Patent US4269780A successfully refreshed from Google Patents.
US4269780A
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Olefin disproportionation
Assignee: Certis USA LLC
•
Filing: 1979-12-06
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Granted: 1981-05-26
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Expires: 1999-12-06
Abstract
Abstract A process for forming non-polymeric disproportionation products of non-conjugated olefins using catalysts comprising (1) at least one of certain neutral carbene complexes, and (2) at least one of certain compounds of Groups IVa, IVb, Vb, VIb, VIIb, VIII, and Ib of the Periodic Table of the Elements.
Inventors
- 👤 Dennis S. Banasiak
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 19:42
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/16; B01J31/20; B01J27/00; B01J27/06; B01J31/22; B01J31/2265; B01J31/2282; B01J31/2295; B01J31/24; B01J31/2404; B01J31/26; B01J2231/00; B01J2231/50; B01J2231/54; B01J2231/543; B01J2531/00; B01J2531/60; B01J2531/62; B01J2531/66; B01J2531/70; B01J2531/74; B01J31/18; B01J31/1805
Claims Analysis
Total Claims: 68
Claim 1
Independent Claim
359 words
A process for forming non-polymeric disproportionation products comprising contacting suitable non-conjugated olefinic reactants under suitable reaction conditions with a catalytic amount of a catalyst composition comprising effective amounts of (1) at least one metal compound component selected from the group consisting of the chlorides and bromides of Groups IVa, IVb, Vb, VIb, VIIb, VIII, and Ib; and the oxychlorides and oxybromides of molybdenum tungsten, vanadium, and chromium, wherein if the metal is vanadium it is in an oxidation state of either 4 or its highest stable common ionic oxidation state, if the metal if molybdenum, tungsten, or rhenium, it is in an oxidation state of either 5 or its highest stable common ionic oxidation state; and if the metal is other than vanadium, molybdenum, tungsten, or rhenium, the metal is in its highest stable common ionic oxidation state; and (2) at least one neutral carbene complex having the general formula ##STR54## wherein R is selected from the group consisting of alkyl or cycloalkyl radicals containing 1 to 10 carbons per radical and aryl or substituted aryl radicals containing 6 to 30 carbon atoms per radical wherein the substituted radicals can have one or more substituents each of which can be the same or different and selected from the group consisting of halides, alkoxides, and alkyl radicals containing 1 to 20 carbon atoms per radical; wherein R I is selected from the group consisting of alkyl, cycloalkyl, aryl, substituted aryl, triarylsilyl, and trialkylsilyl radicals containing 1 to 30 carbon atoms per radical and wherein the aryl substituents are as described for R; M can be Cr, when said metal compound component contains Ti; or M can be W or Re; Y is O, Se, S, N, or P; each L is a neutral ligand individually selected from CO, NO, Pr 3 I , PCl 3 , PF 3 , and pyridine, where R I is as defined above, and L I is cyclopentadienyl; p is 0 or 1; n is 5 when p is 0 or 2 when p is 1; and m is 2 when y is N or P and 1 when Y is 0, Se, or S.
