US4448980A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Preparation of trialkylsilyl ethers
Assignee: EIDP Inc
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Filing: 1983-09-22
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Granted: 1984-05-15
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Expires: 2003-09-22
Abstract
Abstract In an improved catalytic process for preparing trialkylsilyl ethers from trialkylsilyl compounds and carbonyl group-containing compounds, the improvement consisting of using an organic or inorganic bifluoride (HF2(-)) as the catalyst.
Inventors
- 👤 Dotsevi Y. Sogah
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 10:45
CPC Classifications
C; C07; C07F; C07F7/00; C07F7/02; C07F7/08; C07F7/18; C07F7/1804; C07F7/1872; C07F7/1892
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
218 words
Process comprising contacting and reacting (R) 3 SiZ and R 1 --C(O)--R 2 wherein R is C 1-4 alkyl; R 1 is C 1-10 alkyl or C 6-10 cycloalkyl, aryl, alkaryl or aralkyl; R 2 is --H, C 1-10 alkyl or C 6-10 cycloalkyl, aryl, alkaryl, aralkyl or --OR 3 ; R 3 is --Si(R) 3 or C 1-4 alkyl, optionally substituted with --Si(R) 3 or --OSi(R) 3 ; R 1 and R 2 taken together are --CH 2 -- 5 ; and ##STR12## --H, --CN, --N 3 , --Sr, --OP(OR 3 ) 2 , --OP[N(R) 2 ] 2 , ##STR13## --CH 2 CN or --C 6 F 5 ; R 4 and R 5 are independently selected from --H and C 1-4 alkyl; R 6 is --H, C 1-6 alkyl, aryl or --OR 7 ; and R 7 is --Si(R) 3 or C 1-4 alkyl, optionally substituted with --Si(R) 3 or --OSi(R) 3 , in the presence of a catalytic amount of bifluoride (HF 2 .sup.⊖) catalyst to produce the trialkylsilyl ether ##STR14## wherein X is --Si(R) 3 ; R, R 1 and R 2 are as defined above; and ##STR15## --H, --CN, --N 3 , --SR, --OP(OR 3 ) 2 , --OP[N(R) 2 ] 2 , ##STR16## --CH 2 CN or --C 6 F 5 .
Claim 2
Dependent Claim
218 words
Process comprising contacting and reacting (R) 3 SiZ and R 1 --C(O)--R 2 wherein R is C 1-4 alkyl; R 1 is C 1-10 alkyl or C 6-10 cycloalkyl, aryl, alkaryl or aralkyl; R 2 is --H, C 1-10 alkyl or C 6-10 cycloalkyl, aryl, alkaryl, aralkyl or --OR 3 ; R 3 is --Si(R) 3 or C 1-4 alkyl, optionally substituted with --Si(R) 3 or --OSi(R) 3 ; R 1 and R 2 taken together are --CH 2 -- 5 ; and ##STR12## --H, --CN, --N 3 , --Sr, --OP(OR 3 ) 2 , --OP[N(R) 2 ] 2 , ##STR13## --CH 2 CN or --C 6 F 5 ; R 4 and R 5 are independently selected from --H and C 1-4 alkyl; R 6 is --H, C 1-6 alkyl, aryl or --OR 7 ; and R 7 is --Si(R) 3 or C 1-4 alkyl, optionally substituted with --Si(R) 3 or --OSi(R) 3 , in the presence of a catalytic amount of bifluoride (HF 2 .sup.⊖) catalyst to produce the trialkylsilyl ether ##STR14## wherein X is --Si(R) 3 ; R, R 1 and R 2 are as defined above; and ##STR15## --H, --CN, --N 3 , --SR, --OP(OR 3 ) 2 , --OP[N(R) 2 ] 2 , ##STR16## --CH 2 CN or --C 6 F 5 .
Claim 3
Dependent Claim
18 words
Process of claim 1 wherein the molar ratio of HF 2 .sup.⊖ to (R) 3 SiZ is 0.001-0.1:1.0.
Claim 4
Dependent Claim
18 words
Process of claim 1 wherein the molar ratio of HF 2 .sup.⊖ to (R) 3 SiZ is 0.005-0.5:1.0.
Claim 5
Dependent Claim
30 words
Process of claim 1 wherein the bifluoride catalyst is selected from tris(dialkylamino)sulfonium bifluorides, wherein each alkyl contains 1 to 20 carbon atoms, and alkali metal, ammonium and quaternary ammonium bifluorides.
Claim 6
Dependent Claim
11 words
Process of claim 4 wherein the bifluoride catalyst is tris(dimethylamino)sulfonium bifluoride.
Claim 7
Dependent Claim
35 words
Process of claim 1 wherein (R) 3 SiZ, R 1 --C(O)--R 2 and the bifluoride catalyst are admixed at -80° to 100° C. and thereafter the process is carried out at 0° to 80° C.
Claim 8
Dependent Claim
15 words
Process of claim 6 wherein the process is carried out at 15° to 40° C.
Claim 9
Dependent Claim
19 words
Process of claim 1 wherein (R) 3 SiZ and R 1 --C(O)--R 2 are contacted in approximately equimolar quantities.
Claim 10
Dependent Claim
12 words
Process of claim 1 carried out in the presence of a solvent.
Claim 11
Dependent Claim
16 words
Process of claim 9 wherein the molar ratio of solvent to (R) 3 SiZ is 1-500:1.
Claim 12
Dependent Claim
23 words
Process of claim 9 wherein the solvent is selected from tetrahydrofuran, acetonitrile, nitromethane, toluene, xylene, chlorobenzene, benzonitrile, glyme, diglyme and methyl tert-butyl ether.
Claim 13
Dependent Claim
9 words
Process of claim 9 wherein the solvent is tetrahydrofuran.
Claim 14
Dependent Claim
10 words
Process of claim 1 carried out at about atmospheric pressure.
Claim 15
Dependent Claim
17 words
Process of claim 1 comprising the further step of hydrolyzing the silyl ether product to an alcohol.
Claim 16
Dependent Claim
16 words
Process of claim 14 wherein said hydrolysis is carried out in the presence of fluoride ion.
Claim 17
Dependent Claim
8 words
Process of claim 1 wherein Z is ##STR17##
Claim 18
Dependent Claim
46 words
Process of claim 16 wherein R 4 and R 5 , independently, are --H or --CH 3 , R 6 is C 1-6 alkyl, phenyl or --OR 7 and R 7 is C 1-4 alkyl, --Si(R) 3 , or --CH 2 CH 2 OSi(R) 3 .
Claim 19
Dependent Claim
23 words
Process of claim 17 wherein R 1 is C 1-10 alkyl, cyclohexyl or phenyl and R 2 is --H or --CH 3 .
Claim 20
Dependent Claim
10 words
Process of claim 18 wherein the catalyst is tris(dimethylamino)sulfonium bifluoride.
Claim 21
Dependent Claim
8 words
Process of claim 1 wherein Z is ##STR18##
Claim 22
Dependent Claim
19 words
process of claim 20 wherein R is --CH 3 , R 1 is phenyl and R 2 is --H.
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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) | 1987-05-15 | 1987-11-14 | 1988-05-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-05-15 | 1991-11-14 | 1992-05-15 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-05-15 | 1995-11-14 | 1996-05-15 | $7700.00 | Window Closed / Lapsed |