Patent US4283565A successfully refreshed from Google Patents.
US4283565A
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Process for preparing benzylalcohols
Assignee: Dynamit Nobel AG
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Filing: 1978-12-29
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Granted: 1981-08-11
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Expires: 1998-12-29
Abstract
Abstract There is described an essentially two step process for the preparation of benzylalcohols including those benzylalcohols having substituents on the benzyene ring by reaction of a substituted or unsubstituted benzyl halide with a formate typically an alkali or alkaline earth metal formate to form the corresponding substituted or unsubstituted benzyl formate. In the second step of the process the benzyl formate is contacted with an alcohol whereby the same is converted into the desired benzylalcohol. Both steps can be performed employing catalysts. Described in the specification is the realization of the desired product in exceptionally high yields in a short period of time whereby the process is characterized by high space-time yields.
Inventors
- 👤 Gunther Bernhardt
- 👤 Gerhard Daum
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 21:13
CPC Classifications
C; C07; C07C; C07C29/00; C07C29/128; C07C29/1285; C07C67/00; C07C67/03
Claims Analysis
Total Claims: 51
Claim 1
Independent Claim
184 words
A process for preparing benzylalcohol or benzylalcohol having a substituent on the benzene ring which comprises: A. Contacting a benzylchloride and/or bromide or a benzylchloride and/or bromide singularly or multiply substituted on the benzene ring which compound has the formula ##STR2## wherein Y=halogen and/or alkyl n=0 to 5 W=--CH 2 --X a=0 to 5 Z=hydroxy or alkoxy b=0 to 3 A=nitro and/or nitrile c=o to 2 and a+b+n+c=1 to 5, and X represents chlorine or bromine at a temperature of 100° to 250° C. with an alkali metal or alkaline earth metal formate such that said benzylchloride and/or bromide reacted is in the heterogeneous phase in the presence of a catalyst selected from the group consisting of tertiary amines, tertiary phosphines, quaternary ammonium salts and quaternary phosphonium salts and in the absence of a solvent to form benzylformate or a benzylformate which contains a substituent on the benzene ring; and B. Thereafter converting the so formed benzylformate or substituted benzylformate by means of a transesterification step to the corresponding alcohol by contacting the same with an alcohol in the presence of an esterification catalyst.
Claim 2
Dependent Claim
184 words
A process for preparing benzylalcohol or benzylalcohol having a substituent on the benzene ring which comprises: A. Contacting a benzylchloride and/or bromide or a benzylchloride and/or bromide singularly or multiply substituted on the benzene ring which compound has the formula ##STR2## wherein Y=halogen and/or alkyl n=0 to 5 W=--CH 2 --X a=0 to 5 Z=hydroxy or alkoxy b=0 to 3 A=nitro and/or nitrile c=o to 2 and a+b+n+c=1 to 5, and X represents chlorine or bromine at a temperature of 100° to 250° C. with an alkali metal or alkaline earth metal formate such that said benzylchloride and/or bromide reacted is in the heterogeneous phase in the presence of a catalyst selected from the group consisting of tertiary amines, tertiary phosphines, quaternary ammonium salts and quaternary phosphonium salts and in the absence of a solvent to form benzylformate or a benzylformate which contains a substituent on the benzene ring; and B. Thereafter converting the so formed benzylformate or substituted benzylformate by means of a transesterification step to the corresponding alcohol by contacting the same with an alcohol in the presence of an esterification catalyst.
Claim 3
Dependent Claim
35 words
A process according to claim 1 wherein Y=halogen and/or alkyl of 1 to 4 carbon atoms, n is 0 to 2, a=0 to 2, Z=hydroxy or C 1 to C 4 alkoxy b=0 to 2.
Claim 4
Dependent Claim
35 words
A process according to claim 1 wherein the benzyl chloride and/or bromide reactant is a chloro, dichloro, bromo, methyl, dimethyl, methoxy, hydroxy or nitrobenzylchloride and/or bromide or an ortho, meta or para xylylenedichloride and/or xylylenedibromide.
Claim 5
Dependent Claim
32 words
A process according to claim 1 wherein the stoichiometric molar ratio of halogen methyl groups of the benzyl chloride and/or bromide reactant to formate is in the range of 1:1 to 1.5.