Claim 2
Dependent Claim
359 words
A process for forming non-polymeric disproportionation products comprising contacting suitable non-conjugated olefinic reactants under suitable reaction conditions with a catalytic amount of a catalyst composition comprising effective amounts of (1) at least one metal compound component selected from the group consisting of the chlorides and bromides of Groups IVa, IVb, Vb, VIb, VIIb, VIII, and Ib; and the oxychlorides and oxybromides of molybdenum tungsten, vanadium, and chromium, wherein if the metal is vanadium it is in an oxidation state of either 4 or its highest stable common ionic oxidation state, if the metal if molybdenum, tungsten, or rhenium, it is in an oxidation state of either 5 or its highest stable common ionic oxidation state; and if the metal is other than vanadium, molybdenum, tungsten, or rhenium, the metal is in its highest stable common ionic oxidation state; and (2) at least one neutral carbene complex having the general formula ##STR54## wherein R is selected from the group consisting of alkyl or cycloalkyl radicals containing 1 to 10 carbons per radical and aryl or substituted aryl radicals containing 6 to 30 carbon atoms per radical wherein the substituted radicals can have one or more substituents each of which can be the same or different and selected from the group consisting of halides, alkoxides, and alkyl radicals containing 1 to 20 carbon atoms per radical; wherein R I is selected from the group consisting of alkyl, cycloalkyl, aryl, substituted aryl, triarylsilyl, and trialkylsilyl radicals containing 1 to 30 carbon atoms per radical and wherein the aryl substituents are as described for R; M can be Cr, when said metal compound component contains Ti; or M can be W or Re; Y is O, Se, S, N, or P; each L is a neutral ligand individually selected from CO, NO, Pr 3 I , PCl 3 , PF 3 , and pyridine, where R I is as defined above, and L I is cyclopentadienyl; p is 0 or 1; n is 5 when p is 0 or 2 when p is 1; and m is 2 when y is N or P and 1 when Y is 0, Se, or S.
Claim 3
Dependent Claim
39 words
A process in accordance with claim 1 wherein said disproportionation is carried out in the temperature range of about 35° C. to about 200° C. and under pressure in the range of from about atmospheric to about 5,000 psig.
Claim 4
Dependent Claim
295 words
A process in accordance with claim 2 wherein olefinic reactants contain 3 to 40 carbon atoms and one or more non-conjugated carbon-carbon double bonds per molecule and at least one of said reactants contains a maximum of two carbon-carbon double bonds and is either (1) an acyclic olefin of the formula R.sup.III CH═CHR.sup.IV wherein R III and R IV are independently selected from the group consisting of hydrogen, alkyl radicals, alkaryl radicals, and alkenyl radicals where each of said radicals contains 1 to 18 carbon atoms per radical, or (2) a monocyclic olefin represented by the formula ##STR55## wherein R V is an alkylene or alkenylene radical containing 5 to about 16 carbon atoms per radical and wherein each of the radicals R III , R IV , and R V can contain one or more functional groups independently selected from the group consisting of esters, ethers, fluorine, chlorine, bromine, iodine, trisubstituted silyloxy of the formula -OSiR 3 VI , trisubstituted silyl of the formula -SiR 3 VI , and ammonium salts of the formula -N + R 3 VII X - wherein R VI is an alkyl, aryl, or substituted aryl radical containing from 1 to about 20 carbon atoms per radical with the aryl substituents being halides, alkoxides, or alkyl radicals, each R VII is hydrogen or an alkyl radical with at least one alkyl radical being required and containing from 1 to 10 carbon atoms per radical, and X is chloride, bromide, or iodide, wherein said esters, ethers, halides, and trisubstituted silyloxy groups are at least two carbon atoms from the carbon atoms of any olefinic double bond and wherein said trisubstituted silyl and ammonium salt groups are at least one carbon atom from the carbon atoms of any olefinic double bond.
Claim 5
Dependent Claim
90 words
A process in accordance with claim 3 wherein said metal compound component is selected from the group consisting of germanium tetrachloride, tin tetrachloride, tin tetrabromide, lead tetrachloride, titanium tetrachloride, titanium tetrabromide, zirconium tetrachloride, hafnium tetrachloride, vanadium tetrachloride, vanadium oxytrichloride, niobium pentachloride, tantalum pentachloride, chromium trichloride, molybdenum pentachloride, molybdenum pentabromide, molybdenum oxytetrachloride, tungsten hexachloride, tungsten pentabromide, tungsten oxytetrachloride, manganese trichloride, rhenium pentachloride, iron trichloride, iron tribromide, cobalt trichloride, nickel(II) bromide, ruthenium trichloride, rhodium trichloride, palladium dichloride, osmium trichloride, iridium tetrachloride, platinum tetrachloride, copper(II) chloride, copper(II) bromide, silver chloride, and gold(III) chloride.
