US5138081A
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Process for purifying vinylically-unsaturated organosilicon compounds
Assignee: Dow Chemical Co
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Filing: 1991-04-30
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Granted: 1992-08-11
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Expires: 2011-04-30
Abstract
Abstract A process for purifying an impure vinylically-unsaturated organosilicon product compound prepared by reaction between a vinylically-unsaturated organosilicon precursor and a halogenated organic compound in the presence of a homogeneous zerovalent palladium catalyst complex, the catalyst complex including an organophosphine or organoarsine ligand, in the presence of a hydrogen halide acceptor in an essentially anhydrous diluent, comprising treating a mixture containing the impure vinylically-unsaturated organosilicon product compound with a peroxide for a time sufficient to oxidize organophosphine or organoarsine impurities present in a mixture being treated. The peroxide can be selected from aqueous hydrogen peroxide or organic peroxides. The thus-treated mixture can be further treated by chromatography over silica gel or alumina. In optional embodiments, chromatography over silica gel or alumina can precede treatment with the peroxide.
Inventors
- 👤 Robert A. DeVries
- 👤 Mary L. Ash
- 👤 Hughie R. Frick, deceased
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 19:54
CPC Classifications
C; C07; C07F; C07F7/00; C07F7/02; C07F7/08; C07F7/18; C07F7/1896; C07F7/0834; C07F7/0838; C07F7/0872; C07F7/0889; C07F7/089; C07F7/1804; C07F7/1872; C07F7/1892; C07F7/20
Claims Analysis
Total Claims: 43
Claim 1
Independent Claim
86 words
A process for purifying an impure vinylically-unsaturated organosilicon product compound prepared by reaction between a vinylically-unsaturated organosilicon precursor compound and a halogenated organic compound in the presence of a homogeneous zerovalent palladium catalyst complex, the catalyst complex including an organophosphine or organoarsine ligand, in the presence of a hydrogen halide acceptor in an essentially anhydrous diluent, comprising treating a mixture containing the impure vinylically-unsaturated organosilicon product compound with a peroxide for a time sufficient to oxidize organophosphine or organoarsine impurities present in a mixture being treated.
Claim 2
Dependent Claim
86 words
A process for purifying an impure vinylically-unsaturated organosilicon product compound prepared by reaction between a vinylically-unsaturated organosilicon precursor compound and a halogenated organic compound in the presence of a homogeneous zerovalent palladium catalyst complex, the catalyst complex including an organophosphine or organoarsine ligand, in the presence of a hydrogen halide acceptor in an essentially anhydrous diluent, comprising treating a mixture containing the impure vinylically-unsaturated organosilicon product compound with a peroxide for a time sufficient to oxidize organophosphine or organoarsine impurities present in a mixture being treated.
Claim 3
Dependent Claim
20 words
The process of claim 1, wherein the vinylically-unsaturated organosilicon precursor compound is a vinyl, ethynyl, allyl or methallyl organosilicon compound.
Claim 4
Dependent Claim
12 words
The process of claim 1, wherein the peroxide is aqueous hydrogen peroxide.
Claim 5
Dependent Claim
12 words
The process of claim 1, wherein the peroxide is an organic peroxide.
Claim 6
Dependent Claim
11 words
The process of claim 4, wherein the peroxide is tert-butyl hydroperoxide.
Claim 7
Dependent Claim
11 words
The process of claim 4, wherein the peroxide is cumene hydroperoxide.
Claim 8
Dependent Claim
11 words
The process of claim 4, wherein the peroxide is perbenzoic acid.
Claim 9
Dependent Claim
16 words
The process of claim 1, including a preliminary step of chromatographing the mixture over silica gel.
Claim 10
Dependent Claim
15 words
The process of claim 1, including a preliminary step of chromatographing the mixture over alumina.
Claim 11
Dependent Claim
17 words
The process of claim 1, including a further step of chromatographing the thus-purified compound over silica gel.
Claim 12
Dependent Claim
16 words
The process of claim 1, including a further step of chromatographing the thus-purified compound over alumina.
Claim 13
Dependent Claim
41 words
The process of claim 1, wherein the essentially anhydrous diluent comprises an organic solvent selected from the group consisting of linear and cyclic esters, alcohols, nitriles, dialkylformamides, N-alkylpyrrolidinones, alkoxyalkanols, glycol ethers, ketones, dioxane, tetrahydrofuran, tetrahydropyran or hexaalkylphosphoramides, or a mixture thereof.
Claim 14
Dependent Claim
11 words
The process of claim 12, wherein the anhydrous diluent is N,N-dimethylformamide.
Claim 15
Dependent Claim
11 words
The process of claim 12, wherein the anhydrous diluent is N-methylpyrrolidinone.
