US4110362A
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Preparation of esters
Assignee: Shell USA Inc
•
Filing: 1977-02-03
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Granted: 1978-08-29
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Expires: 1997-02-03
Abstract
Abstract Certain carboxylic acid esters also containing a cyano group are prepared by reacting an acid halide, an aldehyde and a water-soluble cyanide in the presence of a water-immiscible aprotic solvent and an onium catalyst.
Inventors
- 👤 Roger A. Sheldon
- 👤 Peter Been
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 05:25
CPC Classifications
C; C07; C07C; C07C253/00; C07C253/14; C07C253/16; C07C255/00; C07C255/01; C07C255/11; C07C255/14; C07C255/32; C07C255/41; C07C2601/00; C07C2601/02
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
188 words
A process for the preparation of an ester of formula I ##STR4## wherein Ar represents a phenoxy substituted phenyl group and R is an alkyl group optionally substituted by halophenyl or alkylphenyl or a cyclopropyl group optionally substituted by alkyl, halogen, isobutenyl, dichlorovinyl or dibromovinyl, which process comprises contacting an aromatic aldehyde of the formula ArC(O)H and a (cyclo)aliphatic acyl halide of the general formula RC(O)Hal, in which formulas Ar and R have the same meaning as in formula I and Hal represents a halogen atom having an atomic number of from 9 to 53, inclusive, with water, a water-soluble cyanide, a substantially water-immiscible aprotic solvent and a quaternary onium phase transfer catalyst of the formula II ##STR5## wherein X represents a nitrogen, phosphorus or arsenic atom, R 1 , R 2 , R 3 and R 4 each an alkyl, aralkyl, alkaryl or aryl group and Y a monovalent ion, or a sulfonium compound of the formula III ##STR6## wherein R 5 R 6 and R 7 each represents an alkyl group and Y a monovalent ion and recovering the desired ester product from the reaction mixture.
Claim 2
Dependent Claim
188 words
A process for the preparation of an ester of formula I ##STR4## wherein Ar represents a phenoxy substituted phenyl group and R is an alkyl group optionally substituted by halophenyl or alkylphenyl or a cyclopropyl group optionally substituted by alkyl, halogen, isobutenyl, dichlorovinyl or dibromovinyl, which process comprises contacting an aromatic aldehyde of the formula ArC(O)H and a (cyclo)aliphatic acyl halide of the general formula RC(O)Hal, in which formulas Ar and R have the same meaning as in formula I and Hal represents a halogen atom having an atomic number of from 9 to 53, inclusive, with water, a water-soluble cyanide, a substantially water-immiscible aprotic solvent and a quaternary onium phase transfer catalyst of the formula II ##STR5## wherein X represents a nitrogen, phosphorus or arsenic atom, R 1 , R 2 , R 3 and R 4 each an alkyl, aralkyl, alkaryl or aryl group and Y a monovalent ion, or a sulfonium compound of the formula III ##STR6## wherein R 5 R 6 and R 7 each represents an alkyl group and Y a monovalent ion and recovering the desired ester product from the reaction mixture.
Claim 3
Dependent Claim
33 words
A process according to claim 1, in which the molar ratio of the amount of phase transfer catalyst to the amount of aromatic aldehyde of the formula ArC(O)H is from 1:5 to 1:500.
Claim 4
Dependent Claim
21 words
A process according to claim 1, which is conducted at a temperature in the range of from 10° to 50° C.
Claim 5
Dependent Claim
20 words
A process according to claim 1, in which the total amount of the water-soluble cyanide is dissolved in the water.
Claim 6
Dependent Claim
21 words
A process according to claim 4, in which the substantially water-immiscible aprotic solvent is a (cyclo)alkane or a mixture of (cyclo)alkanes.
Claim 7
Dependent Claim
12 words
A process according to claim 5, in which the alkane is n-heptane.
Claim 8
Dependent Claim
12 words
A process according to claim 5, in which the cycloalkane is cyclohexane.
Claim 9
Dependent Claim
16 words
A process according to claim 1, which is conducted in the presence of solid water-soluble cyanide.
Claim 10
Dependent Claim
23 words
A process according to claim 8, in which the substantially water-immiscible aprotic solvent is an aromatic hydrocarbon or a mixture of aromatic hydrocarbons.
Claim 11
Dependent Claim
13 words
A process according to claim 9, in which the aromatic hydrocarbon is toluene.
Claim 12
Dependent Claim
17 words
A process according to claim 8, in which the substantially water-immiscible aprotic solvent is a chlorinated hydrocarbon.
