CA1318919C - Formation of vinylbicycloheptane - Google Patents

Formation of vinylbicycloheptane

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CA1318919C
CA1318919C CA000616184A CA616184A CA1318919C CA 1318919 C CA1318919 C CA 1318919C CA 000616184 A CA000616184 A CA 000616184A CA 616184 A CA616184 A CA 616184A CA 1318919 C CA1318919 C CA 1318919C
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mmol
ch2c12
added
ethylene
reaction
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Gunther Wilke
Jaroslaw Monkiewicz
Herbert Kuhn
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Studiengesellschaft Kohle gGmbH
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02Phosphorus compounds
    • C07F9/547Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/31Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of rings
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
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    • C07C2531/12Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00Systems containing only non-condensed rings
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    • C07C2601/10Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00Systems containing two condensed rings
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    • C07C2602/42Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Abstract

FORMATION OF VINYLBICYCLOHEPTANE

ABSTRACT

Optically active vinylbicycloheptane or 3-phenylbutene-1 is formed by the reaction of ethylene with bicycloheptene or a styrene in the presence of a .pi.-allylnickel halide/azaphospholene complex and a Lewis acid.

Description

~ 3~8~

It has been known that olefins can be dimerized or co-dimerized by means of niokel containing and phosphane-modified catalysts. Thusr the co-dimer-ization of cyclic dienes or ~trained ole~ins such as norbornene and ethene by using ~-allylnickel halid,es or nickel~O~ compounds and the activation thereof by means of Lewis acids and the modifiration with acyclic phosph~nes, also optically active acyclic phospha~es, have been described sevPral times ~German Patent 20 39 125, Studiengesellschaft Kohle mbH. ~priority 1970); U.S. patent 3,978,147, StudiengesRllschaft Kohle mbH. (priority 1973); U.S. patent ~,0~8,B34, Studien-gesellschaft Rohle mbH, (priority 1976); G, Wilke et al., Angew. Chem. ~1972, 1070; B. Bogdanovic et al., Angew. Chem. 1973, 1013~; F. Petit et al., Bull. Soc.
Chim. lg79~ 415;: J. Che~. SocO lg80, ~37; Go Buono et al., ~. Org. Chem. 19~5, 50, 1781]. The processes known soi ~ar have technical disadvantages, as the catalysts æhow only :relati~ely low activities and moreover, the accomplished selectivitie~ are in-su~icien~ Tha maximum numbers of catalytic cycles attainable with the processes desaribed so ~ar are too low ~or a co~merolal use.

1 3 ~

Surprisingly, it was now found that said technical defects of the processes known so far can be overcome by using azaphospholenes as modifying ligands, the substituents o~ which azaphospholenes, due to their spatial requirements, will block certain rotations in the catalyst complexes. There~rom ensue relatively rigid arrangements at the catalyst wherein always one nic~el atom is complexed to each phosphorus atom. Such ligands are phospholenes having the .~ollowing s~ructu-re:
I~

\ 1~-- t ~ ' ~

wherein the moieties Rl and R2 may be alkyl, aryl and aralkyl groups which may be varied within wide limits.
Upon the preferred selection of Rl = -CH-C~H5, preferably in the optical R- or S-forms, respe~tively, and R2 = CH3, particularly good results are obtained.
The up to now unknown diastereomer built up with these substituents has the ~ollowing structure and con-figuration according to x-ray structural analysis:

~o C~c4 ~ C~6 C~ 2 C:17 ~""~
~C~O C~C~ .
C~5 C-~ C~7 ~CI~

This diastereomer 6a was obtain d by the following route starting ~rom (-)-a-pinene or r(-)-(lR,5S~-myrtenal 1] and (+~-R-a-phenylethylamine - :

