US5243068A
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Process for preparing vinylically-unsaturated compounds (II)
Assignee: Dow Chemical Co
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Filing: 1992-05-01
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Granted: 1993-09-07
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Expires: 2012-05-01
Abstract
Abstract A process for preparing a vinylically-unsaturated product compound comprises reacting a halogenated organic compound with a hydrolytically-stable, vinylically-unsaturated precursor compound in the presence of (a) a homogeneous zerovalent palladium catalyst complex, (b) an inorganic hydrogen halide acceptor and (c) a diluent, wherein the diluent is water or an aqueous solution containing up to 95% by volume of an organic solvent. The halogenated organic compound is selected from aryl halides, benzyl halides or vinylic halides. The hydrolytically-stable, vinylically-unsaturated precursor compound is selected from hydrocarbon compounds or compounds containing at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a combination thereof.
Inventors
- 👤 Robert A. DeVries
- 👤 Hughie R. Frick, deceased
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 12:45
CPC Classifications
C; C07; C07F; C07F7/00; C07F7/02; C07F7/08; C07F7/20; C07F7/0834; C07F7/0838; C07F7/0872; C07F7/0889
Claims Analysis
Total Claims: 41
Claim 1
Independent Claim
107 words
A process for the preparation of a vinylically-unsaturated product compound, comprising reacting a halogenated organic compound with a hydrolytically-stable, vinylically-unsaturated precursor compound selected from the group consisting of (i) hydrocarbons and (ii) compounds containing one or more of an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom or a combination thereof, in the presence of (a) a homogeneous zerovalent palladium catalyst complex, (b) an inorganic hydrogen halide acceptor and (c) a diluent, wherein the diluent is water or an aqueous solution containing up to 95% by volume of an organic solvent, provided that at least some diluent water is in a second phase.
Claim 2
Dependent Claim
107 words
A process for the preparation of a vinylically-unsaturated product compound, comprising reacting a halogenated organic compound with a hydrolytically-stable, vinylically-unsaturated precursor compound selected from the group consisting of (i) hydrocarbons and (ii) compounds containing one or more of an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom or a combination thereof, in the presence of (a) a homogeneous zerovalent palladium catalyst complex, (b) an inorganic hydrogen halide acceptor and (c) a diluent, wherein the diluent is water or an aqueous solution containing up to 95% by volume of an organic solvent, provided that at least some diluent water is in a second phase.
Claim 3
Dependent Claim
20 words
The process of claim 1, wherein the catalyst complex is formed from a palladium salt and an organophosphine or organoarsine.
Claim 4
Dependent Claim
17 words
The process of claim 1, wherein the catalyst complex is formed from palladium (II) acetate and tris-(o-tolyl)phosphine.
Claim 5
Dependent Claim
19 words
The process of claim 1, wherein the catalyst complex is formed from a palladium (0) complex and a triarylphosphine.
Claim 6
Dependent Claim
20 words
The process of claim 1, wherein the inorganic hydrogen halide acceptor is an alkali metal acetate, propionate, carbonate or hydroxide.
Claim 7
Dependent Claim
14 words
The process of claim 1, wherein the inorganic hydrogen halide acceptor is sodium acetate.
Claim 8
Dependent Claim
14 words
The process of claim 1, wherein the inorganic hydrogen halide acceptor is potassium acetate.
Claim 9
Dependent Claim
19 words
The process of claim 1, further including an organic hydrogen halide acceptor selected from a secondary or tertiary amine.
Claim 10
Dependent Claim
48 words
The process of claim 8, wherein the organic hydrogen halide acceptor is represented by the formula R 1 R 2 R 3 N and each of R 1 , R 2 and R 3 is selected independently from straight-chain and branched-chain alkyl of 1-8 carbon atoms and cycloalkyl.
Claim 11
Dependent Claim
13 words
The process of claim 8, wherein the organic hydrogen halide acceptor is triethylamine.
Claim 12
Dependent Claim
10 words
The process of claim 1, wherein the diluent is water.
Claim 13
Dependent Claim
29 words
The process of claim 1, wherein the diluent is water and is present in amount exceeding 100% by weight of combined halogenated organic compound and hydrolytically-stable, vinylically-unsaturated precursor compound.
Claim 14
Dependent Claim
46 words
The process of claim 1, wherein the diluent is an aqueous solution consisting of up to 90% by volume of an organic solvent selected from the group consisting of nitriles, alcohols, linear or cyclic saturated esters, N,N-dialkylformamides, N-alkylpyrrolidinones, alkoxyalkanols, glycol ethers, dioxane, tetrahydrofuran, tetrahydropyran or hexaalkylphosphoramides.
Claim 15
Dependent Claim
20 words
The process of claim 1, wherein the diluent is an aqueous solution of 10-90% by volume of dimethylformamide or N-methylpyrrolidinone.
Claim 16
Dependent Claim
20 words
The process of claim 1, wherein the diluent is an aqueous solution of 30-70% by volume of dimethylformamide or N-methylpyrrolidinone.