Claim 6
Dependent Claim
15 words
A process according to claim 4 wherein said stoichiometric ratio is 1:>1 than to 1.1.
Claim 7
Dependent Claim
12 words
A process according to claim 1 wherein said formate is sodium formate.
Claim 8
Dependent Claim
28 words
A process according to claim 1 wherein the benzyl chloride and/or bromide is reacted with the formate at a temperature in the range of 110° to 200° C.
Claim 9
Dependent Claim
25 words
A process according to claim 1 wherein the catalyst employed for reaction of the benzyl chloride and/or bromide with the formate is a tertiary amine.
Claim 10
Dependent Claim
20 words
A process according to claim 8 wherein said tertiary amine is triethylamine, tripropylamine, a tributylamine, dimethylaniline, N-methyl-morpholine, hexamethylenetetramine or triethylenediamine.
Claim 11
Dependent Claim
12 words
A process according to claim 9 wherein said tertiary amine is triethylamine.
Claim 12
Dependent Claim
25 words
A process according to claim 1 wherein the catalyst for the reaction of the benzyl chloride and/or bromide with the formate is a tertiary phosphine.
Claim 13
Dependent Claim
16 words
A process according to claim 11 wherein said tertiary phosphine is triethylphosphine, tributylphosphine, triphenylphosphine or tribenzylphosphine.
Claim 14
Dependent Claim
12 words
A process according to claim 12 wherein said tertiary phosphine is triphenylphosphine.
Claim 15
Dependent Claim
28 words
A process according to claim 1 wherein the catalyst employed for the reaction of the benzyl or chloride and/or bromide with the formate is a quaternary ammonium salt.
Claim 16
Dependent Claim
22 words
A process according to claim 14 wherein said quaternary ammonium salt is methyltricaprylylammonium chloride, a tetrabutylammonium chloride, trimethylbenzylammonium chloride or triethylbenzylammonium chloride.
Claim 17
Dependent Claim
26 words
A process according to claim 1 wherein the catalyst employed for reaction of the benzyl chloride and/or bromide with the formate is a quaternary phosphonium salt.
Claim 18
Dependent Claim
17 words
A process according to claim 16 wherein the quaternary phosphonium salt is triphenylmethylphosphonium bromide or triphenylethylphosphonium bromide.
Claim 19
Dependent Claim
42 words
A process according to claim 1 wherein the catalyst employed in the reaction of the benzyl chloride and/or bromide with the formate is employed in an amount of 0.1 to 10 parts by weight per 100 parts of benzylchloride and/or bromide reactant.
Claim 20
Dependent Claim
29 words
A process according to claim 18 wherein said catalyst is employed in an amount of 0.5 to 5 parts by weight per 100 parts of benzylchloride and/or bromide reactant.
Claim 21
Dependent Claim
30 words
A process according to claim 11 wherein in step B, the stoichiometric proportion of formoxymethyl groups to alcohol employed for the esterification is in the range of 1:1.2 to 25.
Claim 22
Dependent Claim
35 words
A process according to claim 20 wherein the stoichiometric proportion of formoxymethyl groups of the formate so formed in step A to alcohol employed in step B is in the range of 1:1.25 to 12.
Claim 23
Dependent Claim
22 words
A process according to claim 1 wherein the alcohol employed for trans-esterification in step B is a primary of secondary univalent alcohol.
Claim 24
Dependent Claim
19 words
A process according to claim 22 wherein said alcohol is methanol, ethanol, n-propanol, n-butanol, isobutanol, isopropanol or secondary butanol.
Claim 25
Dependent Claim
37 words
A process according to claim 1 wherein the trans-esterification of the benzyl formate or xylyleneglcolbisformate formed according to step A with the alcohol in step B is carried out at the boiling temperature of the reaction mixture.
Claim 26
Dependent Claim
39 words
A process according to claim 1 wherein the formic acid ester which forms as a result of contacting the formate formed in step A with alcohol according to step B is continuously distilled off from the trans-esterification reaction mixture.
Claim 27
Dependent Claim
22 words
A process according to claim 1 wherein the esterification of step B is carried out in the presence of an acid catalyst.