0 C, ~ I

: 2 hours ~~
: ~ ~ 3 pen~ane ~ n, ll 3 ~ h~,PI~ ~ ~ t 1~1'", c ~4b ~ ~ 6 -10 'C to , room t~rature ~ ~5b ' In an analogous manner, starting from (+)-a-pinene and (-)-S-a-phenylethylamine there may be prapared the compound 6a' which is the enantiomer oP the afore-mentioned diaætereomer. 6a and 6a' as ligands in nickel-containing catalysts have the effect that, e.g., the co-dimerization of norhornene with ethene may be realized e~en at a temperature of from +50 ~C to -120 C, and preferably of from -20 C to -80 C, with an activity of 20,000 cycles per hour and selectivities o~ ~90~. The (-)-exo-vinylnorbornane formed according to the following reaction equation ~ catalyst ~ C =~
Gl ~ ~ C2H4 > G~

!
by the use of 6a as ligand in the nickal catalyst in CH2C12 has an enantiomeric excess (e.e.) of 57~, i.e.
the ligand ~a causes not only high activity and selectivity, but also a high optical induction, so that according ts the process an optically active product is obtained 78.5~ o~ which consist of on enantiomer.

If, contrary thereto, an analogous phospholene is built up starting ~rom ~ a-pinene and t-~-S-a-phehylethylamine, then another diastereomer 6b results _ 5 _ ~3~

therefrom, the structure of which was also elucidated by X-ray analysis.

~C~

;~C7 ~_~,C24 '~

~) C38 ~C~O C3 6b, as a catalyst component shows the e~fects as indicated above for 6a with respect to catalyst activity to a degree reduced by the fac~or 100, i.e.
under the same conditions there are accomplished about 200 cyc:les instead oP 20,000 cycles. Then the obtained product shows (+)-rotation and is (+)-exo-vinylnor-~ornane with an e.e. of 40%. Molecular modelling investigations on 6a and 6b show that in 6a rotations around certain bonds, ~e.g. the central C~C bond (Cl -C30) are largely restxicted, wh~le this is not the case in 6b. ~n ~a there~rom result the rigid arrangements as men~ioned whlch correspond ~o secondary structures in enzymes.
-- 6 - ~ 3 1 ~ ~

Synthesis of Azaphospholene (lR,5S~-6,6~Dimethyl-2-[(lR)~l-N-phenylethylaza-methino]bicyclo[3.l.l]hept-2-ene 3 34.37 g (0.284 mol) of (+)-(lR)-phenylethylamine 2 are charged in a 250 ml flask and heated ~o 70-80 C.
At this temperature 42.94 g (00286 mol) of ( )-(lR,5S)-myrtenal 1 are dropwise added within 1 h. A two-phase mixture is formed stirring of which is continued for 1 h. After cooling to room temperature 50 ml of lether are added, the aqueous phase is separated (4 ml), and the organic phasa is dried with KOH~Na2S04. Then the ether is condensed of~, and the crude prodllct 3 is distilled under high vacuum.
Yield: 62.3 g (86.7% of theory); b.p. 108-112 C.

5-Bromo-5,9,9-trimethyl-4-[(lR~ phenylethyl]-4-aza~
5-~ -phosphoniatricyclo~6.1.11 8. o2 63-dec-2(3)-ene bromide 4a, 5-Bromo-5,9,9-trimethyl-4-t(lR)-l-phenylethyl~-4-aza-5-~4~phosphoni~tril::yclo~ -8.o2 6~_dec_2(6~-ene bromide 4b 49.40 g (0.195 moll o~ the azadiene _ in 700 ml o~
n-pentane are charged, and 40.14 g (0.195 mol) of MeP~r2 in about 200 ml of n-pPntane are dropwise added~
A yeIlow precipitate is immediately formed. After the MePBr2 addition, the reaction mixture is stirred for 4 days. Then the yellow solid (crude phosphonium salts 4) are filtered o~f, washed three times with 100 ml of n-pentane each and dried in vacuo.
Yield of crudé material: 75.1 g ~84.0~ o~ theory).
~) 31P-NMR: 4a 77~2 ppm (CD2C12); 4b 67.1 ppm (CD2C12 ) -_ 7 _ ~3~

