of chemistry ff b~f olefin metathesis ptlus ...induction of olefin metathesis by phenylacetylene...
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AD-AIIS 945 COLUMBIA UNIV N4EW YORK DEPT OF CHEMISTRY Ff B~fINDUCTION OF OLEFIN METATHESIS BY PHENYLACETYLENE PtLUS TUNGSTEN--CYCCU)JUN 82 T J KATZ, C HAN N00014-79-C-0663
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fSIECURITY CLASSIFICA TION OF TNS WAGE (When, Doea tj.emREPOT DCUMNTATON AGEREAD INSTRUCTIONS
REPOT DOUMENATIO PAG B3.7ORE COMPLETING FORM1. REPOT HUM2. GOVT ACCESSION NO. 3. RECIPICMT*S CATALOG NUMBER
4. 'TITLE (d Sub"111e) S. Type DP REPORT & PZRIOD COVEREDTechnical Report, 8/1/79-
Induction of Olef in Metathesis by Phenylacetylene 6/21/82Plus Tungsten Hexachioride 4. PERFORMING ORG. REPORT NUM86ER
7. AU ?NBRMe 6. CONTRACT OR GRANT NUNbI9R1(e
Thomas J. Katz, Chien-Chung Han N00014-79-C-0683
I4 S. PERFORMING ORGANIZATION AMIE AND ADDRESS 10. PROGRAM ELEMENT, PROJECT. TASKAREA a WORK UNIT NUMBERS
4ff Thomas 3. KatzDepartment of Chemistry, Columbia University NR 356-726
in New York, New York 10027It. CONTROLLING OFFICE NAMIE A140 ADDRESS 12. REPORT DATE
r- Office of Naval Research - Chemistry June 21._198213. "NMBER OF PAGES
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18. SUIPPLEMENTARY NOTES
To be published in Organometallics
DTICI1S1. IKY WORDS (Congiauo an reverse side it necesay -u idetitY by block ninabet)
C) Polymers Metathesis Alkenes ,JUN 2 3 1982C.) Polymerization Metal-carbenes AlkynesLAJ Catalysis Polyacetylenes 60
Initiation PolyalkenamersE
2& ASTRACT (ComeoAs ureverse side to n...esoy and Idmnily by block inumber)
Phenylacetylene induces tungsten hexachloride to initiate metatheses of cis-2-pentene, cyclopentene, cycloheptene, and cyclooctene. In too large amounts, how-ever, it i's ineffective. The reactions are run in the atmosphere. The stereo-selectivities for cis-olefins are moderate.
DD I 1473 EDITION OF I Nov 05 IS 0BSOLETE
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NTIS GFA&IDTIC TAB
ByDist r .u li on/
OFFICE OF NAVAL RESEARCH v t+ Codes... i n.dlor
Contract N00014-79-C-0683 'Dlst 2 1al
Task No. NR 356-726
TECHNICAL REPORT NO. 4
Induction of Olefin Metathesis by Phenylacetylene
Plus Tungsten Hexachloride
by
Thomas J. Katz, Chien-Chung Han
Prepared for Publication
in
Organometallics
Columbia UniversityDepartment of Chemistry
New York, New York
June 21, 1982
Reproduction in whole or in part is permitted forany purpose of the United States Government
This document has been approved for public releaseand sale; its distribution is unlimited
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The discovery by Hasuda et al. that tungsten hexachloride initiates
polymerization of phenylatetylene1 suggests the following proposition:
that phenylacetylene may eifectively replace the highly reactive organo-
aluminum component in the mixture with tungsten hexachloride that is
the archetypical2 *and still standard initiator for olefin metathesis.3
For if the metal-catalyzed polymerization of acetylenes is an olefin
metathesis, 4- 6 a metallic compound that induces an acetylene to
polymerize should itself be induced by the acetylene to metathesize
olefins. The idea was demonstrated recently with phenylacetylene
plus (phenylmethoxycarbene)pentacarbonyltungsten.6 It is shown here
also for phenylacetylene plus tungsten hexachloride, a combination that
is more available, acts faster, induces fair stereoselectivy, and can be
used unprotected in the atmosphere.7
Fig I Figure 1 shows phenylacetylene's effect on the metathesis of
cis-2-pentene 14 according to eq 115 As phenylacetylene is added, the
CH3CHCHC2H5 + WCI 6 + C6H5CBCH200 :1I: x (1)
C6H5CI
C 6 H C o ( C H C H 4 3. + ( Y C2 H N V
amount of reaction, negligible in its absence, rises dramatically
and then falls. Complete reaction is easily achieved, but only when
the amount of acetylene is appropriate.
