US3655768A - Production of alk-1-en-6-ones - Google Patents

Production of alk-1-en-6-ones Download PDF

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US3655768A
US3655768A US775518A US3655768DA US3655768A US 3655768 A US3655768 A US 3655768A US 775518 A US775518 A US 775518A US 3655768D A US3655768D A US 3655768DA US 3655768 A US3655768 A US 3655768A
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alk
ketone
production
reaction
ones
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US775518A
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Horst Pommer
Herbert Mueller
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
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups

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  • alk-1-en-4-o1s' (II) to be used as starting materials those are particularly suitable which have the general formula (Ila) I l H H (Ila) where the radicals R to R denote hydrogen or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon groups having up to'eight carbon atoms, some of these groups if desiredbeing linked together in pairs to form five-membered to. seven-inembered rings.
  • Especially suitable compounds are those in which four of the radicals R to R denote hydrogen-atoms and the remaining radical is one of the said hydrocarbon groupsi
  • R to R denote hydrogen-atoms
  • the remaining radical is one of the said hydrocarbon groupsi
  • IV olefins
  • V aldehydes
  • Preferred starting materials (IIa) are those having four to ten carbon atoms, for examplebut-l-en-4-ol, Z-methylbut-l-en-4-ol, 3-methylbut-l-en 4-ol, pent-Z-en-S-ol and2- cyclohexylbut-1-en-4-ol.
  • the compounds butl-en-4-ol and 3,655,768 Patented Apr. 11, 1972 2-methylbut-l-en-4-ol have particular industrial importance.
  • ketones (III) are those having the general Formula IIIa:
  • Preferred compounds (lIIa) are those having from three to eight carbon atoms, for example acetone, methyl ethyl ketone, diethyl ketone, cyclohexenyl methyl ketone and acetophenone. Diethyl ketone and acetone have particular industrial importance.
  • the preferred reaction temperatures are from 200 to 350 C. Since most of the starting materials (II) and (III) which have special importance industrially would be gaseous at these temperatures at atmospheric pressure and since the reaction in liquid phase is preferred, it is preferable to use superatrnospheric pressure (up to about 1000 atmospheres), preferably the vapor pressure which is set up above the reaction mixture at the temperature chosen.
  • the reaction may be carried out with or without inert solvents or diluents but in general one of the reactants serves as solvent.
  • EXAMPLE 1 290 g. (5 moles) of acetone and 70 g. (0.8 mole) of 2-methylbut- 1-en- 4-ol are heated in an autoclave for fortyfive minutes, a pressure of about 220 atmospheres being set up. The reaction mixture is worked up by distillation. 42 g. of 2-methy1hept-1-en-6-one passes over and 30 g. of 2-methylbut-1-en-4-ol is recovered. This is a yield of 72% with reference to the conversion; the conversion itself is 57%.
  • EXAMPLE 3 280 g. (3.2 moles) of diethyl ketone and 70 g. (0.8 mole) of 2-methylbut-1-en-4-ol are heated for forty-five minutes at 300 C., a pressure of about 250 atmospheres being set up. The reaction mixture is worked up by distillation; 2,5-dimethyloct-1-en-6-one is obtained in a yield of 48% with reference to a conversion of 39%.
  • a process for the production of an alk-l-en-6-one which comprises reacting, at from 100 to 400 C., an alk-1en-4'ol of the formula:
  • each of the radicals R to R when taken alone denotes a hydrogen atom or an aliphatic, cycloaliphatic or aromatic hydrocarbon radical having up to eight carbon atoms and wherein two of the radicals R to R when taken together form a fiveto seven-membered carbocyclic ring and wherein the alkl-en-4ol contains a total of from four to ten carbon atoms, with a ketone of the formula:
  • each of the radicals R to R when taken alone denotes a hydrogen atom or an aliphatic or cycloaliphatic 4 hydrocarbon radical and wherein two of the radicals R to R when taken together form a fiveto seven-membered carbocyclic ring and wherein the ketone contains a total of from three to eight carbon atoms.
  • a process as claimed in claim 1 carried out at from 200 to 350 C.
  • a process as claimed in claim 1 carried out at a pressure of up to about 1000 atmospheres.
  • ketone reactant is selected from the group consisting of diethyl ketone and acetone.
  • ketone reactant is diethyl ketone and the alkenol reactant is 2- methylbut- 1-en-4-ol.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PRODUCTION OF ALK-1-EN-6-ONES BY REACTION OF AN ALK-1EN-4-OL AT FROM 100* TO 400*C. WITH A KETONE BEARING AT LEAST ONE HYDROGEN ATOM ON A CARBON IN VICINAL POSITION TO THE CARBONYL GROUP.