Claim 6
Dependent Claim
31 words
A process is accordance with claim 4 wherein the molar ratio of said metal compound component to said carbene complex component is in the range of about 1/1 to about 500/1.
Claim 7
Dependent Claim
18 words
A process in accordance with claim 5 wherein M is Cr and said metal compound component contains Ti.
Claim 8
Dependent Claim
11 words
A process in accordance with claim 5 wherein M is W.
Claim 9
Dependent Claim
48 words
A process in accordance with claim 7 wherein Y is S and at least one of R and R I is a radical other than aryl or substituted aryl and said olefin reactants do not contain ether, ester, halide, trisubstituted silyloxy, trisubstituted silyl, or ammonium salt functional groups.
Claim 10
Dependent Claim
16 words
A process in accordance with claim 7 wherein said metal compound component contains Ti or W.
Claim 11
Dependent Claim
53 words
A process in accordance with claim 7 wherein R is an aryl radical containing 6 to 12 carbon atoms per radical, R I is an alkyl radical containing 1 to 10 carbon atoms per radical, Y is 0 or S, M is tungsten, L is CO, n is 5, and p is 0.
Claim 12
Dependent Claim
18 words
A process in accordance with claim 10 wherein said metal component is selected from those not containing Ti.
Claim 13
Dependent Claim
17 words
A process in accordance with claim 10 wherein said metal component contains Ti and Y is 0.
Claim 14
Dependent Claim
44 words
A process in accordance with claim 7 wherein R is an alkyl radical containing 1 to 10 carbon atoms per radical, R I is an alkyl radical containing 1 to 10 carbon atoms per radical, Y is 0, and said metal component contains Ti.
Claim 15
Dependent Claim
20 words
A process in accordance with claims 7, 8, 9, 10, 11, 12, and 13 wherein said olefinic reactants are hydrocarbons.
Claim 16
Dependent Claim
27 words
A process according to claim 14 wherein the molar ratio of olefin to carbene complex component is in the range of from about 1/1 to about 5,000/1.
Claim 17
Dependent Claim
40 words
A process according to claim 5 wherein said carbene complex component is selected from the group consisting of (methoxyphenylcarbene)pentacarbonyltungsten(O), (p-chlorophenylmethoxycarbene)-pentacarbonyltungsten(O), (p-methylphenylmethoxycarbene)pentacarbonyltungsten(O), (p-methoxyphenylmethoxycarbene)pentacarbonyltungsten(O), (phenoxyphenylcarbene)pentacarbonyltungsten(O), (cyclohexyloxyphenylcarbene)pentacarbonyltungsten(O), (butoxyphenylcarbene)pentacarbonyltungsten(O), (octyloxyphenylcarbene)pentacarbonyltungsten(O), (hexadecyloxyphenylcarbene)pentacarbonyltungsten(O), (eicosyloxyphenylcarbene)pentacarbonyltungsten(O), (phenyltrimethylsilyloxycarbene)pentacarbonyltungsten(O), (phenyltriphenylsilyloxycarbene)pentacarbonyltungsten(O), (methylthiophenylcarbene)pentacarbonyltungsten(O), (dimethylaminophenylcarbene)pentacarbonyltungsten(O), (methoxyphenylcarbene)pentanitrosyltungsten(O), (methoxyphenylcarbene)η 5 -cyclopentadienyldicarbonyl rhenium(I), (methoxyphenylcarbene)tetracarbonyl(triphenylphosphine)tungsten(O), and (methoxyphenylcarbene)pentacarbonylchromium(O).
Claim 18
Dependent Claim
12 words
A process according to claim 10 wherein said carbene complex is (methoxyphenylcarbene)pentacarbonyltungsten(O).
Claim 19
Dependent Claim
13 words
A process according to claim 17 wherein 1-pentene is reacted to produce 4-octene.