Bis-(3R) 3-{~lR,5R,8R)-5,9,9-trimethyl-4-~(lR)-l-phenylethyl~-4-aza 5-phosphatr~cyclo--[6.1.11 8.o2 6]-dec-2(6)-enyl} 6a 10.05 g ~21.9 mmol) o~ the crude product 4 are suspended in 100 ml of T~F on a ~rit:, the filtrate is collected in a flask, and the residue is discarded. To the'orange-colored filtxate there are added at -10 C
0.66 g (272 mmol) of active magnesium portionwise under vigorous stirring. After the completion o~ the addition the batch is allowed to warm up slowly to room temperature and is stixred overnight. Aftsr the solvent has been condensed off, 200 ml of ether are added to the residue, and the mixture is filtered. The ether is condensed off ~rom the yellow filtrate to obtain 10.62 g of a viscous residue which is dissolved in 4 to 5 parts by volume of met~anol with heating to about 60 C. In a water bath (about 60 GC) the mixture is stirred and allowed to cool to room temperature overnight. A colorless precipitate of 6a is formed.
Yield: 0.84 g (12.9~ of theory~; m.p. 134-135 C
trecrYstalllzed from ethanol).
31P-NMR: 49.9 ppm (toluene); [a]589 ~ -64.69 ~0.64 g/100 ml of C~2C12).

The azaphospholenes of the type 6a are suitable ~or the preparation of catalysts of a highly selective activity which in turn are capable of converting un-saturated hydrocarbons into optically active compounds.
~hus, an optically active ~inyl bicyclohep~ane is obtained ~rom bicycloheptene and ethylene in space-time yields not yet described 80 ~ar. Said optically a~tive vinyl blcycloheptane ln turn may be the starting material for the texpolymerization together with, e.g., ~ 3 ~

ethylene and propylene to give polymers, and more part-icularly optically active polymers. Optically active polymers, due to their high sterica:L regularity, have improved physical and mechanical propert~es. Thus, optically active polymers are suitable as absorbents for the sPparation of enantiomers. In the same manner, an optically active 3-phenylbutene--1 is selectively obtainabl~ in high yield from styrene and ethylene by co-dimexization, and so are substituted 3-phenyl-butenes-l from substituted styrenes and ethylene. The polymerization oX this a-olefin products to optically active polymers i~ effected in the same way as the terpolymerization set forth above.

A further application of the azaphospholenes in the form of the described complex compounds together with organoaluminum compounds is the selective change of the structure of, a.g., heptadiene-1,6 to form l-methyl-2-methylidene-cyclopentene, as well as the co-dimerization of l,3-cyclopentadiene and ethylena leading to optically active 3-phenylpentene-1.

Catalvtic Synthesis of Vinyl Bicycloheptane Example 1 A 2-1 four-neck ~lask e~uipped with stirrer, drop-ping funnel and a Clalsen head with thermometer is evacuated with heating and filled with argon. The flask is charged with 600 ml of CH2C12, and the drop-ping funnel is filled with 600 ml of a H2C12 solution o~ 400 g (4.25 mol) bicyalo[2.2.1]heptene. The flask is cooled to -65 C while its content ls stirred, and 0.047 g (0.108 mmol) of ~-allylnickel chloride/phospha-ne 6a complex (Ni:P = 1:1) dissolved in about 10 ml of 9 ~ 3 ~

cooled CH2C12 and 0.239 ml (1 mmol) o~ Et3A12C13 (P:Ni:Al = 1:1:20) are added, whereupon the complex solution becomes violet in color After briefly evacuating with an oil pump, the vacuum is removed with dry ethylene, and the solution of bicycloheptene is dropwise added with stirring wlthin 60 minutes. In the course thereof a high heat evolution is observed.
During the reaction period ~90 mimltes) ethylene is introduced into the apparatus whereby the reaction temperature is increased to -58 C.