Description

United States Patent 3,655,768 PRODUCTION OF ALK-l-EN-G-ONES Horst Pommer, Ludwigshafen, Herbert Mueller, Frankenthal, and Hermann Overwien, Ludwigshafen, Germany, assignors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany No Drawing. Filed Nov. 13, 1968, Ser. No. 775,518 Int. Cl. C07c' 49/20, 49/45, 49/ 76 US. Cl. 260593 R 9 Claims ABSTRACT OF THE DISCLOSURE Production of alk-l-en-6-ones by reaction of an alk-len-4-ol at from 100 to 400 C. with a ketone bearing at least one hydrogen atom on a carbon atom in vicinal position to the carbonyl group.
The free valencies in the formulae are occupied by hydrogen or hydrocarbon radicals.
Among the alk-1-en-4-o1s' (II) to be used as starting materials, those are particularly suitable which have the general formula (Ila) I l H H (Ila) where the radicals R to R denote hydrogen or aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon groups having up to'eight carbon atoms, some of these groups if desiredbeing linked together in pairs to form five-membered to. seven-inembered rings. Especially suitable compounds are those in which four of the radicals R to R denote hydrogen-atoms and the remaining radical is one of the said hydrocarbon groupsi A large n'umberof com pounds (11a) is easily accessible by reaction of olefins (IV) with aldehydes (V) asshown:
Preferred starting materials (IIa) are those having four to ten carbon atoms, for examplebut-l-en-4-ol, Z-methylbut-l-en-4-ol, 3-methylbut-l-en 4-ol, pent-Z-en-S-ol and2- cyclohexylbut-1-en-4-ol. The compounds butl-en-4-ol and 3,655,768 Patented Apr. 11, 1972 2-methylbut-l-en-4-ol have particular industrial importance.
Particularly suitable ketones (III) are those having the general Formula IIIa:
R R (IIIa) where the radicals R to R each denotes a hydrogen atom or an aliphatic, cycloaliphatic, araliphatic or arm matic hydrocarbon group having up to eight carbon atoms, these groups if desired being combined in pairs to form five-membered to seven-membered rings. Preferred compounds (lIIa) are those having from three to eight carbon atoms, for example acetone, methyl ethyl ketone, diethyl ketone, cyclohexenyl methyl ketone and acetophenone. Diethyl ketone and acetone have particular industrial importance.
When the ketone (III) is unsymmetrical and bears at least one hydrogen atom on both of the carbon atoms adjacent to the carbonyl group, a mixture of two different compounds (I) is obtained.
According to observations made so far, the success of the process acording to this invention is not perceptibly dependent on the nature of the substituents on (III) and (HI), particularly on (11a) and (Illa) provided it is borne in mind that the reaction rate generally decreases as the molecular size of these compounds increases. Undesired secondary reactions, in particular the polymerization of (I) and (II) or (Ila) or the intramolecular elimination of water from (H) or (IIa), may be suppressed as usual by operating in the presence of polymerization inhibitors or in the presence of water under pressure. Moreover, it is often advisable to accelerate the reaction in the desired direction by using one of the reactants in an excess of up to twenty times.
The preferred reaction temperatures are from 200 to 350 C. Since most of the starting materials (II) and (III) which have special importance industrially would be gaseous at these temperatures at atmospheric pressure and since the reaction in liquid phase is preferred, it is preferable to use superatrnospheric pressure (up to about 1000 atmospheres), preferably the vapor pressure which is set up above the reaction mixture at the temperature chosen.
Since the products (I) of the process are themselves ketones which fall under the definition for (III) and thus can undergo further reaction, it is advantageous to aim at low conversions or to use a large excess of (III). This procedure may best be carried out semicontinuously or continuously by a conventional method.
The reaction may be carried out with or without inert solvents or diluents but in general one of the reactants serves as solvent.
When water is used as solvent or diluent, it is advantageous to maintain a constant pH value of from about 5 to 8 by means of-buffer substances.
Many alk-l-en-6-onesfare accessible by the process according to this invention and some of them are valuable perfumes or can be used as intermediates for the synthesis of the same. i v v The invention is illustratedby the following examples.
