GB2260980A - Preparation of unsaturated cyclic ketones - Google Patents

Preparation of unsaturated cyclic ketones Download PDF

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Publication number
GB2260980A
GB2260980A GB9222664A GB9222664A GB2260980A GB 2260980 A GB2260980 A GB 2260980A GB 9222664 A GB9222664 A GB 9222664A GB 9222664 A GB9222664 A GB 9222664A GB 2260980 A GB2260980 A GB 2260980A
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Prior art keywords
compound
process according
general formula
group
defined above
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GB9222664D0 (en
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Paul Howard Briner
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/603—Unsaturated compounds containing a keto groups being part of a ring of a six-membered ring
    • 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
    • C07C45/72—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 of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—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 of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

Ketones of the general formula <IMAGE> in which R represents an option ally substituted alkyl or cycoalkyl group and R<1> and R<2> independently represent a hydrogen atom or an optionally substituted alkyl, cycloalkyl or aryl group, are prepared by heating a compound of the general formula <IMAGE> in which X represents a chlorine or bromine atom and R is as defined above, with a compound of the general formula <IMAGE> in which R<1> and R<2> are as defined above, in the presence of an organic acid.

Description

PROCESS FOR THE PREPARATION OF CYCLIC KETONES This invention relates to a process for the preparation of certain cyclic ketones.
According to the present invention there is provided a process for the preparation of a compound of the general formula
in which R represents an optionally substituted alkyl or cycloalkyl group and R and R independently represent a hydrogen atom or an optionally substituted alkyl, cycloalkyl or aryl group, which comprises heating a compound of the general formula
in which X represents a chlorine or bromine atom and R is defined above, with a compound of the general formula
in which R1 and R2 are as defined above, in the presence of an organic acid.
When the compounds of formula I contain an alkyl substituent group, this may be linear or branched and may contain up to 12, preferably up to 6, and especially up to 4, carbon atoms. A cycloalkyl group may contain 3 to 8, especially 3 to 6, carbon atoms.
When any of the foregoing substituents are designated as being optionally substituted, the substituent groups which are optionally present may be any one or more of those customarily employed in the development of pesticidal compounds and/or the modification of such compounds to influence their structure/activity, persistence, penetration or other property. Specific examples of such substituents include, for example, halogen atoms, nitro, cyano, hydroxyl, cycloalkyl, alkyl, haloalkyl, alkoxy, haloalkoxy, amino, alkylamino, dialkylamino, formyl, alkoxycarbonyl, carboxyl, alkanoyl, alkylthio, alkylsulphinyl, alkylsulphonyl, carbamoyl and alkylamido groups. When any of the foregoing substituents represents or contains an alkyl substituent group, this may be linear or branched and may contain up to 12 preferably up to 6, and especially up to 4, carbon atoms.
It is preferred that R represents a C16 alkyl or C36 cycloalkyl group. More preferably, R represents a C 1-4 alkyl group.
It is also preferred that R1 and R2 independently represent a hydrogen atom or a C14 alkyl or C36 cycloalkyl group. More preferably, R1 and R2 independently represent a hydrogen atom or a C14 alkyl group.
It is especially preferred that R represents a methyl or propyl group, R1 represents a hydrogen atom or a methyl group, R represents a methyl group and X represents a chlorine atom.
Preferably, the organic acid is an organic sulphonic acid such as methyl sulphonic acid or, especially, para-toluenesulphonic acid.
It is further preferred that the reaction is carried out in a solvent which has the ability to remove water azeotropically from the reaction mixture.
Suitable solvents include aromatic solvents and chlorinated solvents, such as 1,2-dichloroethane.
The reaction is conveniently carried out at the reflux temperature of the solvent used.
It is also preferred that the compound of formula II is prepared by reacting ethene with a compound of the general formula
in which R and X are as previously defined, in a solvent in the presence of A1X3 where X is as defined above.
The solvent is preferably a chlorinated solvent, such as 1,2-dichloroethane, and it is particularly preferred that the solvent is the same as that to be used in the subsequent reaction of the compound of formula II thus obtained with a compound of formula III.
Conveniently, the reaction is carried out at a temperature in the range from 0 to 30 C, preferably 5 to 25 C.
Most preferably, the compound of formula II is prepared in situ. Preferably, it is then used in the reaction with a compound of formula III without further purification.
The invention is further illustrated by the following Examples.
Example 1 Preparation of 3,6-dimethylcyclohex-2-en-l-one (R=CH R1=H, R2=CH3) Aluminium chloride (140g, 1.05 moles) was added to l,2-dichloroethane (390ml) and the mixture cooled to about 0 C. Ethanoyl chloride (78.5g, 1 mole) was then added over a period of 20 minutes and the temperature of the reaction mixture allowed to rise to 200C. This solution was stirred for 30 minutes and ethene (28g, 1 mole) was then bubbled into the solution over a period of about 1k hours. The mixture was then quenched in a mixture of concentrated hydrochloric acid (150ml) and ice (750g) and the organic phase separated.An aliquot (containing 87.5 mmoles of chlorobutanone) was then added to a mixture of butan-2-one (20mls, 0.28 moles) and para-toluenesulphonic acid (0.3g, 1.6 mmoles) and the resulting mixture refluxed overnight on a Dean-Stark separator. After purification by chromatography on silica gel using dichloromethane as eluant, 2.2g 3,6-dimethylcyclohex-2-en-l-one was isolated (Yield: 20%).
NMR: (in CDCl3 solvent, tetramethylsilane as reference) Characteristic peaks at: 6(ppm): 1.03(3H, doublet, J=7Hz), 1.84(3H, singlet), 1.5-2.4(5H, complex), 5.74(1H, broad singlet).
Example 2 Preparation of 2,3, 6-trimethylcyclohex-2-en-l-one (R=Rl=R2=cH ) 4-Chlorobutan-2-one(5g, 46. 9mmol) ,pentan-3-one(4g, 47mmol), 1,2-dichloroethane(25ml) and para-toluenesulphonic acid (o.2g, 0.9minol) were heated together on a Dean and Stark separator overnight.
1.5g 2,3,6-trimethylcyclohex-2-en-l-one were obtained (Yield: 23%) NMR: (in CDC13 solvent, tetramethylsilane as reference). Characteristic peaks at:6(ppm): 1.04(3H, doublet, J=7Hz), 1.68(3H, singlet), 1.81(3H, singlet), 1.5-2.4(5H, complex).
Example 3 Preparation of 2,6-dimethyl-3-pro ylcyclohex-en-1-one (R=nC pZ.RZICH Using l-chlorohexan-3-one (20g, 0.148 moles), pentan-3-one (13g, 0.148 moles), para-toluenesulphonic acid (0.6g, 3.0 mmoles) and 1,2-dichloroethane (lOOml), 9.0g 2, 6-dimethyl-3-propylcyclohex- 2-en-l-one (Yield: 40%) were prepared by a method entirely analogous to those described in Examples 1 and 2.
NMR: (in CDC13 solvent, tetramethylsilane as reference). Characteristic peaks at:6(ppm): 0.86(3H, triplet, J=7Hz), 1.03(3H, doublet, J=7Hz), 1.40(2H, quartet, J=7Hz), 1.67(3H,singlet), 1.4-2.4 (7H, complex).