Then the reaction is terminated by introducing gaseous ammonia, and the product is condensed off ln vacuo. From the condensate thus obtained the solvent is distilled off under normal pressure, and the residue is distilled through a Vigreux column.
Yield: 384 g (74% of theory).
~ exo-2-vinyl bicyclo~2.2.1~heptane ~54~ e.eO);
conversion numher: 29,140.
~20max (+~ 51 ; b.p. 54 C/30 m~r;
D - 0.8726 ~/cm .
xample 2 The procedure is as in Example 1, using a 0.5-1 four neck flask~ The flask is charged with 150 ml o~
CH2C12, and the dropping funnel is filled with 30 ml (0.32 mol) of bicyclo~2.2.1]heptene in 50 ml of CH2C12.
The solven~ is cooled to -70 C, and 0.0961 g ~0.352 mmol) of bis-cyclooctadienenickel and 0.105 g (0.352 mmol) of the phosphane 6a are added. The reaction mixture is allowed to warm up slowly to -15 C, until a strongly yellow alear solution is ~ormed, and then is again cooled to -70 ~C, and Q-080 ml (0-352 mmol) of Et3A12C13 (P:Ni:Al = 1:1:2~

~ 3 ~

are added. After renewed heating to -20 C the solution is saturated with ethylene , and the solution of hicycloheptene is dropwisa added within 15 minutes.
The reaction mixture is kept saturatad with ethylene by vigorous stirring for 60 minutes. The reaction is terminated with gaseous ammonia~ The product is condensed o~, the solvent is withdrawn, and the residue is dlstilled through a Vigreux column about 30 cm in length.
Yield: 35 g (90% of theory).
~ exo-2-vinyl bicyclo r 2 . 2.1]heptane (8.2% e.e.);
conversion number: 815.

Example 3 The procedure is as in Example 1. A l-liter flask is charged with 500 ml of chlorobenzene, and the drop-ping funnel is filled with 30 g ~0.32 mol) of bicyclo-heptene in 50 ml of chlorobenzene. The chlorobenzene is stirred and cooled to -40 C~ and 0.090 g ~0.186 mmol) of ~-allylnickel/phosphane~6a complex in about 15 ml of cooled chlorobenzene and 0.135 (1.12 mmol) o~ Et2AlCl (P:Ni:Rl = 1:1:6) ara added thereto. ~han the solution of bicycloheptene is drop-wise added within about 15 minutes, and ethylene is introduced into the apparatus. In the course o~ 2 h the reaction mixture is heated to ~4V C.

The catalysis is terminated by introducing gaseous ammonia, and the product ls condensed off m vacuo.
From the condensate thus obtained the solvent is distilled of~ under normal pressure, and tha residua i5 distilled through a Vigreux column.
Yield: 34 g (87.5% of theory).
(+)-exo-~-vinyl bicyclo[2.2.1]heptane (10.8% e.e.);

~ 3 ~

conversion number: 14980 Thus, in chlorobenzene th~
formation of the ~ orm is preferred.

Example 4 The procedure is as in Example 1. A 0.5-1 ~lask is charged with 150 ml of CHC13, and the dropping ~unnsl is ~illed with 30 g (0.32 mol) o~ bicyclo-heptene ln 50 ml of CHC13. The solvent is cooled to -30 ~C, and 0.020 g (0.114 mmol) o~ ;nickel acetate and 0.0678 g (0.228 mmol) of phosphane 6a are added. The reaction mixture is stirred for 30 m~nutes at -30 oc, and then 0.133 g (0.684 mmol) o~ AgBF4 ~P:Ni:BF4 --2:1:63 are added. After stirring for another 30 minutes the solution of bicycloheptene is dropwise added within 10 minutes, and ethylene is simultaneously introduced into the apparatus. After 60 minute the reaction is terminated by introducing gaseous ammonia.
The product is condensed off, the solvent is withdrawn, and the residue is distilled.
Yi21d: 32 g ~85% of theory).
exo-2-vinyl bicyclo[2.2.1]heptane (29~ e.e~);
conversion number: 23000 The procedure is as in Example 1. A 0.5-1 ~lask is charged with 150 ml of CH2C12, and the dropping funnel is filled wi~h 15 g (0.16 mol3 of bicycloo heptene. The solvent is stirred and cooled to -72 C, and 0.287 g (0.66 mmol~ of ~-allylnickel/phosphane~6b complex in about 20 ml o~ cooled CH2~12 and 0.150 ml (0-66 mm~l) v~ Et3A12C13 tp:Ni:A~ 1:2) are added thereto, whereby the complex solution becomes violet in color. Then at -72 C the solution o~ bicycloheptene - 12 ~ 3 ~