Claim 20
Dependent Claim
13 words
A process according to claim 17 wherein 1-hexene is reacted to produce 5-decene.
Claim 21
Dependent Claim
13 words
A process according to claim 17 wherein cyclooctene is reacted to produce 1,9-cyclohexadecadiene.
Claim 22
Dependent Claim
13 words
A process according to claim 17 wherein cis-2-pentene is reacted to produce 3-hexene.
Claim 23
Dependent Claim
13 words
A process according to claim 17 wherein 1-decene is reacted to produce 9-octadecene.
Claim 24
Dependent Claim
13 words
A process according to claim 17 wherein propene is reacted to produce 2-butene.
Claim 25
Dependent Claim
13 words
A process according to claim 17 wherein 1-tetradecene is reacted to produce 12-hexacosene.
Claim 26
Dependent Claim
14 words
A process according to claim 17 wherein 4-penten-1-yl acetate is reacted to produce 1,8-diacetoxy-4-octene.
Claim 27
Dependent Claim
14 words
A process according to claim 17 wherein methyl 10-undecenoate is reacted to produce 10-eicosen-1,20-dioate.
Claim 28
Dependent Claim
17 words
A process according to claim 17 wherein methyl oleate is reacted to produce 9-octadecene and dimethyl 9-octadecen-1,18-dioate.
Claim 29
Dependent Claim
17 words
A process according to claim 17 wherein cyclopentene is reacted with 4-penten-1-yl acetate to produce 4,9-decadien-1-yl acetate.
Claim 30
Dependent Claim
18 words
A process according to claim 17 wherein said olefinic reactant is 5-chloro-1-pentene, ethyl oleyl ether, or methyl 10-undecenoate.
Claim 31
Dependent Claim
19 words
A process according to claim 17 wherein methyl oleate is reacted with ethylene to produce 1-decene and methyl 9-decen-1-oate.
Claim 32
Dependent Claim
20 words
A process according to claim 17 wherein at least one of said olefinic reactants contains chlorine, bromine, or iodine substituents.
Claim 33
Dependent Claim
13 words
A process according to claim 17 wherein said olefinic reactants are all hydrocarbons.
Claim 34
Dependent Claim
17 words
A process according to claim 17 wherein at least one of said olefinic reactants contains ester functions.
Claim 35
Dependent Claim
17 words
A process according to claim 17 wherein at least one of said olefinic reactants contains ether functions.
Claim 36
Dependent Claim
26 words
A process according to claim 5 wherein said carbene complex components are selected from the group consisting of (ethoxyphenylcarbene)pentacarbonyltungsten(O), (methoxymethylcarbene)-pentacarbonyltungsten(O), (methoxybutylcarbene)pentacarbonyltungsten(O), (methoxyphenylcarbene)tetracarbonyl (triphenylphosphine)tungsten(O), (phenyltrimethylsilyloxycarbene)pentacarbonyltungsten(O), and (methoxyphenylcarbene)pentacarbonylchromium(O).
Claim 37
Dependent Claim
18 words
A process according to claim 35 wherein said metal compound component is TiCl 4 or WCl 6 .
Claim 38
Dependent Claim
21 words
A process according to claim 5 wherein said carbene complex is (phenylthiophenylcarbene)pentacarbonyltungsten(O) and said metal compound component is TiCl 4 .
Claim 39
Dependent Claim
41 words
A process according to claim 5 wherein Y is oxygen or sulfur, m is 1, M is W or Re, L is CO or NO, and R and R I are not both aryl or substituted aryl when Y is S.
Claim 40
Dependent Claim
46 words
A process according to claim 38 wherein said metal compound component is selected from the group consisting of tin tetrachloride, tin tetrabromide, germanium tetrachloride, germanium tetrabromide, lead tetrachloride, and lead tetrabromide and wherein said catalyst composition includes a promoting amount of silicon tetrachloride or silicon tetrabromide.
