US3655735A - Production of 3-methylbut-2-en-1-ol or 3-methylbut-2-en-1-yl acetate - Google Patents

Production of 3-methylbut-2-en-1-ol or 3-methylbut-2-en-1-yl acetate Download PDF

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US3655735A
US3655735A US782420A US3655735DA US3655735A US 3655735 A US3655735 A US 3655735A US 782420 A US782420 A US 782420A US 3655735D A US3655735D A US 3655735DA US 3655735 A US3655735 A US 3655735A
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methylbut
acetate
compounds
production
mixture
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US782420A
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Horst Pommer
Herbert Mueller
Dietrich Mangold
Hermann Overwien
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton

Definitions

  • 3-methylbut-2-en-1-ol or 3- methylbut-Z-en-l-yl acetate can be obtained in a simple way and in high yields by treating 3-methylbut-3-en-1-ol or 3-methylbut-3-en-1-yl acetate with a catalytic amount of a carbonyl compound of a metal of subgroups 6 to 8 of the Periodic System.
  • the starting compounds are known and obtainable particularly advantageously by reaction of isobutene with formaldehyde followed if necessary by acetylation.
  • Suitable compounds which act as isomerization catalysts are particularly those of zerovalent metals in accordance with the definition, more particularly, complexes having one or two central atoms such as chromium hexacarbonyl, iron pentacarbonyl, diiron nonacarbonyl, and nickel tetracarbonyl.
  • complexes having one or two central atoms such as chromium hexacarbonyl, iron pentacarbonyl, diiron nonacarbonyl, and nickel tetracarbonyl.
  • Compounds in which some of the carbonyl groups have been replaced by other ligands, as in dihydrogen iron tetracarbonyl or hydrogen cobalt tetracarbonyl are also suitable.
  • Suitable ligands in such compounds are those which bear basic nitrogen or phosphorus atoms.
  • Examples of such carbonyl compounds are bistriphenylphosphine iron tricarbonyl and tripyridine diiron tetracarbonyl.
  • Iron pentacarbonyl is particularly preferred as the catalyst.
  • the amount of carbonyl compound required for the isomerization is from 0.01 to 20% by weight, preferably from 1 to by weight, with reference to the amount of starting material to be isomerized. It is possible however to use larger or smaller amounts of these catalysts, the isomerization merely being accelerated or retarded thereby.
  • the reaction may be carried out at temperatures of from about 100 to 300 C., preferably from 150 to 200 C. at atmospheric pressure or at superatmospheric pressure up to about 50 atmospheres with or without a solvent and batchwise or continuously.
  • Suitable basic compounds include, in addition to inorganic bases such as sodium hydroxide, barium hydroxide or ammonia and in addition to the salts of strong bases and weak acids such as sodium carbonate or ammonium carbonate, particularly nitrogenous basic compounds such as alkylamines or arylamines and also compounds which are capable of splitting ofl bases, such as piperidine acetate or acid amides such as acetamide or urea.
  • Hexamethylenetetramine (urotropine) is preferred as the basic compound.
  • the basic compound is generally used in an amount of from 0.01 to 20%, preferably from 1 to 10%, by weight with reference to the compound to be isomerized.
  • Hydrocarbons which are liquid under the reaction conditions concerned, as for example hexane, heptane, ligroin, benzene, toluene or xylene, are especially suitable as solvents.
  • high boiling point ether' such as diphenyl ether, 2,2'-dimethoxydiethyl ether and 2,2'-diet.hoxydiethyl ether are also suitable.
  • reaction mixture When the isomerization is over, the reaction mixture may be worked up by conventional methods, preferably by distillation.
  • the products of the process are valuable intermediates for organic synthesis, particularly for the production of compounds of the carotenoid and vitamin A series and of perfumes.
  • EXAMPLE 1 A mixture of 50 g. of 3-methylbut-3-en-l-yl acetate and 3.5 g. of iron pentacarbonyl is heated for fifteen hours at 150 C. and the desired product (3-methylbut-2-en-1-yl, B.P. to 112 C. at 200 mm.) is isolated from the mixture in the usual way by fractional distillation. The yield of pure products is 86% at a conversion of 42%.
  • EXAMPLE 3 A mixture of 1000 g. of 3-methylbut-3-en-1-ol, 10 g. of iron pentacarbonyl and 50 g. of urotropine is heated for ninety minutes at 200 C. and the desired product is isolated from this mixture in the usual way by fractional distillation.
  • EXAMPLE 4 A mixture of g. of 3-methylbut-3-en-1-ol, 22 g. of iron pentacarbonyl and 9 g. of urotropine is heated for thirty minutes at 200 C. and B-methylbut-Z-en-l-ol is isolated in the usual way by fractional distillation. The yield of pure product is 89% at a conversion of 31%.
  • EXAMPLE 5 A mixture of 1000 g. of 3-methylbut-3-en-1-ol, 15 g. of iron pentacarbonyl and 60 ml. of liquid ammonia is heated at 175 C. in an autoclave for two hours and the 3-methylbut-2-en-1-ol is then isolated by fractional distillation. The yield of pure product is 73% at a conversion of 40%.
  • EXAMPLE 6 An isomerizing process for the production of 3-methylbut-Z-en-l-ol or 3-methylbut-2-en-1-y1 acetate which comprises treating 3-methylbut-3-en-1-ol or 3-methyl-3-enl-yl acetate at a temperature of about 100 C. to 300 C. with a catalytic amount of iron pentacarbonyl and in the presence of a catalytic amount of a basic reacting compound selected from the class consisting of sodium hydroxide, barium hydroxide, ammonia, sodium carbonate, ammonium carbonate, piperidine acetate, acetamide, urea, alkyl and aryl amines and phosphines.
  • a basic reacting compound selected from the class consisting of sodium hydroxide, barium hydroxide, ammonia, sodium carbonate, ammonium carbonate, piperidine acetate, acetamide, urea, alkyl and aryl amines and phosphines.