is dropwise added within 30 minutes, and ethylene is simultan~ously introduced into the solution. Upon completion of the bicycloheptene addition, the introduction of ethylene is continued for another 30 min. The reaction is terminated by introducing gaseous ammonia, and the product is condensecl o~ in vacuo, the solvent is withdrawn, and the residue is distilled.
Yield: 18 g (g2% o~ theory).
(+3-exo-2-vinyl bicycloE2.2.13heptane (38~ e.e.);
conversion number: 224.

Exam~le 6 The procedure is as in Example 1. A 0.5-1 flask is charged with 150 ml of CH~C12, and the dropping funnel is filled with 13 g ~0.19 mol) of bicyclo-heptene in 20 ml of CH2C12. The solvent is stlrred and cooled to -30 C, and 0.283 g (0.946 ~mol) of the mixture of the phosphane isomers 5a and 5b and ~.128 y (O0473 mmol) o~ bis-~allylnickel chloride are added.
The reaction mixture is stirred for 30 minutes and then cooled to -70 C, and 0.454 ml ~1.892 mmol) of Et3A12C13 lP:Ni:Al = 1:1:4) are added theretoO A~ter briefly evacuating wi~h an oil pump, the vacuum is removed with dry ethylene, and the solution of bicyclo-heptene is dropwise added within 15 minutes. Then the introduction of ethylene into thP apparatus is con tinued for another 15 min. The reaction is terminated by introducing gaseous ammonia, the product is con-densed o~f in vacuo, the solvent is withdrawn, and the residue is distilled.
Yield: 6 g (26% o~ theory)~
t-)-exo-2-vinyl bicyclo~2.2.1]heptane ~3.4% e.e.);
conversion number: 52.

- 13 ~

Example 7 The procedure is as in Example 1. A 0.5-1 ~lask is charged with 150 ml of CH2C12, and the dropping funnel is filled with 30 g (0.32 :mol) of bicyclo-heptene in 50 ml of CH2C12. The solvent is cooled to -65 C, and 0.0$6 g (0.197 mmol) of ~-allylnickel chloride/phosphane- _ complex dissolved in 10 ml of cooled CH2C12 and 0.227 ml of Et3A12C13 are added. The reaction mixture ist stirred at -65 C for 15 minutes.
Then 0.118 g (0.394 mmol) of the phosphane 6a (P:Ni:Al = 3:1:10) are added, and the solution is stirred for another 10 minutes. ~hen the solution of bicyclo-heptene is dropwise added within 15 minutes, and ethylene is simultaneously introduced into the appara-tus. The reaction is terminated by introducing gaseous ammonia, the product is condensed off in vacuo, the solvent is withdrawn, and the residue is distilled.
Yield: 34 g (~7~ of theory).
~ exo-2 vinyl bicyclo~2.2.1]heptane (57~ e.e.), conversion numker: 1413.

Example 8 A 100 1 glass reaction vessel equipped with ~tirrer, a ~5-1 feed tank and an internal thermometer is provided with an argon atmosphere. The reaotion vessel is charged with 50 1 of CH2Cl~, and the feed tank is filled with 10.13 kg (107.7 mol~ o~ bicyclo-heptene in 10 1 of CH2C12. The charged solvent is cooled to -40 C by means of a refrigerating machine, and the bicycloheptene solution is cooled to -13 C.

Thsn ethylene ls introduced, and 23 ml (0.102 mol) of Et3A12C13 and 4.448 g (0.0127 mol) of ~~allylnickel 1 3 ~ 8 ~ ~ ~

chloride/phosphane-6a compl~x dissolved in 50 ml of CH2C12 (P:Ni:Al = 1:1:20) are added. Then, with simultaneous introduction of ethylene, the solution of bicycloheptene i5 allowed to run in within 6 hours~
With ~ull output oP the connected re~.rigerating machine the reaction temperature increases to ~31 C. After 6.5 h the reaction is te~minated by the introduction of gaseous ammonia. Then the solvent is distilled off under normal pressure, and the residue is fractioned through a column.
Yield: 8.0 kg (65.6 mol; 60.9% of theory) ~ exo-2-vinyl bicycloE2.2.1]heptane (32~6% e.e.);
con~ersion number: 6388.