Table I Table I similarly shows phenylacetylene's ability to stimulate
tungsten hexachloride to polymerize three cyclic olefins (eq 2), reactions
that (as seen in the table) occur inavoreciably, if at all, when
.... ... • . " , "
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100F
80
70
2Iu60-
502
0 40
30-
20-
10
1 2 3 4 5 6 7 8
200 X [c6H =CcH]/[WCI6]
Fu . The extent of reaction according to eq I as a function of x.
precent metathesis is recorded as 200r/(1 + 2r), where r is the ratio in
moles of either 2-butene to 2-pentene or 3-hexene to 2-pentene. The
bars span the two values associated with r measured in the two ways.
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+' WCI 6 + P615 cM4 -(2)2 O I : X n
phenylacetylene is absent. That the polymers formed are indeed
polyalkenamers, not saturated vinyl polymers, is attested to by their
IH NHR spectra displaying only the required resonances and
intensities. The latter measure contamination by saturated hydrocarbon
amounting to no more than 4-9% (±4%).
Table II Table 1I shows that for cyclopentene, as for 2-pentene, while small
amounts of phenylacetylene induce metathesis, larger amounts quench
reaction. The decreased molecular weights (also recorded there) when the
amount of acetylene is large imply that growing chains rather than
initiating centers are being extinguished. This termination may involve
eq 3, the transformation of a simpler metal-carbene into one more highly66
substituted and with conjugating groups. One might speculate that
the initiation involves eq 4, possibly accompanied by
+ C 6 H 5 C=CM (3)
wc1 5wo 4 (4)
-CWC-+ WI6 - -C-CCl- - -C-CC 2-
,I
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reaction with additional acetylene reducing the tungsten's oxidation
state.1 8
A hypothesis associating diminished stereoselectivity with the
presence of Lewis acids3e ,1 9 suggests that stereoselectivity should
increase when an aluminum halide is replaced by phenylacetylene and
decrease when (phenylmethoxycarbene) pentacarbonyltungsten is replaced
by tungsten hexachloride. The stereoselectivities recorded in Table II
and the stereochemistries of the 2-butenes (initially 69.6% cis) and
3-hexenes (initially ca. 54% cis) in Figure 1 accord with this hypothesis. 20
Acknowledments. We are grateful to the National Science Foundation
(CHE-81-08998) and the U.S. Office of Naval Research for support.
Referegnces and__Notes
(1) Masuda, T.; Hasegawa, K.; Higashimura, T. Macromolecules
1974, 7, 728.
(2) Natta, G.; Dall'Asta, G.; Mazzanti, G. Angew. Chem. Int. Ed.
Engl. 1964, 3, 723.
(3) (a) Banks, R.L. Catalysis (London) 1981, 4, 100. (b) Calderon,
N.; Lawrence, J. P.; Ofstead, E. Adv. Organomet. Chem. 1979, 17, 449.
(c) Grubbs, R. H. Prog. Inorg. Chem. 1978, 24, L. (d) Rooney, J. J.;
Stewart, A. Catalysis (London) 1977, 1, 277. (e) Katz, T. J. Adv.
Organomet. Chem. 1977, 16, 283. (f) Haines, R. J.; Leigh, G.J. Chem.
Soc. Rev. 975 , 1. (g) Mol, J. C.; Moulijn, J. A. Adv. Catal. 1975,
24, 131. (h) Dall'Asta, G. Rubber Chem. Techn. 1974, 47, 511.
