US3907852A
Expired / Lapsed
US
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Silylhydrocarbyl phosphines and related compounds
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1972-06-23
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Granted: 1975-09-23
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Expires: 1992-06-23
Abstract
Abstract Novel heterogeneous silylhydrocarbyl phosphine transition metal complex catalysts and intermediates therefore are prepared by (a) the selective monoaddition of silanes having chlorine, alkoxy or acyloxy groups to an Alpha , omega -diene (b) followed by the addition of a phosphine to the resulting omega -alkenyl silanes to form the corresponding silylalkyl phosphines (c) which are then covalently anchored as such or in the form of their transition metal complexes via condensation of their reactive silane substituents with hydroxy groups of silica and metal oxides, (d) optionally followed by complexing the free phosphine groups of anchored silylalkyl phosphines with transition metal compounds.
Inventors
- 👤 Alexis A Oswald
- 👤 Lawrence L Murrell
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 19:03
CPC Classifications
C; C07; C07F; C07F9/00; C07F9/02; B; B01; B01J; B01J31/00; B01J31/16; B01J31/1616; B01J31/1625; B01J31/1633; B01J31/20; B01J31/24; B01J31/2404; C07C; C07C5/00; C07C5/02; C07C5/03; C07C51/00; C07C51/10; C07C51/12; C07F7/00; C07F7/02; C07F7/08; C07F7/12; C07F7/14; C07F7/18; C07F7/1804; C07F7/1872; C07F7/1876; C07F7/188; C07F7/1892; B01J2231/00; B01J2231/60; B01J2231/64; B01J2231/641; B01J2231/645; B01J2531/00; B01J2531/80; B01J2531/82; B01J2531/822; B01J2531/824; B01J2531/84; B01J2531/845; C07C2531/00; C07C2531/16; C07C2531/24
Claims Analysis
Total Claims: 37
Claim 1
Independent Claim
18 words
A METHOD FOR THE PREPARATION OF SILYALKYL PHOSPHINES COMPRISING THE STEP OF SELECTIVELY REACTING PHOSPHINE OFF THE FORMULA
Claim 2
Independent Claim
18 words
A METHOD FOR THE PREPARATION OF SILYALKYL PHOSPHINES COMPRISING THE STEP OF SELECTIVELY REACTING PHOSPHINE OFF THE FORMULA
Claim 3
Dependent Claim
22 words
The method of claim 1 wherein x is 1 or 2, R is chlorine, methyl, phenyl, and l is 3 to 12.
Claim 4
Dependent Claim
24 words
A method of claim 1 wherein the phosphine is of the formula R''2PH and the omega -alkenyl silane is of the formula R3Si(CH2)1CH CH2.
Claim 5
Dependent Claim
24 words
A method of claim 1 wherein the phosphine is of the formula R''PH2 and the omega -alkenyl silane is of the formula R3Si(CH2)1CH CH2.
Claim 6
Independent Claim
76 words
A method for the preparation of silylalkylphosphines comprising the step of selectively reacting phosphines of the general formula: R''2PH wherein R'' is selected from the group of C1 to C4 alkyl, cyclohexyl and phenyl; with omega -alkenyl trichlorosilanes of the formula: Cl3Si(CH2)1CH CH2 wherein 1 is 3 to 32; at temperatures between -100* and +16*C with radiation initiation, to a phosphine conversion in excess of 50% to yield the corresponding free radical adducts of anti-Markovnikov orientation.
Claim 7
Independent Claim
76 words
A method for the preparation of silylalkylphosphines comprising the step of selectively reacting phosphines of the general formula: R''2PH wherein R'' is selected from the group of C1 to C4 alkyl, cyclohexyl and phenyl; with omega -alkenyl trichlorosilanes of the formula: Cl3Si(CH2)1CH CH2 wherein 1 is 3 to 32; at temperatures between -100* and +16*C with radiation initiation, to a phosphine conversion in excess of 50% to yield the corresponding free radical adducts of anti-Markovnikov orientation.