Claim 28
Dependent Claim
24 words
A process according to claim 21 wherein the acid catalyst is nitric acid, sulphuric acid, phosphoric acid, hydrochloric acid, formic acid or acetic acid.
Claim 29
Dependent Claim
17 words
A process according to claim 27 wherein said acid is in the form of an aqueous solution.
Claim 30
Dependent Claim
20 words
A process according to claim 1 wherein the esterification of step B takes place in the presence of an alcoholate.
Claim 31
Dependent Claim
22 words
A process according to claim 29 wherein the alcohol component of the alcoholate is derived from a primary, secondary or tertiary alcohol.
Claim 32
Dependent Claim
25 words
A process according to claim 30 wherein the alcohol component of the alcoholate, is methanol, ethanol, propanol, isopropanol or one of the isomeric butyl alcohols.
Claim 33
Dependent Claim
20 words
A process according to claim 1 wherein the trans-esterification of step B takes place in the presence of a phenolate.
Claim 34
Dependent Claim
30 words
A process according to claim 32 wherein said phenolate is derived from phenol, an ortho, meta or para cresol, salicylic aldehyde or an ortho, meta or para hydroxybenzoic acid ester.
Claim 35
Dependent Claim
32 words
A process according to claim 1 wherein the trans-esterification of step B is carried out in the presence of an alcoholate or phenolate of an alkali metal, alkaline earth metal or aluminium.
Claim 36
Dependent Claim
22 words
A process according to claim 34 wherein said alcoholate or phenolate is an alcoholate or phenolate of sodium, potassium, calcium or magnesium.
Claim 37
Dependent Claim
37 words
A process according to claim 1 wherein the catalyst employed in the trans-esterification step B is employed in an amount of 0.01 to 10 weight percent based upon the amount of benzyl formate in the reaction mixture.
Claim 38
Dependent Claim
21 words
A process according to claim 1 wherein the esterification catalyst is present in an amount of 0.05 to 5 weight percent.
Claim 39
Dependent Claim
19 words
A process according to claim 1 wherein the trans-esterification takes place in the presence of a metallic acid ester.
Claim 40
Dependent Claim
16 words
A process according to claim 38 wherein said metallic acid ester is a titanic acid ester.
Claim 41
Dependent Claim
14 words
A process according to claim 39 wherein said titanic acid ester is a tetrabutyltitanate.
Claim 42
Dependent Claim
11 words
A process according to claim 40 wherein said tetrabutyltitanate is tetra-n-prim.-butyltitanate.
Claim 43
Dependent Claim
32 words
A process according to claim 38 wherein said metallic acid ester is employed in an amount of 0.01 to 5 weight percent, based upon the amount of benzylformate in the reaction mixture.
Claim 44
Dependent Claim
32 words
A process according to claim 42 wherein said metallic acid ester is present in an amount of 0.02 to 3 weight percent, based upon the amount of benzylformate in the reaction mixture.
Claim 45
Dependent Claim
17 words
A process according to claim 26 wherein the trans-esterification is carried out in an aqueous alcoholic medium.
Claim 46
Dependent Claim
22 words
A process according to claim 44 wherein the amount of water in the aqueous alcoholic medium is 2 to 80 volume percent.
Claim 47
Dependent Claim
22 words
A process according to claim 45 wherein the amount of water in the aqueous alcoholic medium is 5 to 50 volume percent.
Claim 48
Dependent Claim
181 words
A process for preparing benzylalcohol or a benzylalcohol having a substituent on the benzyl ring which comprises: A. Contacting a benzylchloride and/or bromide or a benzylchloride and/or bromide singularly or multiply substituted on the benzene ring which compound has the formula ##STR3## wherein Y=halogen and/or alkyl n=0 W=--CH 2 --X a=0 to 5 Z=hydroxy, alkoxy or phenoxy b=0 to 3 A=nitro and/or nitrile c=0 a+b+n+c=1 to 5, and X represents chlorine or bromine at a temperature of 100° to 250° C. with an alkali metal or alkaline earth metal formate such that said benzylchloride and/or bromide reacted is in the heterogeneous phase in the presence of a catalyst selected from the group consisting of tertiary amines, tertiary phosphines, quaternary ammonium salts and quaternary phosphonium salts and in the absence of a solvent to form benzylformate or a benzylformate which contains a substituent on the benzene ring; and B. Thereafter converting the so formed benzylformate or substituted benzylformate by means of a transesterification step to the corresponding alcohol by contacting the same with an alcohol in the presence of an esterification catalyst.
