Patent US4110363A successfully refreshed from Google Patents.
US4110363A
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Preparation of esters
Assignee: Shell USA Inc
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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 a macrocylic polyether catalyst.
Inventors
- 👤 Roger A. Sheldon
- 👤 Peter Been
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 23:43
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: 30
Claim 1
Independent Claim
143 words
A process for the preparation of an ester of the formula ##STR5## wherein Ar represents a phenoxy substituted phenyl group and R 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 aryl halide of the formula RC(O)Hal, in which formulas Ar and R have the same meaning as in the formula I and Hal represents a halogen atom having an atomic number from 9 to 53, inclusive, with water, a water-soluble cyanide, a substantially water-immiscible aprotic solvent and a macrocyclic polyether phase transfer catalyst containing a total of from 4 to 80 atoms and 14 to 28 ring atoms at least 4 of which are oxygen atoms and recovering the desired ester from the reaction mixture.
Claim 2
Dependent Claim
143 words
A process for the preparation of an ester of the formula ##STR5## wherein Ar represents a phenoxy substituted phenyl group and R 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 aryl halide of the formula RC(O)Hal, in which formulas Ar and R have the same meaning as in the formula I and Hal represents a halogen atom having an atomic number from 9 to 53, inclusive, with water, a water-soluble cyanide, a substantially water-immiscible aprotic solvent and a macrocyclic polyether phase transfer catalyst containing a total of from 4 to 80 atoms and 14 to 28 ring atoms at least 4 of which are oxygen atoms and recovering the desired ester 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 (cyclo)alkane 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 1, 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
19 words
A process according to claim 18, in which the group R is a 1-(4-chlorophenyl)-2-methylpropyl group or an isopropyl group.
Claim 21
Dependent Claim
17 words
A process according to claim 18, in which the group R is an optionally substituted cyclopropyl group.
Claim 22
Dependent Claim
19 words
A process according to claim 20, in which the group R is a 2,2,3,3-tetramethylcyclopropyl group or a 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropyl group.
Claim 23
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 24
Dependent Claim
36 words
A process according to claim 21, which is carried out by gradual addition of a 2,2,3,3-teteramethylcyclopropanecarbonyl halide to a stirred mixture of the aromatic aldehyde, the water, the water-soluble cyanide and the substantially water-immiscible aprotic solvent.
Claim 25
Dependent Claim
16 words
A process according to claim 1, wherein the macrocyclic polyether catalyst is 1,4,7,10,13,16-hexaoxacyclooctadecane, 3,4-benzo-1,6,9,12,15,18,21-heptaoxacyclotricos-3-ene or 3,4-benzo-1,6,9,12-tetraoxacyclotetradec-3-ene.
Claim 26
Dependent Claim
18 words
A process according to claim 1 wherein the macrocyclic polyether catalyst contains 5 to 8 ring oxygen atoms.
Claim 27
Dependent Claim
31 words
A process according to claim 25 wherein the water soluble cyanide is sodium cyanide and the solvent is an alkane, a cycloalkane, an aromatic hydrocarbon, chlorinated hydrocarbon or a mixture thereof.
Claim 28
Dependent Claim
68 words
A process according to claim 26 which is conducted at a temperature in the range of from 10° C to 50° C, with the molar ratio of the amount of (cyclo)aliphatic acyl halide to the amount of the aromatic aldehyde is 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 29
Dependent Claim
16 words
A process according to claim 27 wherein the macrocyclic polyether catalyst is 1,4,7,10,13,16-hexaoxacyclooctadecane, 3,4-benzo-1,6,9,12,15,18,21-heptaoxacyclotricos-3-ene or 3,4-benzo-1,6,9,12-tetraoxacyclotetradec-3-ene.
Claim 30
Dependent Claim
15 words
A process according to claim 28 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 |