Claim 8
Dependent Claim
11 words
The method of claim 3 wherein l is 3 to 12.
Claim 9
Independent Claim
41 words
A method for preparing omega -trichlorosilyloctyl diphenyl phosphine, said method comprising the step of selectively reacting diphenyl phosphine with omega -trichlorosilyloctene-1at temperatures between -100* and +16*C with radiation initiation to a phosphine conversion in excess of 50% to produce said compound.
Claim 10
Independent Claim
41 words
A method for preparing omega -trichlorosilyloctyl diphenyl phosphine, said method comprising the step of selectively reacting diphenyl phosphine with omega -trichlorosilyloctene-1at temperatures between -100* and +16*C with radiation initiation to a phosphine conversion in excess of 50% to produce said compound.
Claim 11
Independent Claim
159 words
A method for the preparation of silylalkyl phosphines comprising the steps of selectively reacting silanes of the formula: R4 ySiHy wherein R is chlorine, C1 to C6 hydrocarbyl, providing that at least one of the R groups is chlorine; y is 1 and 2; with Alpha , omega -dienes of the formula: CH2 CH(CH2)kCH CH2 wherein k is 1 to 30; at temperatures between -90* and 90*C using reactant ratios of 2 to 6 moles of diolefin per mole silane to yield omega -alkenyl silanes of the formula: R4 ySi((CH2)1CH CH2)y wherein l is k + 2; and adding a phosphine of the formula: (R''3 xP)Hx wherein R'' is selected from the group consisting of C1 to C4 alkyl, cyclohexyl and phenyl; x is 1 to 3; to said omega -alkenyl silane; at temperatures between -100* and +16*C with radiation initiation to a phosphine conversion in excess of 50% to yield the corresponding free radical adducts of anti-Markovnikov orientation.
Claim 12
Independent Claim
159 words
A method for the preparation of silylalkyl phosphines comprising the steps of selectively reacting silanes of the formula: R4 ySiHy wherein R is chlorine, C1 to C6 hydrocarbyl, providing that at least one of the R groups is chlorine; y is 1 and 2; with Alpha , omega -dienes of the formula: CH2 CH(CH2)kCH CH2 wherein k is 1 to 30; at temperatures between -90* and 90*C using reactant ratios of 2 to 6 moles of diolefin per mole silane to yield omega -alkenyl silanes of the formula: R4 ySi((CH2)1CH CH2)y wherein l is k + 2; and adding a phosphine of the formula: (R''3 xP)Hx wherein R'' is selected from the group consisting of C1 to C4 alkyl, cyclohexyl and phenyl; x is 1 to 3; to said omega -alkenyl silane; at temperatures between -100* and +16*C with radiation initiation to a phosphine conversion in excess of 50% to yield the corresponding free radical adducts of anti-Markovnikov orientation.
Claim 13
Dependent Claim
21 words
The method of claim 8 wherein R is chlorine, methyl, phenyl; k is 1 to 10; x is 1 or 2.
Claim 14
Dependent Claim
25 words
The method of claim 8 wherein the silane is trichlorosilane and the phosphine is of the formula R''2PH wherein R'' is C1 to C4 alkyl.
Claim 15
Independent Claim
74 words
A method for preparing omega -trichlorosilyloctyl diphenyl phosphine, said method comprising the steps of adding trichlorosilane to 1,7-octadiene, at temperatures between -90* and 90*C using reactant ratios of 2 to 6 moles of diolefin per mole silane, to yield 8-octenyl trichlorosilane, adding diphenyl phosphine to said 8-octenyl trichlorosilane to a phosphine conversion in excess of 50% under free radical conditions at temperatures between -100* to +16*C with radiation initiation to produce said final product.
