t* . , * ^ ruioi»00 as yntlietio ftefiggntft-" Steaisii wc April 1 XXSJM*

.AjSari-eyi

•soil a 1 J# 1 0* Holllngo ortti, aM H« 3# 3essyt "tbs abaction of l*i&Jkys&a yitk OrgauoiastaXiic CoapotMiSs# v, 2h# Boactlon of othylznagzioslUEi \jtth Heayno-1 la tho Pr&s«2K5© of iifegrwatura Bromide*" Journal uf »)giygale £tastaftX» m(October, 1956)» l35J38?k» '

aaJshar'kiiii L« , o« Oldilobystia* and B* atnaula* "Applications of O gftoonagooalum Compounds for tiie tfynthosls of Grganit itorivatlves of Group XX-V Slyemats is % Kon-otharoal Kediunf" k tfsaa

^ **%

3-1919

r ... m ft0jTg@IIO» a«slu» Coapouads from Iimgss@st4* and Alkyl I&XMes

. - if 1 62), In Hydre-csrboa Keiiat,t

1X-€>33.

**3

Public Docmeats

Clan, a,, United states Patent 3,095,^0, Juno 25* 1963.

RichardS) D# and £• Moltt United States Patent 3»080t32^-» March 5» 1963*