(4) Masuda, T.; Sasaki, N.; Higashimura, T. Macromolecules 1975,
8, 717.
(5) Katz, T. J.; Lee, S. J. J. Am. Chem. Soc. 1980, 102, 422.
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(6) (a) Katz, T. J. ; Lee, S. J. ; Nair, M.; Savage, E. B. Ibid.
U8 0, 102, 7940. (b) Katz, T. J.; Savage, E. B.; Lee, S. J.; Nair, M.
Ibid. U80102, 7942.
(7) Tungsten hexachloride alone does not metathesize olefins that
are unstrained,a but it does metathesize examples that are strained (like norbornene
and dicyclopentadiene).p Klpper demonstrated that combined with more
reactive olefins it would induce the reactions of those that are less
reactivel and Makovetsldi et al. very recently discovered results
similar to some of those reported here, in which it is effective in
12combination with acetylenes. Phenylacetylene is also recorded among
additives that enhance the reactivity of tungsten hexachloride
plus tetrabutyltin.13
(8) In the presence of oxygen, but not in its absence, WCI 6 is
reported to polymerize cyclopentene to polypentenamer. 9 Similar, but not
identical, experiments (see Table I) failed for us. After a long time
(22 h) at 30 OC with WC16 in air in the absence of solvent, cyclopentene
1gave a 2.6% yield of polymer that was 80% saturated ( H NMR analysis).
In an equal volume of chlorobenzene (not toluene and not distilled from
triethylaluminum) after the same amount of time it did not polymerize
appreciably.
(9) Amass, A.J.; McGourtey, T.A. Eur. Polym. j. 1980, 16, 235.
(10) Oshika, T.; Tabushi, H. Bull. Chem. Soc. Jpn. 1968, 41, 211.
(11) Kpper, F.-W. Ansew. Makromol. Chem. 9, 80, 207.
(12) Makovetskii, K. L.; Red'kina, L. I.; Oreshkin, I. A. Izv. Akad.
Nauk SSSR, Ser. Khim. 1981, 1928.
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(13) Ichikava, K.; Watanabe, 0.; Takagi, T.; Fukuzumi, K. J. Cacal.
97 44, 416.
(14) 99.6% cis, containing 0.25% n-pentane.
(15) The volume of chlorobenzene equalled that of the cis-2-pentene.
No precaution was taken to exclude air.
(16) Katz, T. J.; Lee, S. J.; Acton, N. Tetrahedron Lett. 1976, 4247.
(17) The 13C NMR spectra of polyalkenamers are described in reference
14, in the references in its footnote 18, and in (a) Carmen, C. J.;
Wilkes, C.E. Macromolecules 1974, 7, 40. (b) Chen, H. Y. Appl. Polym.
Spectrosc. I 7.
(18) (a) Greco, A.; Pirinoli, F.; Dall'Asta, G. J. Organometal.
Chem. 1973, 60, 115. (b) San Fillipo, Jr., J.; Sowinski, A. F.; Romano,
L. J. 3. Am. Chem. Soc. 1974, 97, 1599.
(19) Katz, T. J.; Hersh, W. H. Tetrahedron Lett. 1977, 585.
(20) See the results and sumaries in references 3e, 6a, 16 , and 19.
KUpper's aluminum-free catalysts induce stereochemistries like those
here.11 For cyclopentene's metathesis decreasing amounts of aluminum
halides decrease the stereoselectivity, and metals (like S22 and Si )
whose halides are less acidic than aluminum's enhance stereoselectivity.
(21) (a) Ganther, P. et al. Angew. Makromol. Chem. 1971, 4, 87 and
16/17, 27. (b) tvin, K. J.; Laverty, D. T.; Rooney, J. J. Makromol.
Chem. "7,178 , 1543.
(22) Ivin, K. J.; Lapienis, G.; Rooney, J. J. Polymer 1980, 21, 367.
(23) Oreshkin, I. A. et al. Eur. Polm. J. 1 , 13, 447.
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