EXAMPLE 1 290 g. (5 moles) of acetone and 70 g. (0.8 mole) of 2-methylbut- 1-en- 4-ol are heated in an autoclave for fortyfive minutes, a pressure of about 220 atmospheres being set up. The reaction mixture is worked up by distillation. 42 g. of 2-methy1hept-1-en-6-one passes over and 30 g. of 2-methylbut-1-en-4-ol is recovered. This is a yield of 72% with reference to the conversion; the conversion itself is 57%.
3 EXAMPLE 2 290 g. moles) of acetone and 73 g. (1 mole) of but- 1-en-4-ol are heated for one hour at 270 C. in an autoclave, a pressure of about 250 atmospheres being set up. The reaction mixture is worked up by distillation; hept-len-6-one is obtained in a yield of 63% with reference to a conversion of 50%.
EXAMPLE 3 280 g. (3.2 moles) of diethyl ketone and 70 g. (0.8 mole) of 2-methylbut-1-en-4-ol are heated for forty-five minutes at 300 C., a pressure of about 250 atmospheres being set up. The reaction mixture is worked up by distillation; 2,5-dimethyloct-1-en-6-one is obtained in a yield of 48% with reference to a conversion of 39%.
We claim:
1. A process for the production of an alk-l-en-6-one which comprises reacting, at from 100 to 400 C., an alk-1en-4'ol of the formula:
R I l H wherein each of the radicals R to R when taken alone denotes a hydrogen atom or an aliphatic, cycloaliphatic or aromatic hydrocarbon radical having up to eight carbon atoms and wherein two of the radicals R to R when taken together form a fiveto seven-membered carbocyclic ring and wherein the alkl-en-4ol contains a total of from four to ten carbon atoms, with a ketone of the formula:
wherein each of the radicals R to R when taken alone denotes a hydrogen atom or an aliphatic or cycloaliphatic 4 hydrocarbon radical and wherein two of the radicals R to R when taken together form a fiveto seven-membered carbocyclic ring and wherein the ketone contains a total of from three to eight carbon atoms.
2. A process as claimed in claim 1 wherein four of the radicals R to R denote hydrogen atoms and the remaining radical denotes one of the said hydrocarbon radicals.
3. A process as claimed in claim 1 wherein but-1-en-4- 01 or 2-methylbut-l-en-4-ol is used as the alk-l-en-4-ol.
4. A process as claimed in claim 1 carried out at from 200 to 350 C.
5. A process as claimed in claim 1 carried out at a pressure of up to about 1000 atmospheres.
6. A process as claimed in claim 1 wherein said ketone reactant is selected from the group consisting of diethyl ketone and acetone.
7. A process as claimed in claim 1 wherein the ketone reactant is acetone and the alkenol reactant is Z-methylbut-1-en-4ol.
8. A process as claimed in claim 1 wherein the ketone reactant is acetone and the alkenol reactant is but-l-en- 4-ol.
9. A process as claimed in claim 1 wherein the ketone reactant is diethyl ketone and the alkenol reactant is 2- methylbut- 1-en-4-ol.
References Cited UNITED STATES PATENTS 3,326,978 6/1967 Dunkel 260593 R DANIEL D. HORWIT Z, Primary Examiner US. Cl. X.R.
- $55533 K UNITED y-xurzss PATENT OFF CE CERTIFICATE OF CORRECTION jI ce'np No. j 3,655,768 Dated Ap il 11.. 1972 ",Iflwuibfls)ffiorst; Pommer, Herbert Mueller, and HemnanLQve 91-min 1 i"; 'i s 'certified that error appears in the above-identified patent 'and that said Letters Paten; are hereby correcteias shown below:
Cqlumn '1, line 8, in the heading, after 775,518 insert-- Claims priority, application Germany, November 17, 1967,
,P 16 #3 696.! lines 33 to &2, should read (II)- 1 (III) L I j Signed-and sealed thi 28th day of NbIfer r Iber 1972.
SEAL) v t'es tz' I I EDWA D MJLEIGEIR R; ROBERT eo'rsrsmix I flj i te sting" ()izt'i'cem Commissioner of Patents
US775518A 1968-11-13 1968-11-13 Production of alk-1-en-6-ones Expired - Lifetime US3655768A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3890390A (en) * 1972-06-13 1975-06-17 Union Carbide Corp Process for the production of methyl ketones
US3932462A (en) * 1972-11-17 1976-01-13 Basf Aktiengesellschaft Manufacture of unsaturated ketones
US4602117A (en) * 1984-11-13 1986-07-22 Bayer Aktiengesellschaft Process for the preparation of halogenated 3,3-dimethyl-5-hexen-2-ones

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3890390A (en) * 1972-06-13 1975-06-17 Union Carbide Corp Process for the production of methyl ketones
US3932462A (en) * 1972-11-17 1976-01-13 Basf Aktiengesellschaft Manufacture of unsaturated ketones
US4602117A (en) * 1984-11-13 1986-07-22 Bayer Aktiengesellschaft Process for the preparation of halogenated 3,3-dimethyl-5-hexen-2-ones

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