Catalytic Synthesis of OPticall~ Active 3-Phenyl-butene 1 _ _ Example 9 A 2-1 four-neck flasX equipped with stirrer, drop-ping ~unnel and a Claisen head with thermometer is evacuated with heating and filled with argon. The flask i~ charged with 700 ml of CH2C12, and the drop-ping funnel is filled with 460 ml of a CH2C12 solution cooled to -30 ~C of 275 g (2.6~ mol) of styrene. The flask is cooled ~o -70 C while ~ts content is stirred, and 0.590 g (1.36 mmol) of ~-allylnickel chloride/phos-phane 6a complex ~Ni:P = 1:1) dissolved in about 15 ml of cooled CH2C12 and 0.70 ml (3.0 mmol~ of Et3A12C13 ~P:Ni:Al = 1:1:3) are added. After briefly evacuating with an oil pump, the ~acuum is remove~ with dry ethylene, and the solution o~ styrene is dropwise added with stixring withi~ 45 minutes. In the course thereof the solution becomes warmed up to -60 ~C. During the L
-- 15 ~

reaction period (150 minut~s~ ethylene i~ introduced into the apparatus. The catalysis is terminated by introducin~ gaseous ammonia, and the product is condensed of~ in vacuo. From ~he condensate thus obtained the solvent is distilled off under normal pressura, and the residue is distilled through a Vigreux column. Yield: 340 g (97% of theory).
~ (R)~3-phenylbutene-1 (93% e.e.);
conversion number: 1890~

Example 10 The procedure is as in Example 1, using a 0.5-1 four-neck flask. The flask is charged with 150 ml of CH2C12, and the dropping funnel is ~illed with 18 g (0.17 mol) of styrene in 30 ml o~ CH2C12. ~he solvent is cooled to -70 C, and 0.0553 g (0.13 mmol) of ~-allylnickel chloride/phosphane 6a complex in about 15 ml of cooled CH2C12 and 0.030 ml (0.13 mmol) of Et3A12C13 are added, Therea~ter the reaction mixture is warmed up to 0 CC within 60 minutes. ~t 0 C the solution of styrene is dropwise added within 15 minutes, and ethylene is introduced into the apparatus.
The reaction is terminated by ~ntroduclng gaseous ammonia, and the produrt is condensed o~ in vacuo.
Then, the solvent is withdrawn, and the residue is distilled. Yield: 20.9 g (93% of theory).
~ (R)-~phenylbutene-l (76% e.e.);
conversion number: 1216.

Example 11 The procedure ls as in Example 1, using a 0.5-1 four-neck ~lask. The ~lask is charged with 150 ml of toluene, and the dropping ~unnel is filled with 20 ~

(o.l9 mol) of styrene in 40 ml of toluene. At room temperature 0.120 g (0.44 mmol) of bis-cyclooctadiene-nickel and 0~131 g (0.44 mmol) o~ the phosphane 6a are added. The reaction mixture is stirred ~or 30 minutes, and then 0.106 g (0.88 mmol) of Et:2AlCl (P:Ni:A1 -1:1:4) are add~d. Then the solution o~ styrene is dropwise added within 30 minutes, and ethylene i~
introduced into the apparatus~ By way of vigorous stirring the reaction mixture i5 kept saturated with ethylene for 4 hours. The catalysis is termlnated by the addition o~ ethanol, and the product is condensed off ln vacuo~ From the condensate the ~olvent is distill~d of~ through a Vigreux column under normal pressure, and the residue is fractionated under vacuum.
Yield: 15.1 g (60.2% of theory).
~ (R~-3-phenylbutene-1 (53% e.e.);
conversion number: 260.