Claims (10)

1. A process for the preparation of a compound of the general formula
in which R represents an optionally substituted alkyl or cycloalkyl group and R1 and R2 independently represent a hydrogen atom or an optionally substituted alkyl, cycloalkyl or aryl group, which comprises heating a compound of the general formula
in which X represents a chlorine or bromine atom and R is as defined above, with a compound of the general formula
in which R1 and R2 are as defined above, in the presence of an organic acid.
2. A process according to claim 1 in which R represents a C1 - 6 alkyl or C3 6 cycloalkyl group.
3. A process according to claim 1 or claim 2 in which R1 and R2 which independently represent a hydrogen atom or a C14 alkyl or C 3-6 cycloalkyl group.
4. A process according to any one of the preceding claims in which R represents a methyl or propyl group, R1 represents a hydrogen atom or a methyl group, R2 represents a methyl group and X represents a chlorine atom.
5. A process according to any one of the preceding claims in which the organic acid is an organic sulphonic acid.
6. A process according to any one of the preceding claims in which the organic acid is para-toluenesulphonic acid.
7. A process according to any one of the preceding claims in which the compound of formula II is prepared by reacting ethene with a compound of the general formula
in which R and X are as defined in any one of the preceding claims, in a solvent in the presence of A1X3 where X is as defined above.
8. A process according to any one of the preceding claims in which the compound of formula II is generated in situ.
9. A process substantially as hereinbefore described and with reference to any one of Examples 1 to 3.
10. A compound of formula I whenever prepared by a process according to any one of the preceding claims.
GB9222664A 1991-10-31 1992-10-28 Preparation of unsaturated cyclic ketones Withdrawn GB2260980A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP91310060 1991-10-31

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GB2260980A true GB2260980A (en) 1993-05-05

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE42802E1 (en) 2000-04-18 2011-10-04 H. Lundbeck A/S Phenylethylamines and condensed rings variants as prodrugs of catecholamines, and their use

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0455304A1 (en) * 1990-05-01 1991-11-06 Shell Internationale Researchmaatschappij B.V. Process for the preparation of cyclic ketones

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0455304A1 (en) * 1990-05-01 1991-11-06 Shell Internationale Researchmaatschappij B.V. Process for the preparation of cyclic ketones

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE42802E1 (en) 2000-04-18 2011-10-04 H. Lundbeck A/S Phenylethylamines and condensed rings variants as prodrugs of catecholamines, and their use
JP4819280B2 (en) * 2000-04-18 2011-11-24 ハー．ルンドベック アー／エス Phenylethylamine and fused ring variant as catecholamine prodrug and use thereof
USRE43244E1 (en) 2000-04-18 2012-03-13 H. Lundbeck A/S Phenylethylamines and condensed rings variants as prodrugs of catecholamines, and their use

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