Abstract

PRODUCTION OF 3-METHYLBUT-2-EN-1-01 AND 3 METHYLBUT2-EN-1-YL ACETATE BY ISOMERIZING 3-METHYL-3-BUTEN-1-01 OR 3-METHYL-3-BUTEN-1-YL ACETATE WITH A CATALYTIC AMOUNT OF A CARBONYL COMPOUND OF A METAL OF SUBGROUPS 6 TO 8 OF THE PERIODIC SYSTEM.

Description

United States Patent US. Cl. 260-491 2 Claims ABSTRACT OF THE DISCLOSURE Production of 3-methylbut-2-en-l-ol and 3-methylbut- 2-en-1-yl acetate by isomerizing 3-methyl-3-buten-1-ol or 3-methyl-3-buten-1-yl acetate with a catalytic amount of a carbonyl compound of a metal of subgroups 6 to 8 of the Periodic System.
The present invention relates to a new process for the production of 3-methylbut-2-en-1-ol or 3-methylbut-2-enl-yl acetate.
It is known that these compounds (also known as prenol and prenyl acetate) can be prepared in a multistage synthesis. This method is troublesome however and gives only unsatisfactory yields.
We have now found that 3-methylbut-2-en-1-ol or 3- methylbut-Z-en-l-yl acetate can be obtained in a simple way and in high yields by treating 3-methylbut-3-en-1-ol or 3-methylbut-3-en-1-yl acetate with a catalytic amount of a carbonyl compound of a metal of subgroups 6 to 8 of the Periodic System.
The starting compounds are known and obtainable particularly advantageously by reaction of isobutene with formaldehyde followed if necessary by acetylation.
Suitable compounds which act as isomerization catalysts are particularly those of zerovalent metals in accordance with the definition, more particularly, complexes having one or two central atoms such as chromium hexacarbonyl, iron pentacarbonyl, diiron nonacarbonyl, and nickel tetracarbonyl. Compounds in which some of the carbonyl groups have been replaced by other ligands, as in dihydrogen iron tetracarbonyl or hydrogen cobalt tetracarbonyl, are also suitable.
Other suitable ligands in such compounds are those which bear basic nitrogen or phosphorus atoms. Examples of such carbonyl compounds are bistriphenylphosphine iron tricarbonyl and tripyridine diiron tetracarbonyl.
Iron pentacarbonyl is particularly preferred as the catalyst.
The amount of carbonyl compound required for the isomerization is from 0.01 to 20% by weight, preferably from 1 to by weight, with reference to the amount of starting material to be isomerized. It is possible however to use larger or smaller amounts of these catalysts, the isomerization merely being accelerated or retarded thereby.
The reaction may be carried out at temperatures of from about 100 to 300 C., preferably from 150 to 200 C. at atmospheric pressure or at superatmospheric pressure up to about 50 atmospheres with or without a solvent and batchwise or continuously.
We have further found that particularly good results are obtained in the process by carrying out the reaction in the presence of catalytic amounts of a base or a compound having a basic reaction.
"ice
Suitable basic compounds include, in addition to inorganic bases such as sodium hydroxide, barium hydroxide or ammonia and in addition to the salts of strong bases and weak acids such as sodium carbonate or ammonium carbonate, particularly nitrogenous basic compounds such as alkylamines or arylamines and also compounds which are capable of splitting ofl bases, such as piperidine acetate or acid amides such as acetamide or urea. Basic compounds of phosphorus, such as alkyl and aryl phosphines, for example triphenyl phosphine, are also suitable.
Hexamethylenetetramine (urotropine) is preferred as the basic compound.
The presence of basic compounds causes a more rapid and more specific isomerization in the desired direction, i.e. from the 3-ene compound to the isomeric 2-ene compound. Since there is one more possibility of isomerization with the free alcohol than with the acetate (namely to isovaleraldehyde), the addition of base is particularly advantageous in the rearrangement of 3-methylbut-3-en-1-ol to 3-methylbut-2-en-1-ol.
The basic compound is generally used in an amount of from 0.01 to 20%, preferably from 1 to 10%, by weight with reference to the compound to be isomerized.