Claim 49
Dependent Claim
181 words
A process for preparing benzylalcohol or a benzylalcohol having a substituent on the benzyl ring which comprises: A. Contacting a benzylchloride and/or bromide or a benzylchloride and/or bromide singularly or multiply substituted on the benzene ring which compound has the formula ##STR3## wherein Y=halogen and/or alkyl n=0 W=--CH 2 --X a=0 to 5 Z=hydroxy, alkoxy or phenoxy b=0 to 3 A=nitro and/or nitrile c=0 a+b+n+c=1 to 5, and X represents chlorine or bromine at a temperature of 100° to 250° C. with an alkali metal or alkaline earth metal formate such that said benzylchloride and/or bromide reacted is in the heterogeneous phase in the presence of a catalyst selected from the group consisting of tertiary amines, tertiary phosphines, quaternary ammonium salts and quaternary phosphonium salts and in the absence of a solvent to form benzylformate or a benzylformate which contains a substituent on the benzene ring; and B. Thereafter converting the so formed benzylformate or substituted benzylformate by means of a transesterification step to the corresponding alcohol by contacting the same with an alcohol in the presence of an esterification catalyst.
Claim 50
Dependent Claim
184 words
A process for preparing benzylalcohol or a benzylalcohol having a substituent on the benzene ring which comprises: A. Contacting a benzylchloride and/or bromide or a benzylchloride and/or bromide singularly or multiply substituted on the benzene ring which compound has the formula ##STR4## wherein Y=halogen and/or alkyl n=0 to 2 W=--CH 2 --X a=0 to 5 Z=hydroxy or alkoxy b=0 to 3 A=nitro and/or nitrile c=0 to 2 and a+b+n+c=1 to 5, and X represents chlorine or bromine at a temperature of 100° to 250° C. with an alkali metal or alkaline earth metal formate such that said benzylchloride and/or bromide reacted is the heterogeneous phase in the presence of a catalyst selected from the group consisting of tertiary amines, tertiary phosphines, quaternary ammonium salts and quaternary phosphonium salts and in the absence of a solvent to form benzylformate or a benzylformate which contains a substituent on the benzene ring; and B. Thereafter converting the so formed benzylformate or substituted benzylformate by means of a transesterification step to the corresponding alcohol by contacting the same with an alcohol in the presence of an esterification catalyst.
Claim 51
Dependent Claim
184 words
A process for preparing benzylalcohol or a benzylalcohol having a substituent on the benzene ring which comprises: A. Contacting a benzylchloride and/or bromide or a benzylchloride and/or bromide singularly or multiply substituted on the benzene ring which compound has the formula ##STR4## wherein Y=halogen and/or alkyl n=0 to 2 W=--CH 2 --X a=0 to 5 Z=hydroxy or alkoxy b=0 to 3 A=nitro and/or nitrile c=0 to 2 and a+b+n+c=1 to 5, and X represents chlorine or bromine at a temperature of 100° to 250° C. with an alkali metal or alkaline earth metal formate such that said benzylchloride and/or bromide reacted is the heterogeneous phase in the presence of a catalyst selected from the group consisting of tertiary amines, tertiary phosphines, quaternary ammonium salts and quaternary phosphonium salts and in the absence of a solvent to form benzylformate or a benzylformate which contains a substituent on the benzene ring; and B. Thereafter converting the so formed benzylformate or substituted benzylformate by means of a transesterification step to the corresponding alcohol by contacting the same with an alcohol in the presence of an esterification catalyst.
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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) | 1984-08-10 | 1985-02-09 | 1985-08-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-08-10 | 1989-02-09 | 1989-08-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-08-10 | 1993-02-09 | 1993-08-11 | $7700.00 | Window Closed / Lapsed |