Claim 17
Dependent Claim
45 words
The process of claim 1, wherein the diluent is an aqueous solution of 30-70% by volume of dimethylformamide or N-methylpyrrolidinone and the diluent is present in an amount equal to at least 70% by weight of combined halogenated organic compound and hydrolytically-stable, vinylically-unsaturated precursor compound.
Claim 18
Dependent Claim
36 words
The process of claim 1, wherein the halogenated organic compound is a bromo or iodo mono- or polycyclic substituted or unsubstituted carbocyclic or heterocyclic aromatic compound or a substituted or unsubstituted benzyl chloride, bromide or iodide.
Claim 19
Dependent Claim
71 words
The process of claim 1, wherein the halogenated organic compound is a brominated benzocyclobutene represented by the formula ##STR9## wherein R 2 is alkyl of 1-6 carbon atoms, alkoxy of 1-6 carbon atoms, trifluoroacetoxy, acyloxy of 1-6 carbon atoms, nitro or chloro; each R 3 is alkyl of 1-6 carbon atoms, aryl, nitro, chloro or cyano; q is 0, 1, 2 or 3 and each r is independently 0 or 1.
Claim 20
Dependent Claim
12 words
The process of claim 1, wherein the halogenated organic compound is 4-bromobenzocyclobutene.
Claim 21
Dependent Claim
24 words
The process of claim 1, wherein the halogenated organic compound is of the formula ArBr, wherein Ar is phenyl or o-, m- or p-tolyl.
Claim 22
Dependent Claim
19 words
The process of claim 1, wherein the halogenated organic compound is a substituted or unsubstituted benzyl chloride or bromide.
Claim 23
Dependent Claim
14 words
The process of claim 1, wherein the halogenated organic compound is a vinylic bromide.
Claim 24
Dependent Claim
14 words
The process of claim 1, wherein the hydrolytically-stable, vinylically-unsaturated precursor compound is a hydrocarbon.
Claim 25
Dependent Claim
13 words
The process of claim 1, wherein the hydrolytically-stable, vinylically-unsaturated precursor compound is ethylene.
Claim 26
Dependent Claim
13 words
The process of claim 1, wherein the hydrolytically-stable, vinylically-unsaturated precursor compound is styrene.
Claim 27
Dependent Claim
20 words
The process of claim 1, wherein the hydrolytically-stable, vinylically-unsaturated precursor compound is o-, m- or p-vinyltoluene or a mixture thereof.
Claim 28
Dependent Claim
20 words
The process of claim 1, wherein the hydrolytically-stable, vinylically-unsaturated precusor compound is o-, m- or p-divinylbenzene or a mixture thereof.
Claim 29
Dependent Claim
33 words
The process of claim 1, wherein the hydrolytically-stable, vinylically-unsaturated precursor compound contains one or more of an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom or a combination thereof.
Claim 30
Dependent Claim
15 words
The process of claim 1, wherein the hydrolytically-stable, vinylically-unsaturated precursor compound is acrylonitrile or methacrylonitrile.
Claim 31
Dependent Claim
34 words
The process of claim 1, wherein the hydrolytically-stable, vinylically-unsaturated precursor compound is an acrylate or methacrylate ester, wherein the alcohol moiety is alkyl of 1-30 carbon atoms or substituted or unsubstituted mono-or bicyclic aryl.
Claim 32
Dependent Claim
22 words
The process of claim 1, wherein the vinylically-unsaturated product compound is a reaction product of 4-bromobenzocyclobutene and a mixture of m-and p-vinyltoluene.
Claim 33
Dependent Claim
18 words
The process of claim 1, wherein the vinylically-unsaturated product compound is a reaction product of 4-bromobenzocyclobutene and divinylbenzene.
Claim 34
Dependent Claim
18 words
The process of claim 1, wherein the vinylically-unsaturated product compound is a reaction product of ethylene and o-bromotoluene.
Claim 35
Dependent Claim
18 words
The process of claim 1, wherein the vinylically-unsaturated product compound is a reaction product of ethylene and 4-bromobenzocyclobutene.
Claim 36
Dependent Claim
18 words
The process of claim 1, wherein the vinylically-unsaturated product compound is a reaction product of styrene and 4-bromobenzocyclobutene.
Claim 37
Dependent Claim
18 words
The process of claim 1, including a further step of treating a resulting crude product with a peroxide.
Claim 38
Dependent Claim
19 words
The process of claim 1, including a further step of chromatographing a resulting crude product over silica or alumina.
Claim 39
Dependent Claim
12 words
The process of claim 37, wherein the peroxide is aqueous hydrogen peroxide.
Claim 40
Dependent Claim
10 words
The process of claim 37, wherein the peroxide is tert-butylhydroperoxide.
Claim 41
Dependent Claim
27 words
The process of claim 1, including the further steps of treating a resulting product with a peroxide and chromatographing the thus-treated crude product over silica or alumina.
References Cited (Backward Citations)
No citation records indexed.
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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) | 1996-09-06 | 1997-03-08 | 1997-09-07 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2000-09-06 | 2001-03-08 | 2001-09-07 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2004-09-06 | 2005-03-08 | 2005-09-07 | $7700.00 | Window Closed / Lapsed |