Claim 16
Independent Claim
74 words
A method for preparing omega -trichlorosilyloctyl diphenyl phosphine, said method comprising the steps of adding trichlorosilane to 1,7-octadiene, at temperatures between -90* and 90*C using reactant ratios of 2 to 6 moles of diolefin per mole silane, to yield 8-octenyl trichlorosilane, adding diphenyl phosphine to said 8-octenyl trichlorosilane to a phosphine conversion in excess of 50% under free radical conditions at temperatures between -100* to +16*C with radiation initiation to produce said final product.
Claim 17
Dependent Claim
4 words
COMPOUNDS OR THE FORMULA
Claim 18
Dependent Claim
4 words
COMPOUNDS OR THE FORMULA
Claim 19
Dependent Claim
11 words
Compounds of claim 12 wherein x, y and z are 1.
Claim 20
Dependent Claim
10 words
Compounds of claim 12 wherein m is 8 to 30.
Claim 21
Dependent Claim
8 words
Compounds of claim 13 wherein R is chloro.
Claim 22
Dependent Claim
37 words
Compounds of the formula: R''2P(CH2)mSiR3 wherein R'' is C1 to C4 alkyl, cyclohexyl and phenyl, m is 5 to 30, R is chloro, methyl and phenyl, provided that at least one of the R groups is chloro.
Claim 23
Dependent Claim
37 words
Compounds of the formula: R''2P(CH2)mSiR3 wherein R'' is C1 to C4 alkyl, cyclohexyl and phenyl, m is 5 to 30, R is chloro, methyl and phenyl, provided that at least one of the R groups is chloro.
Claim 24
Dependent Claim
10 words
Compounds of claim 16 wherein m is 8 to 30.
Claim 25
Dependent Claim
36 words
Compounds of the formula: R''P((CH2)mSiR3)2 wherein R'' is C1 to C4 alkl, cyclohexyl, phenyl; m is 5 to 30; R is chloro, methyl and phenyl provided that at least one of the R groups is chloro.
Claim 26
Dependent Claim
36 words
Compounds of the formula: R''P((CH2)mSiR3)2 wherein R'' is C1 to C4 alkl, cyclohexyl, phenyl; m is 5 to 30; R is chloro, methyl and phenyl provided that at least one of the R groups is chloro.
Claim 27
Dependent Claim
34 words
Compounds of the formula: (R''3 xP)z((CH2)m)ySiR4 y wherein R'' is C1 to C4 alkyl, cyclohexyl, phenyl; m is 5 to 30; z is 1 to 3; y is 1 or 2; R is chloro.
Claim 28
Dependent Claim
34 words
Compounds of the formula: (R''3 xP)z((CH2)m)ySiR4 y wherein R'' is C1 to C4 alkyl, cyclohexyl, phenyl; m is 5 to 30; z is 1 to 3; y is 1 or 2; R is chloro.
Claim 29
Dependent Claim
10 words
Compounds of claim 19 wherein m is 8 to 30.
Claim 30
Dependent Claim
5 words
Compound of the formula: (C6H5)2P(CH2)8SiCl3
Claim 31
Dependent Claim
5 words
Compound of the formula: (C6H5)2P(CH2)8SiCl3
Claim 32
Dependent Claim
5 words
Compound of the formula: (C6H5)2P(CH2)8Si(CH3)Cl2
Claim 33
Dependent Claim
5 words
Compound of the formula: (C6H5)2P(CH2)8Si(CH3)Cl2
Claim 34
Dependent Claim
5 words
Compound of the formula: (C6H5)2P(CH2)14SiCl3
Claim 35
Dependent Claim
5 words
Compound of the formula: (C6H5)2P(CH2)14SiCl3
Claim 36
Dependent Claim
4 words
Compound of the formula:
Claim 37
Dependent Claim
4 words
Compound of the formula:
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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) | 1978-09-22 | 1979-03-24 | 1979-09-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-09-22 | 1983-03-24 | 1983-09-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-09-22 | 1987-03-24 | 1987-09-23 | $7700.00 | Window Closed / Lapsed |