Example 12 The procedure is as in Example 1. A 0.5-1 ~lask is charged with 150 ml of CH2C12, and the dropping funnel is filled with 20.3 g (0.195 mol) of styrene in 20 ml of CH2C12. ~he solvent is cooled to -60 ~C with stirring, and 0. 05~9 g ~0.122 mmol) of ~-allylnickel bromide/phosphane 6a in 20 ml of cooled CH2C12 and 0.028 ml (0.122 mmol) of Et3A12C13 (P:Ni:Al = 1:1:2) are added. After warming up to room temperature (+22 C) the catalyst ~olution is saturated with ethylene, and the solution o~ styrene is dropwise added within 15 minutes. The reaction mixture is kept in contact with ethylene by vigorous stirring ~or 3~ mlnutes. Then the reaction is terminated by intro-ducing gaseous a~monia, and the product is condensed -of~ in vacuo. From the condensate thus obtained the solv~nt is withdrawn, and the residue is distille~.

- 17 - ~3 Yield: 24.7 g (96% of theory).
~ (S)-3-phenylbutene-1 (70~ e.e.~;
conversion number: 1533.

xample 13 The procedure ls a~ in Example 1. ~ 0.5~1 ~lask is charged with 150 ml of CH2C12, and the dropping ~unnel is filled with 20 g ~0.196 mol~ of ~tyrene in about 30 ml of CH2C12. The solve.nt is cooled to -30 C, and 0.050 g (0.286 mmol~ o~ nickel acetate and 0.086 g (0.286 mmol) of phosphane 6a are added. The reaction mixtura is stirred at -30 7C for 60 minutes, and then 0.222 g (1~144 mmol). of AgBF4 are added (P~Ni:BF4 = 1:1:4). After another 30 minutes of stirring the solution of styrena ls dropwis2 added within 20 minutes, and ethylene i3 ~lmultaneously introduced into the apparatus. After 60 minutes the reaction is terminated by introducing gaseous ammonia, the product is condensed off in vacuo, the solvent is withdrawn, and the residue is distilled through a Vigreux column.
Yi~ld: 12 g (46~ o theory).
~ 3-phenylbutene~l (75% e.e.);
conversion number: 317.

Catalytic Synthesis of Optically _Active l-MethYl-2-methylidenecyclopentene Example 14 The procedure i~ as in Example 1 using a 0.5-1 ~our neck flask. ~he flask i~ charged with about 150 ml o~ CH2C12, and the dropping funnel is ~illed with 10 g ~0.104 mol) of heptadiene-1,6 in about 20 ml of CH2C12. The ~olvent is cooled to -30 ~C, and ~ 3 ~

0.079 g (0.182 mmol) of ~allylnickel chloride/phospha-n~ 6a complex in 15 ml of cool~d CH~C12 and 0.045 ml (0.197 mmol) of Et3A12C13 are added. The solution becomes orange in color. The catalyst mixture is stirr~d at -30 ~C for 30 minukes, and then khe ~olution of heptadiene-1,6 is dropwise added within 15 minutes~
After 3 hours at -30 C the reaction is ~topped with gaseous ammonia. The crude product is condensed off in vacuo, the solvent is withdrawn, and the residue is distilled through a Vigreux column.
Yield: 9.~ g (94% of theory).
l-(S)~ methyl-2-methylidenecyclopentene, b.p. 96 ~C; Ca]D2 ~61.6~ ~undiluted) (93 % e.e.);
conversion number: 1540 Example 15 A 100 1 glass reaction vessel equipped with stirrer, a 25-1 ~eed tank and an lnternal thermometer is provided with an argon atmosphere. The reaction vessel is charged with 40 1 of CH2C12, and the feed tank is filled with 8.26 kg ~79.5 mol) of styrene cooled to -20 C in 16 1 of CH2C12. The charged ~olvent i5 cooled to -62 C by means of a re~rigerating machine. The liquid is stirred~ while 20.3 g (0.047 mol) of ~ allylnickel chloride/phosphane 6a complex di~solved in 100 ml o~ CH2C12 cooled to -60 C
and 25 ml (0.109 mol) of Et3A12C13 (P:Ni:Al = 1:1:4.6) are added. Then ethylene is introduced, and th~
solution of ~tyrene cooled to -20 C by means of a second refrigerating machine is allowed to run in within 6 hours. The reaction temperature is maintained within a range o~ fxom -60 'C to -65 C. After 7 hours the reaction is termina ed by the introduction of gaseous ammonia. The solvent i~ distilled off under :1 3 ~ 8 9 ~ ~