Claim 16
Dependent Claim
11 words
The process of claim 12, wherein the anhydrous diluent is acetonitrile.
Claim 17
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 18
Dependent Claim
18 words
The process of claim 1, wherein the catalyst complex is formed from palladium (II) acetate and a triarylphosphine.
Claim 19
Dependent Claim
19 words
The process of claim 1, wherein the catalyst complex is formed from a palladium (0) complex and a triarylphosphine.
Claim 20
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 21
Dependent Claim
16 words
The process of claim 1, wherein the hydrogen halide acceptor is a secondary or tertiary amine.
Claim 22
Dependent Claim
47 words
The process of claim 20, wherein the 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 23
Dependent Claim
12 words
The process of claim 20, wherein the hydrogen halide acceptor is triethylamine.
Claim 24
Dependent Claim
35 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 or bromide.
Claim 25
Dependent Claim
71 words
The process of claim 1, wherein the halogenated organic compound is a brominated benzocyclobutene represented by the formula ##STR8## 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 26
Dependent Claim
12 words
The process of claim 24, wherein the halogenated organic compound is 4-bromobenzocyclobutene.
Claim 27
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 28
Dependent Claim
19 words
The process of claim 1, wherein the halogenated organic compound is a substituted or unsubstituted benzyl chloride or bromide.
Claim 29
Dependent Claim
23 words
The process of claim 1, wherein the vinylically-unsaturated organosilicon precursor compound is a trialkoxyvinylsilane, wherein alkyl or alkoxy is of 1-6 carbon atoms.
Claim 30
Dependent Claim
10 words
The process of claim 28, wherein the trialkoxysilane is trimethoxyvinylsilane.
Claim 31
Dependent Claim
10 words
The process of claim 28, wherein the trialkoxyvinylsilane is triethoxyvinylsilane.
Claim 32
Dependent Claim
13 words
The process of claim 1, wherein the vinylically-unsaturated organosilicon precursor compound is triacetoxyvinylsilane.
Claim 33
Dependent Claim
48 words
The process of claim 1, wherein the vinylically-unsaturated organosilicon precursor compound is of the formula ##STR9## wherein each R is independently alkyl of 1-6 carbon atoms, cycloalkyl, aralkyl or aryl; each R 1 is independently vinyl, allyl or methallyl and n is an integer from 1 to 4500.
Claim 34
Dependent Claim
21 words
The process of claim 1, wherein the vinylically-unsaturated organosilicon precursor compound is [CH 2 ═CH--Si(CH 3 ) 2 ] 2 O.
Claim 35
Dependent Claim
19 words
The process of claim 1, wherein the vinylically-unsaturated organosilicon product compound is a reaction product of 4-bromobenzocyclobutene and 1,1'-divinyltetramethyldisiloxane.
Claim 36
Dependent Claim
26 words
The process of claim 1, wherein the vinylically-unsaturated organosilicon compound is a reaction product of 4-bromobenzocyclobutene and a trialkoxyvinylsilane and alkoxy is of 1-6 carbon atoms.
Claim 37
Dependent Claim
19 words
The process of claim 35, wherein the vinylically-unsaturated organosilicon product compound is a reaction product from 4-bromobenzocyclobutene and triethoxyvinylsilane.
Claim 38
Dependent Claim
19 words
The process of claim 35, wherein the vinylically-unsaturated organosilicon product compound is a reaction product from 4-bromobenzocyclobutene and trimethoxyvinylsilane.
Claim 39
Dependent Claim
19 words
The process of claim 1, wherein the vinylically-unsaturated organosilicon product compound is a reaction product of 4-bromobenzocyclobutene and triacetoxyvinylsilane.
Claim 40
Dependent Claim
28 words
The process of claim 1, wherein the vinylically-unsaturated organosilicon product compound is a reaction product of 4-bromobenzocyclobutene and trimethoxyvinylsilane or triethoxyvinylsilane and the peroxide is aqueous hydrogen peroxide.
Claim 41
Dependent Claim
27 words
The process of claim 1, wherein the vinylically-unsaturated organosilicon product compound is a reaction product of 4-bromobenzocyclobutene and trimethoxyvinylsilane or triethoxyvinylsilane and the peroxide is tert-butyl hydroperoxide.
Claim 42
Dependent Claim
16 words
The process of claim 39, wherein the thus-purified mixture is chromatographed over silica gel or alumina.
Claim 43
Dependent Claim
16 words
The process of claim 40, wherien the thus-purified mixture is chromatographed over silica gel or alumina.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1995-08-11 | 1996-02-10 | 1996-08-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1999-08-11 | 2000-02-10 | 2000-08-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2003-08-11 | 2004-02-10 | 2004-08-11 | $7700.00 | Window Closed / Lapsed |