Claim 41
Dependent Claim
28 words
A process according to claim 39 wherein the molar ratio of silicon tetrahalide to said metal compound component is in the range of about 0.1/1 to about 200/1.
Claim 42
Dependent Claim
10 words
A process according to claim 40 wherein M is W.
Claim 43
Dependent Claim
24 words
A process according to claim 41 wherein said carbene complex component is selected from the group consisting of (methoxymethylcarbene)pentacarbonyltungsten(O), (methoxybutylcarbene)-pentacarbonyltungsten(O), (thiophenylmethylcarbene)pentacarbonyltungsten(O), (phenylthiophenylcarbene)pentacarbonyltungsten(O) and (methoxyphenylcarbene)pentacarbonyltungsten(O).
Claim 44
Dependent Claim
15 words
A process according to claim 42 wherein said metal compound component is SnCl 4 .
Claim 45
Dependent Claim
13 words
A process according to claim 43 wherein said olefinic reactant is a hydrocarbon.
Claim 46
Dependent Claim
77 words
A process according to claim 38 wherein said metal compound component is selected from the group consisting of tin tetrachloride, tin tetrabromide, zirconium tetrabromide, tungsten hexachloride, tungsten hexabromide, tungsten pentachloride, tungsten oxytetrabromide, tungsten oxytetrachloride, and tungsten pentabromide and wherein said catalyst composition includes a promoting amount of at least one tetraorganogermanium compound of the formula GeR 4 II wherein R II is an alkyl, aryl, or alkaryl radical containing from 1 to 10 carbon atoms per radical.
Claim 47
Dependent Claim
30 words
A process according to claim 45 wherein the molar ratio of said tetraorganogermanium compound component to said metal compound component is in the range of about 0.1/1 to about 100/1.
Claim 48
Dependent Claim
10 words
A process according to claim 46 wherein M is W.
Claim 49
Dependent Claim
13 words
A process according to claim 47 wherein said carbene complex component is (methoxyphenylcarbene)pentacarbonyltungsten(O).
Claim 50
Dependent Claim
35 words
A process according to claim 38 wherein said metal compound component is selected from the tetrachlorides and tetrabromides of germanium, tin, and lead and wherein said catalyst composition includes a promoting amount of carbon tetrachloride.
Claim 51
Dependent Claim
29 words
A process according to claim 49 wherein the molar ratio of said carbon tetrachloride to said metal compound component is in the range of about 0.1/1 to about 200/1.
Claim 52
Dependent Claim
10 words
A process according to claim 50 wherein M is W.
Claim 53
Dependent Claim
12 words
A process according to claim 51 wherein said carbene complex is (methoxyphenylcarbene)pentacarbonyltungsten(O).
Claim 54
Dependent Claim
63 words
A process according to claim 38 wherein said metal compound component is selected from the group of germanium tetrachloride and zirconium tetrabromide and wherein said catalyst composition further includes a promoting amount of at least one tetraorganotin compound of the formula SnR 4 II wherein R II is an alkyl, aryl, or alkaryl radical containing from 1 to 10 carbon atoms per radical.
Claim 55
Dependent Claim
29 words
A process according to claim 53 wherein the molar ratio of said tetraorganotin compound to said metal compound component is in the range of about 0.1/1 to about 200/1.
Claim 56
Dependent Claim
10 words
A process according to claim 54 wherein M is W.
Claim 57
Dependent Claim
18 words
A process according to claim 55 wherein said carbene complex is (methoxyphenylcarbene)phenyltungsten(O) and said tetraorganotin is tetramethyl tin.
Claim 58
Dependent Claim
20 words
A process according to claim 5 wherein said metal compound component comprises a mixture of tin tetrachloride and germanium tetrachloride.
Claim 59
Dependent Claim
21 words
A process according to claim 57 wherein said carbene complex component is (methoxyphenylcarbene)pentacarbonyltungsten(O) and said olefin reactant is selected from hydrocarbons.
