US4309557A
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Process for the preparation of alkyl and aryl substituted oligosiloxanes suitable for use as diffusion pump oils
Assignee: Nusil Technology LLC
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Filing: 1981-02-12
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Granted: 1982-01-05
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Expires: 2001-02-12
Abstract
Abstract An improved process for preparing 1,3-dialkyl-1,1,3,3-tetraryldisiloxanes and 1,3,5-trialkyl-1,1,3,5,5-pentaaryltrisiloxanes is disclosed. The process utilizes an aryl Grignard reagent to affect displacement of alkoxy, preferably methoxy, groups in the corresponding alkyl-alkoxy substituted di-, and trisiloxanes. Alternatively, partial replacement of the alkoxy groups in an alkyltrialkoxysilane with aryl groups in a Grignard reaction, and subsequent hydrolyis of the remaining alkoxy groups yield the above-noted desired compounds.
Inventors
- 👤 Richard A. Compton
- 👤 Del J. Petraitis
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 19:09
CPC Classifications
C; C07; C07F; C07F7/00; C07F7/02; C07F7/08; C07F7/0834; C07F7/0838; C07F7/0872; C07F7/0874; C07F7/0876; C07F7/0878
Claims Analysis
Total Claims: 60
Claim 1
Independent Claim
180 words
A process for preparing compounds of the general formula: ##STR6## wherein n equals 0 or 1, Alkyl 1 is an alkyl group having 1-2 carbons and R is an aryl, or alkylaryl group said alkylaryl group having 1-2 carbons in the alkyl chain, the process comprising the steps of: reacting a compound of the general formula of Alkyl 1 --Si--(OAlkyl 2 ) 3 wherein Alkyl 1 is defined as above and Alkyl 2 is an alkyl group having 1-6 carbon atoms, with a Grignard reagent derived from a compound having the general formula of R--X, wherein R is defined as above and X is Cl, Br or I, said reaction with the Grignard reagent giving rise to a mixture containing the compounds of the following two general formulae: ##STR7## wherein Alkyl 1 , Alkyl 2 and R have the same definition as above; subjecting a mixture containing at least the compounds of the two general formulae: ##STR8## to hydrolysis to remove the OAlkyl 2 groups, and substantially simultaneously with said hydrolysis allowing condensation of the respective siloxanes moieties to occur.
Claim 2
Dependent Claim
180 words
A process for preparing compounds of the general formula: ##STR6## wherein n equals 0 or 1, Alkyl 1 is an alkyl group having 1-2 carbons and R is an aryl, or alkylaryl group said alkylaryl group having 1-2 carbons in the alkyl chain, the process comprising the steps of: reacting a compound of the general formula of Alkyl 1 --Si--(OAlkyl 2 ) 3 wherein Alkyl 1 is defined as above and Alkyl 2 is an alkyl group having 1-6 carbon atoms, with a Grignard reagent derived from a compound having the general formula of R--X, wherein R is defined as above and X is Cl, Br or I, said reaction with the Grignard reagent giving rise to a mixture containing the compounds of the following two general formulae: ##STR7## wherein Alkyl 1 , Alkyl 2 and R have the same definition as above; subjecting a mixture containing at least the compounds of the two general formulae: ##STR8## to hydrolysis to remove the OAlkyl 2 groups, and substantially simultaneously with said hydrolysis allowing condensation of the respective siloxanes moieties to occur.
Claim 3
Dependent Claim
9 words
The process of claim 1 wherein n is 0.
Claim 4
Dependent Claim
16 words
The process of claim 2 wherein Alkyl 1 is CH 3 , and R is phenyl.
Claim 5
Dependent Claim
12 words
The process of claim 3 wherein Alkyl 2 is CH 3 .
Claim 6
Dependent Claim
9 words
The process of claim 1 wherein n is 1.
Claim 7
Dependent Claim
12 words
The process of claim 5 wherein Alkyl 1 is CH 3 .
Claim 8
Dependent Claim
12 words
The process of claim 5 wherein Alkyl 2 is CH 3 .
Claim 9
Dependent Claim
18 words
The process of claim 5 wherein Alkyl 1 is CH 3 and Alkyl 2 is CH 3 .