Hydrocarbons which are liquid under the reaction conditions concerned, as for example hexane, heptane, ligroin, benzene, toluene or xylene, are especially suitable as solvents. Moreover, high boiling point ether'such as diphenyl ether, 2,2'-dimethoxydiethyl ether and 2,2'-diet.hoxydiethyl ether are also suitable.
Since both the starting compounds and the products of the process are sensitive to oxygen, it is advisable to carry out the reaction while exluding oxygen, for example under nitrogen or argon. When readily decomposable carbonyl compounds are used as isomerization catalysts, it may be advantageous to use carbon monoxide.
When the isomerization is over, the reaction mixture may be worked up by conventional methods, preferably by distillation.
The products of the process are valuable intermediates for organic synthesis, particularly for the production of compounds of the carotenoid and vitamin A series and of perfumes.
The invention is illustrated by the following examples.
EXAMPLE 1 A mixture of 50 g. of 3-methylbut-3-en-l-yl acetate and 3.5 g. of iron pentacarbonyl is heated for fifteen hours at 150 C. and the desired product (3-methylbut-2-en-1-yl, B.P. to 112 C. at 200 mm.) is isolated from the mixture in the usual way by fractional distillation. The yield of pure products is 86% at a conversion of 42%.
EXAMPLE 2 A mixture of 2000 g. of 3-methylbut-3-en-1-ol and 10 g. of iron pentacarbonyl is heated for four hours at C. and from the mixture the desired product is isolated in the usual way by fractional distillation (3-methylbut-2- en-l-ol, B.P. 102 to 105 C. at 200 mm.; n =1.4408). The yield of pure product is 63% at a conversion of 34%.
EXAMPLE 3 A mixture of 1000 g. of 3-methylbut-3-en-1-ol, 10 g. of iron pentacarbonyl and 50 g. of urotropine is heated for ninety minutes at 200 C. and the desired product is isolated from this mixture in the usual way by fractional distillation. The yield of pure 3-methylbut-2-en-1-ol (B.P. 102 to 105 C. at 200 mm.; n =1.4408) is 75% at a conversion of 50%.
EXAMPLE 4 A mixture of g. of 3-methylbut-3-en-1-ol, 22 g. of iron pentacarbonyl and 9 g. of urotropine is heated for thirty minutes at 200 C. and B-methylbut-Z-en-l-ol is isolated in the usual way by fractional distillation. The yield of pure product is 89% at a conversion of 31%.
EXAMPLE 5 A mixture of 1000 g. of 3-methylbut-3-en-1-ol, 15 g. of iron pentacarbonyl and 60 ml. of liquid ammonia is heated at 175 C. in an autoclave for two hours and the 3-methylbut-2-en-1-ol is then isolated by fractional distillation. The yield of pure product is 73% at a conversion of 40%.
EXAMPLE 6 1. An isomerizing process for the production of 3-methylbut-Z-en-l-ol or 3-methylbut-2-en-1-y1 acetate which comprises treating 3-methylbut-3-en-1-ol or 3-methyl-3-enl-yl acetate at a temperature of about 100 C. to 300 C. with a catalytic amount of iron pentacarbonyl and in the presence of a catalytic amount of a basic reacting compound selected from the class consisting of sodium hydroxide, barium hydroxide, ammonia, sodium carbonate, ammonium carbonate, piperidine acetate, acetamide, urea, alkyl and aryl amines and phosphines.
2. A process as claimed in claim 1 wherein said basic reacting compound is hexamethylenetetramine.
References Cited UNITED STATES PATENTS 3,344,191 9/1967 Chappell et a1 260--586 2,837,577 6/1958 Blaser et al 260-491 LORRAINE A. WEINBERGER, Primary Examiner V. GARNER, Assistant Examiner US. Cl. X.R.
mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,655,755 Dated April 11 1972 Inventor(s) H 'S Pommer et 8.1
It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shownhelow:
Column '1, lines 10 to 11, Claims priority, application Ger-man Mar. 22, 1968, P 77 68 023.8" should read Claims priority, applications Germany, Dec. 8, 1967, P 16 43 709.5; Mar. 22, 1968, P 17 68 023.8
Column 3, line 22, claim 1, "3-methyl-3-enshould read Y B-methylbut-B-env Signed and sealed this 21st day of November 1972.
'(SEAL) Attest: p I I v EDWARD M.FLETCHER,JH. ROBERT GOTTSCHALK Attesting Officer 7 Commissioner of Patents
US782420A 1967-12-08 1968-12-09 Production of 3-methylbut-2-en-1-ol or 3-methylbut-2-en-1-yl acetate Expired - Lifetime US3655735A (en)

