US4983679A
Expired / Lapsed
US
⏱️ 0.0 years remaining
β-(keto or sulfonyl)esters from reaction of silylketene acetal and acyl or sulfonyl compound
Assignee: EIDP Inc
•
Filing: 1989-04-11
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Granted: 1991-01-08
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Expires: 2009-04-11
Abstract
Abstract Silylketene acetals, including "living" GTP polymers, are acylated or sulfonylated in the presence of GTP-effective catalysts with acyl or sulfonyl compounds to produce beta -ketoesters or beta -sulfonylesters; polymeric products, including capped, coupled and chain-extended polymers and block copolymers can be prepared.
Inventors
- 👤 Gordon M. Cohen
- 👤 Hans J. Reich
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 00:58
CPC Classifications
C; C08; C08G; C08G59/00; C08G59/18; C08G59/20; C08G59/32; C08G59/3209; C08F; C08F293/00; C08F293/005
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
219 words
Process for preparing beta-ketoesters or beta-sulfonylesters comprising contacting and reacting a silylketene acetal with an acyl or sulfonyl compound in the presence of a catalyst which is a source of, (1) an anion selected from the group comprising fluoride, difluorotrimethylsilicate, bifluoride, cyanide and azide ions; or (2) an oxyanion which forms a conjugate acid having a pKa measured in dimethylsulfoxide at 25° C., of about 5 to about 24, the silylketene acetal being of the formula ##STR9## wherein: each Q, independently, is selected from --R 1 , --OR 1 , --N(R 1 ) 2 and --SR 1 ; each R 1 , independently, is a hydrocarbyl or substituted hydrocarbyl radical; R 3 is H, hydrocarbyl or substituted hydrocarbyl; each of R 2 and R 4 , independently, is a hydrocarbyl, substituted hydrocarbyl, or a polymeric radical, the acyl or sulfonyl compound being selected from the group consisting of [XC(O)] n R 5 and [YS(O) 2 ] n R 5 wherein: X is a silicon activating group; Y is --F or --OAr; Ar is aryl or substituted aryl; R 5 is a hydrocarbyl, substituted hydrocarbyl or polymeric radical, of valence n, wherein the carbon adjacent to the C(O) or S(O) 2 is not part of a carbon-carbon double or triple bond; and n is an integer of at least 1.
Claim 2
Dependent Claim
219 words
Process for preparing beta-ketoesters or beta-sulfonylesters comprising contacting and reacting a silylketene acetal with an acyl or sulfonyl compound in the presence of a catalyst which is a source of, (1) an anion selected from the group comprising fluoride, difluorotrimethylsilicate, bifluoride, cyanide and azide ions; or (2) an oxyanion which forms a conjugate acid having a pKa measured in dimethylsulfoxide at 25° C., of about 5 to about 24, the silylketene acetal being of the formula ##STR9## wherein: each Q, independently, is selected from --R 1 , --OR 1 , --N(R 1 ) 2 and --SR 1 ; each R 1 , independently, is a hydrocarbyl or substituted hydrocarbyl radical; R 3 is H, hydrocarbyl or substituted hydrocarbyl; each of R 2 and R 4 , independently, is a hydrocarbyl, substituted hydrocarbyl, or a polymeric radical, the acyl or sulfonyl compound being selected from the group consisting of [XC(O)] n R 5 and [YS(O) 2 ] n R 5 wherein: X is a silicon activating group; Y is --F or --OAr; Ar is aryl or substituted aryl; R 5 is a hydrocarbyl, substituted hydrocarbyl or polymeric radical, of valence n, wherein the carbon adjacent to the C(O) or S(O) 2 is not part of a carbon-carbon double or triple bond; and n is an integer of at least 1.
Claim 3
Dependent Claim
19 words
Process of claim 1 wherein the silylketene acetal is reacted with the acyl compound [XC(O)] n R 5 .
Claim 4
Dependent Claim
20 words
Process of claim 2 wherein X is --F, --OAr or --OC(O)R 6 wherein R 6 is hydrocarbyl or substituted hydrocarbyl.
Claim 5
Dependent Claim
27 words
Process of claim 1 wherein Q in the silylketene acetal is R 1 , R 2 is C 1-8 hydrocarbyl and R 3 is H or methyl.
Claim 6
Dependent Claim
11 words
Process of claim 4 wherein R 4 is a polymeric radical.
Claim 7
Dependent Claim
13 words
Process of claim 5 wherein the polymeric radical is comprised of acrylic units.
Claim 8
Dependent Claim
12 words
Process of claim 6 wherein the polymeric radical contains a functional substituent.
Claim 9
Dependent Claim
17 words
Process of claim 6 wherein the silylketene acetal is a "living" polymer prepared by Group Transfer Polymerization.
Claim 10
Dependent Claim
13 words
Process of claim 8 wherein X is --F, --OAr or --OC(O)R 6 .
Claim 11
Dependent Claim
11 words
Process of claim 9 wherein R 5 is C 1-8 hydrocarbyl.
Claim 12
Dependent Claim
10 words
Process of claim 10 wherein n is 1 or 2.
Claim 13
Dependent Claim
8 words
Process of claim 11 wherein n is 2.
Claim 14
Dependent Claim
19 words
Process of claim 12 wherein R 5 is 1,4-phenylene and X is --F or --OAr wherein Ar is phenyl.
Claim 15
Dependent Claim
13 words
Process of claim 9 wherein the catalyst is fluoride, bifluoride or a oxyanion.
Claim 16
Dependent Claim
14 words
Process of claim 14 wherein the oxyanion is acetate, biacetate, m-chlorobenzoate, benzoate or bibenzoate.
Claim 17
Dependent Claim
9 words
Process of claim 15 wherein the oxyanion is biacetate.
Claim 18
Dependent Claim
16 words
Process of claim 11 wherein different polymeric silylketene acetals are coupled to form a block copolymer.
Claim 19
Dependent Claim
15 words
Process of claim 9 wherein a stoichiometric excess of acyl or sulfonyl compound is employed.
Claim 20
Dependent Claim
23 words
Process of claim 12 wherein the acyl or sulfonyl compound is employed in a molar ratio to the silylketene acetal not exeeding 1:2.
Claim 21
Dependent Claim
24 words
Process of claim 12 wherein the acyl or sulfonyl compound is employed in a molar ratio to the silylketene acetal of 1:2 to 1:1.
Claim 22
Dependent Claim
31 words
The process of claim 1 wherein the catalyst contains a selected anion or oxyanion in an amount of about 0.0001 mol % to about 50 mol % of the silylketene acetal.
References Cited (Backward Citations)
CA701643A
Cited
GB842725A
Cited
DE1076133B
Cited
US3730930A
Cited
US3817946A
Cited
US4027066A
Cited
JPS5334719A
Cited
US4346144A
Cited
US4388448A
Cited
US4417034A
Cited
US4681918A
Cited
US4508880A
Cited
DE3302847A1
Cited
US4414372A
Cited
US4581428A
Cited
US4524196A
Cited
US4598161A
Cited
JPS59213701A
Cited
US4711942A
Cited
US4482729A
Cited
US4656233A
Cited
US4605716A
Cited
US4588795A
Cited
US4622372A
Cited
US4822859A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1994-01-07 | 1994-07-09 | 1995-01-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1998-01-07 | 1998-07-09 | 1999-01-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2002-01-07 | 2002-07-09 | 2003-01-08 | $7700.00 | Window Closed / Lapsed |