Claim 10
Dependent Claim
9 words
The process of claim 5 wherein R is phenyl.
Claim 11
Dependent Claim
21 words
The process of claim 5 wherein Alkyl 1 is CH 3 , Alkyl 2 is CH 3 and R is phenyl.
Claim 12
Dependent Claim
9 words
The process of claim 10 wherein X is Br.
Claim 13
Dependent Claim
24 words
The process of claim 10 wherein in the reacting step the molar ratio of CH 3 --Si--(OCH 3 ) 3 PhX is approximately 1:1.5-1.75.
Claim 14
Dependent Claim
33 words
The process of claim 12 additionally comprising the step of isolating by fractional distillation after the reacting step a fraction essentially consisting of compounds selected from a class consisting of methylmethoxydiphenylsilane and methyldimethoxyphenylsilane.
Claim 15
Dependent Claim
21 words
The process of claim 12 further comprising the step of isolating after the reacting step a fraction essentially consisting of methyl-dimethoxyphenysilane.
Claim 16
Dependent Claim
24 words
The process of claim 15 wherein in the reacting step said methyl-dimethoxyphenylsilane is added to the reaction mixture to increase the yield of methylmethoxydiphenylsilane.
Claim 17
Dependent Claim
29 words
The process of claim 13 further comprising the step of adjusting by fractional distillation prior to said hydrolysing step the molar ratio of methyl-methoxydiphenylsilane and methyl-dimethoxyphenysilane to approximately 2:1.2.
Claim 18
Dependent Claim
21 words
The process of claim 16 wherein the hydrolysis step is performed with aqueous alkali metal or alkali earth metal hydroxide solution.
Claim 19
Dependent Claim
17 words
The process of claim 17 wherein the step of hydrolysis is performed with aqueous potassium hydroxide solution.
Claim 20
Dependent Claim
22 words
The process of claim 1 wherein the step of hydrolysis is performed with aqueous alkali metal or alkali earth metal hydroxide solution.
Claim 21
Dependent Claim
17 words
The process of claim 19 wherein the step of hydrolysis is performed with aqueous potassium hydroxide solution.
Claim 22
Dependent Claim
148 words
A process for preparing compounds of the general formula ##STR9## wherein n equals 0 or 1, and Alkyl 1 is an alkyl group having 1-2 carbons, and R is an aryl or alkylaryl group, said alkylaryl group having 1-2 carbons in the alkyl chain, the process comprising the steps of: hydrolysing and substantially simultaneously condensing a compound of the general formula of Alkyl.sub.1 --Si--(OAlkyl.sub.2).sub.3 wherein Alkyl 1 is defined as above and Alkyl 2 is an alkyl group having 1-6 carbons, to yield linear oligosiloxanes of the general formula ##STR10## wherein n equals 0 or 1, and Alkyl 1 and Alkyl 2 are defined as above, and reacting at least one of the linear oligosiloxanes of the above defined general formula with a Grignard reagent derived from a compound having the general formual of R-X wherein R is defined as above and X is Cl, Br or I.
Claim 23
Dependent Claim
148 words
A process for preparing compounds of the general formula ##STR9## wherein n equals 0 or 1, and Alkyl 1 is an alkyl group having 1-2 carbons, and R is an aryl or alkylaryl group, said alkylaryl group having 1-2 carbons in the alkyl chain, the process comprising the steps of: hydrolysing and substantially simultaneously condensing a compound of the general formula of Alkyl.sub.1 --Si--(OAlkyl.sub.2).sub.3 wherein Alkyl 1 is defined as above and Alkyl 2 is an alkyl group having 1-6 carbons, to yield linear oligosiloxanes of the general formula ##STR10## wherein n equals 0 or 1, and Alkyl 1 and Alkyl 2 are defined as above, and reacting at least one of the linear oligosiloxanes of the above defined general formula with a Grignard reagent derived from a compound having the general formual of R-X wherein R is defined as above and X is Cl, Br or I.
Claim 24
Dependent Claim
9 words
The process of claim 21 wherein n equals 0.
Claim 25
Dependent Claim
12 words
The process of claim 22 wherein Alkyl 1 is CH 3 .