Claim 13
Dependent Claim
28 words
A process according to claim 8, in which the starting molar ratio of the amount of water to the total amount of water-soluble cyanide is higher than 0.05.
Claim 14
Dependent Claim
33 words
A process according to claim 12, in which the starting molar ratio of the amount of water to the total amount of water-soluble cyanide is in the range of from 0.05 to 1.
Claim 15
Dependent Claim
42 words
A process according to claim 1, in which the molar ratio of the amount of (cyclo)aliphatic acyl halide of the formula RC(O)Hal to the amount of the aromatic aldehyde of the formula ArC(O)H is in the range of from 1.1 to 1.0.
Claim 16
Dependent Claim
35 words
A process according to claim 14, in which the molar ratio of the amount of (cyclo)aliphatic acyl halide of the formula RC(O)Hal to the amount of the aromatic aldehyde of the formula ArC(O)H is 1.0.
Claim 17
Dependent Claim
14 words
A process according to claim 1, in which the water-soluble cyanide is sodium cyanide.
Claim 18
Dependent Claim
17 words
A process according to claim 1, in which Hal in the formula RC(O)Hal represents a chlorine atom.
Claim 19
Dependent Claim
33 words
A process according to claim 1, in which the group R in the formula RC(O)Hal is an optionally substituted (cyclo)alkyl group having a tertiary or quaternary carbon atom bound to the group --C(O)Hal.
Claim 20
Dependent Claim
15 words
A process according to claim 18, in which the group R is a 1-(4-chlorophenyl)-2-methylpropyl group.
Claim 21
Dependent Claim
15 words
A process according to claim 18, in which the group R is an isopropyl group.
Claim 22
Dependent Claim
17 words
A process according to claim 18, in which the group R is an optionally substituted cyclopropyl group.
Claim 23
Dependent Claim
15 words
A process according to claim 21, in which the group R is a 2,2,3,3-tetramethylcyclopropyl group.
Claim 24
Dependent Claim
15 words
A process according to claim 21, in which the group R is a 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropyl group.
Claim 25
Dependent Claim
43 words
A process according to claim 19, which is carried out by forming a mixture of the total amounts of the aromatic aldehyde, the (cyclo)aliphatic acyl halide, the water, the water-soluble cyanide and the substantially water-immiscible aprotic solvent, and stirring the mixture thus formed.
Claim 26
Dependent Claim
37 words
A process according to claim 22, which is carried out by gradual addition of the cycloaliphatic acyl halide to a stirred mixture of the aromatic aldehyde, the water, the water-soluble cyanide and the substantially water-immiscible aprotic solvent.
Claim 27
Dependent Claim
63 words
A process according to claim 1 wherein the catalyst is a quaternary ammonium compound of formula II in which R 1 , R 2 , R 3 and R 4 each independently is an alkyl group containing 1 to 20 carbon atoms, an aralkyl or alkaryl group containing 7 to 9 carbon atoms or an aryl group containing 6 to 12 carbon atoms.
Claim 28
Dependent Claim
14 words
A process according to claim 26 wherein the water soluble cyanide is sodium cyanide.
Claim 29
Dependent Claim
23 words
A process according to claim 27 wherein the solvent is an alkane, a cycloalkane, an aromatic hydrocarbon, chlorinated hydrocarbon or a mixture thereof.
Claim 30
Dependent Claim
66 words
A process according to claim 28 which is conducted at a temperature in the range of from 10° to 50° C, with the molar ratio of the amount of (cyclo)aliphatic acyl halide to the amount of the aromatic aldehyde from 1.1 to 1.0 and in which the starting molar ratio of the amount of water to the total amount of water-soluble cyanide is higher than 0.05.
Claim 31
Dependent Claim
44 words
A process according to claim 29 wherein the ammonium catalyst of formula II is one in which R 1 , R 2 , R 3 and R 4 each independently is an alkyl group containing from 1 to 8 carbon atoms, phenyl or benzyl.
Claim 32
Dependent Claim
15 words
A process according to claim 30 wherein the ester of formula I is α-cyano-3-phenoxybenzyl 2-(-4-chlorophenyl)-3-methylbutanoate.
References Cited (Backward Citations)
US3835176A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-08-28 | 1982-02-27 | 1982-08-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-08-28 | 1986-02-27 | 1986-08-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-08-28 | 1990-02-27 | 1990-08-29 | $7700.00 | Window Closed / Lapsed |