Claim 60
Dependent Claim
241 words
A process for forming non-polymeric disproportionation products comprising contacting suitable non-conjugated olefinic reactants under suitable reaction conditions with a catalytic amount of a catalyst composition comprising effective amounts of (1) silicon tetrachloride, (2) at least one neutral carbene complex having the general formula ##STR56## wherein R is selected from the group consisting of alkyl or cycloalkyl radicals containing 1 to 10 carbon per radical and aryl or substituted aryl radicals containing 6 to 30 carbon atoms per radical wherein the substituted radicals can have one or more substituents each of which can be the same or different and selected from the group consisting of halides, alkoxides, and alkyl radicals containing 1 to 20 carbon atoms per radical; wherein R I is selected from the group consisting of alkyl, cycloalkyl, aryl, substituted aryl, triarylsilyl, and trialkylsilyl radicals containing 1 to 30 carbon atoms per radical and wherein the aryl substituents are as described for R I , Y is 0 or S, L is CO or NO, and R and R I are not both aryl or substituted aryl when Y is S and non-functional olefin reactant is employed; and (3) a promoting amount of carbon tetrachloride, wherein the molar ratio of said silicon tetrachloride to said carbene complex component is in the range of about 1/1 to about 500/1 and the molar ratio of said carbon tetrachloride to said silicon tetrachloride is in the range of about 0.1/1 to about 200/1.
Claim 61
Dependent Claim
241 words
A process for forming non-polymeric disproportionation products comprising contacting suitable non-conjugated olefinic reactants under suitable reaction conditions with a catalytic amount of a catalyst composition comprising effective amounts of (1) silicon tetrachloride, (2) at least one neutral carbene complex having the general formula ##STR56## wherein R is selected from the group consisting of alkyl or cycloalkyl radicals containing 1 to 10 carbon per radical and aryl or substituted aryl radicals containing 6 to 30 carbon atoms per radical wherein the substituted radicals can have one or more substituents each of which can be the same or different and selected from the group consisting of halides, alkoxides, and alkyl radicals containing 1 to 20 carbon atoms per radical; wherein R I is selected from the group consisting of alkyl, cycloalkyl, aryl, substituted aryl, triarylsilyl, and trialkylsilyl radicals containing 1 to 30 carbon atoms per radical and wherein the aryl substituents are as described for R I , Y is 0 or S, L is CO or NO, and R and R I are not both aryl or substituted aryl when Y is S and non-functional olefin reactant is employed; and (3) a promoting amount of carbon tetrachloride, wherein the molar ratio of said silicon tetrachloride to said carbene complex component is in the range of about 1/1 to about 500/1 and the molar ratio of said carbon tetrachloride to said silicon tetrachloride is in the range of about 0.1/1 to about 200/1.
Claim 62
Dependent Claim
10 words
A process according to claim 59 wherein L is CO.
Claim 63
Dependent Claim
13 words
A process according to claim 60 wherein said carbene complex component is (methoxyphenylcarbene)pentacarbonyltungsten(O).
Claim 64
Dependent Claim
14 words
A process according to claim 61 wherein said olefinic reactants are selected from hydrocarbons.
Claim 65
Dependent Claim
26 words
A process according to claim 62 wherein the molar ratio of carbon tetrachloride to silicon tetrachloride is in the range of about 1.5/1 to about 50/1.
Claim 66
Dependent Claim
13 words
A process according to claim 63 wherein 1-pentene is reacted to produce 4-octene.
Claim 67
Dependent Claim
18 words
A process according to claim 9 wherein at least one of said olefinic reactants contains an ester function.
Claim 68
Dependent Claim
18 words
A process according to claim 10 wherein at least one of said olefinic reactants contains an ester function.
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1984-05-25 | 1984-11-24 | 1985-05-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-05-25 | 1988-11-24 | 1989-05-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-05-25 | 1992-11-24 | 1993-05-26 | $7700.00 | Window Closed / Lapsed |