Claim 26
Dependent Claim
12 words
The process of claim 22 wherein Alkyl 2 is CH 3 .
Claim 27
Dependent Claim
18 words
The process of claim 22 wherein Alkyl 1 is CH 3 and Alkyl 2 is CH 3 .
Claim 28
Dependent Claim
9 words
The process of claim 22 wherein R is phenyl.
Claim 29
Dependent Claim
21 words
The process of claim 22 wherein Alkyl 1 is CH 3 , Alkyl 2 is CH 3 and R is phenyl.
Claim 30
Dependent Claim
9 words
The process of claim 27 wherein X is Br.
Claim 31
Dependent Claim
9 words
The process of claim 21 wherein n equals 1.
Claim 32
Dependent Claim
12 words
The process of claim 29 wherein Alkyl 1 is CH 3 .
Claim 33
Dependent Claim
12 words
The process of claim 29 wherein Alkyl 2 is CH 3 .
Claim 34
Dependent Claim
15 words
The process of claim 29 wherein Alkyl 1 and Alkyl 2 are CH 3 .
Claim 35
Dependent Claim
9 words
The process of claim 29 wherein R is phenyl.
Claim 36
Dependent Claim
15 words
The process of claim 29 wherein Alkyl 1 is CH 3 and R is phenyl.
Claim 37
Dependent Claim
12 words
The process of claim 34 wherein Alkyl 2 is CH 3 .
Claim 38
Dependent Claim
9 words
The process of claim 35 wherein X is Br.
Claim 39
Dependent Claim
30 words
The process of claim 35 further comprising the step of separating prior to the reacting step a mixture comprising 1,3-dimethyl, 1,1,3,3-tetramethoxydisiloxane, and 1,3,5 trimethyl, 1,1,3,5,5-pentamethoxytrisiloxane from unreacted methyltrimethoxysilane and methanol.
Claim 40
Dependent Claim
23 words
The process of claim 37 further comprising the step of isolating prior to said reacting step substantially pure 1,3,5-trimethyl, 1,1,3,5,5-pentamethoxytrisiloxane from said mixture.
Claim 41
Dependent Claim
17 words
The process of claim 37 wherein the step of hydrolysing is conducted with aqueous sodium hydroxide solution.
Claim 42
Dependent Claim
17 words
The process of claim 21 wherein the step of hydrolysing is conducted with aqueous sodium hydroxide solution.
Claim 43
Dependent Claim
130 words
A process for preparing a 1,3,5 trimethyl-1,1,3,5,5 pentaphenyltrisiloxane, said process comprising the steps of: hydrolysing and substantially simultaneously condensing a compound having the general formula of CH 3 --Si--(OAlkyl 2 ) 3 , wherein Alkyl 2 is an alkyl group having 1-6 carbons, with water in the presence of a catalyst selected from a group consisting of strong bases, strong acids, weak acids and acid anhydrides; isolating from the medium of said hydrolysis and condensation and in a state substantially free of methanol and unreacted CH 3 --Si--(OAlkyl 2 ) 3 ) a mixture comprising 1,3,5-trimethyl-1,1,3,5,5-pentaalkoxytrisiloxane and 1,3-trimethyl, 1,1,3,3 tetraalkoxydisiloxane; reacting said 1,3,5-trimethyl-1,1,3,5,5-pentaalkoxytrisiloxane with a Grignard reagent derived from Ph-X, wherein X is Cl, Br or I, and isolating by fractional distillation from the products of said Grignard reaction 1,3,5-trimethyl-1,1,3,5,5-pentaphenyltrisiloxane.
Claim 44
Dependent Claim
130 words
A process for preparing a 1,3,5 trimethyl-1,1,3,5,5 pentaphenyltrisiloxane, said process comprising the steps of: hydrolysing and substantially simultaneously condensing a compound having the general formula of CH 3 --Si--(OAlkyl 2 ) 3 , wherein Alkyl 2 is an alkyl group having 1-6 carbons, with water in the presence of a catalyst selected from a group consisting of strong bases, strong acids, weak acids and acid anhydrides; isolating from the medium of said hydrolysis and condensation and in a state substantially free of methanol and unreacted CH 3 --Si--(OAlkyl 2 ) 3 ) a mixture comprising 1,3,5-trimethyl-1,1,3,5,5-pentaalkoxytrisiloxane and 1,3-trimethyl, 1,1,3,3 tetraalkoxydisiloxane; reacting said 1,3,5-trimethyl-1,1,3,5,5-pentaalkoxytrisiloxane with a Grignard reagent derived from Ph-X, wherein X is Cl, Br or I, and isolating by fractional distillation from the products of said Grignard reaction 1,3,5-trimethyl-1,1,3,5,5-pentaphenyltrisiloxane.