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DEB0095759 1967-12-08
DE19681768023 DE1768023C3 (en) 1967-12-08 1968-03-22 Process for the preparation of 3-methyl-2-buten-1-ol or 3-methyl-2-buten-1-ylacetate

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4117016A (en) * 1977-05-27 1978-09-26 Phillips Petroleum Company Process for structural modification of unsaturated alcohols
US4122291A (en) * 1976-06-08 1978-10-24 Kuraray Co., Ltd. Method for the production of alken-2-ol-1 or of alken-2-ol-1 and alkanol-1
US4387047A (en) * 1980-02-13 1983-06-07 Firmenich Sa Esters of 1,3-dimethyl-but-3-en-1-yl, their utilization as perfuming and flavoring ingredients and compositions containing same
CN102701910A (en) * 2012-05-24 2012-10-03 南开大学 Method for preparing prenol by isomerizing 3-methyl-3-butene-1-ethanol
CN104994949A (en) * 2013-01-23 2015-10-21 弗门尼舍有限公司 Process for the preparation of 4-methylpent-3-en-1-ol derivatives
CN107141197A (en) * 2017-06-23 2017-09-08 万华化学集团股份有限公司 A kind of method for preparing the butenol of 3 methyl 2
US10974225B1 (en) * 2020-01-17 2021-04-13 Zhejiang Nhu Company Ltd. Metal oxide coated ceramic corrugated plate catalyst, preparation and application in preparation of key intermediates of citral

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4122291A (en) * 1976-06-08 1978-10-24 Kuraray Co., Ltd. Method for the production of alken-2-ol-1 or of alken-2-ol-1 and alkanol-1
US4117016A (en) * 1977-05-27 1978-09-26 Phillips Petroleum Company Process for structural modification of unsaturated alcohols
US4387047A (en) * 1980-02-13 1983-06-07 Firmenich Sa Esters of 1,3-dimethyl-but-3-en-1-yl, their utilization as perfuming and flavoring ingredients and compositions containing same
CN102701910A (en) * 2012-05-24 2012-10-03 南开大学 Method for preparing prenol by isomerizing 3-methyl-3-butene-1-ethanol
CN104994949A (en) * 2013-01-23 2015-10-21 弗门尼舍有限公司 Process for the preparation of 4-methylpent-3-en-1-ol derivatives
CN104994949B (en) * 2013-01-23 2018-02-23 弗门尼舍有限公司 The method for preparing the 01 derivatives of 4 methylpent, 3 alkene 1
CN107141197A (en) * 2017-06-23 2017-09-08 万华化学集团股份有限公司 A kind of method for preparing the butenol of 3 methyl 2
CN107141197B (en) * 2017-06-23 2020-08-28 万华化学集团股份有限公司 Method for preparing 3-methyl-2-butenol
US10974225B1 (en) * 2020-01-17 2021-04-13 Zhejiang Nhu Company Ltd. Metal oxide coated ceramic corrugated plate catalyst, preparation and application in preparation of key intermediates of citral

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CH525173A (en) 1972-07-15
NL167408B (en) 1981-07-16
DE1768023A1 (en) 1972-01-13
DE1768023B2 (en) 1972-11-30
GB1239434A (en) 1971-07-14
NL6817562A (en) 1969-06-10
DE1768023C3 (en) 1973-06-28
DE1643709B1 (en) 1971-07-08
BE725088A (en) 1969-06-06
NL167408C (en) 1981-12-16
FR1594968A (en) 1970-06-08

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