normal pressure, and the residue is ~ractioned through a column.
Yleld: 4.3 kg t32~5 mol; 41% vf theory; ~7.4% e.e.).
3-phenylbutene-1; conversion number: 6910 Example 16 The procedure is a~ in Example 1. A 0.5-1 flask is chaxged with 150 ml o~ CH2C12, and the dropping ~unnel is filled wi~h 10 g (0.085 mol) o~ 4-methyl-styrene in about 40 ml of CH2C12~ The solvent is cooled to -70 'C with stirr~ng, and 0.109 g (0.25 mmol) of ~-allylnickel/phosphane 6a complex in about 20 ml sf CH2C12 and 0.115 ml (0.50 mmol) of Et3A12C13 (P:Ni~ 4) are added. At -70 ~C the solution of 4-methylstyrene i6 dropwise added within 15 minutes, and ethylene is 6imultaneously introduced into the solution. The reaction i~ terminated by introducing gaseous ammonia, and the reaction mixture is condensed off in vacuo. The solvent is withdrawn, and the re-sidue is distilled in vacuo.
Yield: 11.7 g (94.4% of theory).
~ (R)-p-tolylbutene-l);
conversion num~er: 320; ~a]22 -9.89- in substance (95.2 % e.e.).
:
ExamPle 17 Ths procedure is as in Example 1. A 0.5 1 flask is charged with 150 ml o~ CH2C12, and the dropping funnel ls ~illed wi~h 16 g ~0.242 mol~ of monomeria cylopentadiene-1.3 in lS ml of cooled CH2C12. The ~olvent i~ cooled to -70 C, and 1.22 g ~2.81 mmol) of ~-allylnickel/phosphane 6a complex in 25 ml of aooled C~2C12 and 0.3~3 ml (2.81 mmol) of Et~AlCl are added ~L3~3~

(P:Ni:Al = 1:1:1) . The reaction mixture is ~tirred at 70 C ~or 30 minutes~ Then ethylene is introduced into the apparatus ~or 1 minute, and then the solution vf cyclopentadiene-1,3 is slowly added dropwise with simul~aneous introduction of ethylene. The addi~ion of the cyclopentadiene-1,3 solutlon takes 1 hvur. Then the reaction mixture was stlrrend for another hour. The reaction is terminated by introducing gaseous ammonia, and the pr~duct is condensed of~ in vacuo. The solvent is wlthdrawn, and the residue is distilled.
Yield: 8 g (0.084 mol; 35~ o~ theory).
~ (R)-3-~inylpentene-1 (92% e.e.);
conversion number: 30.

This is a divisional of application serial No. 538,306 filed May 28, 1987.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. In the reaction of ethylene with bicycloheptene or a styrene to form optically active vinylbicycloheptane or 3-phenylbutene-1, the improvement which comprises effecting the reaction in the presence of a .pi.-allylnickel halide/
azaphospholene complex and a Lewis acid.

2. A process according to claim 1, wherein the styrene is styrene per se.

3. A process according to claim 1, wherein the styrenes is a benzostyrene.

4. A process according to claim 2, wherein the benzostyrene is 2-methoxy-6-vinyl-naphthalene.

5. A process according to claim 1, wherein the styrene is an alkyl styrene.

6. A process according to claim 5, wherein the alkyl styrene is 4-isobutylstyrene.

7. A process according to claim 1, wherein the Lewis acid is an alkyl or aryl aluminum halide or BF4.
CA000616184A 1986-05-30 1991-09-26 Formation of vinylbicycloheptane Expired - Fee Related CA1318919C (en)

Applications Claiming Priority (2)

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DE3618169.2 1986-05-30

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CA000616184A Expired - Fee Related CA1318919C (en) 1986-05-30 1991-09-26 Formation of vinylbicycloheptane
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