Claim 45
Dependent Claim
12 words
The process of claim 41 wherein Alkyl 2 is CH 3 .
Claim 46
Dependent Claim
11 words
The process of claim 42 wherein the catalyst is sodium hydroxide.
Claim 47
Dependent Claim
9 words
The process of claim 42 wherein X is Br.
Claim 48
Dependent Claim
28 words
The process of claim 41 wherein Alkyl 2 is CH 3 and wherein the process additionally comprises the step of separating by distillation 1,3, dimethyl-1,1,3,3-tetramethoxydisiloxane from said mixture.
Claim 49
Dependent Claim
146 words
A process for preparing compounds having the general formula of ##STR11## wherein n is 0 or 1, Alkyl 1 is an alkyl group having 1-2 carbons and R is an aryl, or alkylaryl group, said alkylaryl group having 1-2 carbons in the alkyl chain, and Y is the same as R, or is an alkyl group having 1-2 carbons, the process comprising the step of: reacting with a Grignard reagent derived from R-X wherein X is Cl, Br or I and R is defined as above, compounds having the general formula of ##STR12## wherein n and Alkyl 1 are defined as above, Alkyl 2 is an alkyl group having 1-6 carbons, and Z is an alkoxy group having 1-6 carbons or is an alkyl group having 1-2 carbons, with the further restriction that when Z is an alkyl group then Y is the same as Z.
Claim 50
Dependent Claim
146 words
A process for preparing compounds having the general formula of ##STR11## wherein n is 0 or 1, Alkyl 1 is an alkyl group having 1-2 carbons and R is an aryl, or alkylaryl group, said alkylaryl group having 1-2 carbons in the alkyl chain, and Y is the same as R, or is an alkyl group having 1-2 carbons, the process comprising the step of: reacting with a Grignard reagent derived from R-X wherein X is Cl, Br or I and R is defined as above, compounds having the general formula of ##STR12## wherein n and Alkyl 1 are defined as above, Alkyl 2 is an alkyl group having 1-6 carbons, and Z is an alkoxy group having 1-6 carbons or is an alkyl group having 1-2 carbons, with the further restriction that when Z is an alkyl group then Y is the same as Z.
Claim 51
Dependent Claim
12 words
The process of claim 46 wherein Alkyl 1 is CH 3 .
Claim 52
Dependent Claim
12 words
The process of claim 46 wherein Alkyl 2 is CH 3 .
Claim 53
Dependent Claim
15 words
The process of claim 46 wherein Alkyl 1 and Alkyl 2 are CH 3 .
Claim 54
Dependent Claim
9 words
The process of claim 46 wherein R is phenyl.
Claim 55
Dependent Claim
19 words
The process of claim 46 wherein n is 1, R is phenyl and Alkyl 1 is CH 3 .
Claim 56
Dependent Claim
27 words
The process of claim 46 wherein n is 1, R is phenyl, Y is phenyl, Z is OCH 3 , and Alkyl 2 is CH 3 .
Claim 57
Dependent Claim
9 words
The process of claim 52 wherein X is Br.
Claim 58
Dependent Claim
28 words
The process of claim 46 wherein n is 1, Z is CH 3 , Y is CH 3 Alkyl 1 is CH 3 , and R is phenyl.
Claim 59
Dependent Claim
12 words
The process of claim 54 wherein Alkyl 2 is CH 3 .
Claim 60
Dependent Claim
9 words
The process of claim 55 wherein X is Br.
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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) | 1985-01-04 | 1985-07-06 | 1986-01-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-01-04 | 1989-07-06 | 1990-01-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-01-04 | 1993-07-06 | 1994-01-05 | $7700.00 | Window Closed / Lapsed |