1193-18-6

Usage

Uses

Used in Pharmaceutical Industry:
3-Methyl-2-cyclohexen-1-one is used as a starting material for the synthesis of 19-nor-1α, 25-dihydroxyvitamin D(3) derivatives, which have potential applications in the pharmaceutical industry.
Used in Pheromone Production:
3-Methyl-2-cyclohexenone is an insect sex pheromone of the Douglas-fir beetle, making it useful in the field of pest control and ecology.
Used in Flavor Industry:
3-Methyl-2-cyclohexen-1-one is used in the nut flavor industry due to its nutty, musty, phenolic, and woody taste characteristics.
Used in Fragrance Industry:
3-Methyl-2-cyclohexen-1-one is used as an organic building block in the total synthesis of various natural compounds, such as (?)-ar-tenuifolene, a naturally occurring aromatic sesquiterpene, and natural diterpenoids (+)-taiwaniaquinone H and (+)-dichroanone, which have applications in the fragrance industry.
Used in Food Industry:
3-Methyl-2-cyclohexen-1-one is reported to be found in oil of Mentha pulegium, cocoa, coffee, filbert, sweet corn, dried bonito, katsuobushi, wild rice, and clam, indicating its potential use in the food industry for flavor enhancement.
Occurrence:
3-Methyl-2-cyclohexen-1-one can be found in various natural sources, such as Mentha pulegium oil, cocoa, coffee, filbert, sweet corn, dried bonito, katsuobushi, wild rice, and clam. It is also produced by some animals in vivo.
Production Methods:
3-Methyl-2-cyclohexen-1-one may be prepared by acid hydrolysis and decarboxylation of the corresponding 4-carbetoxy derivative; by oxidation of 1-methylcyclohex-l-ene with chromium trioxide in acetic acid; or by cyclization of 3-carbetoxy-6-chlorohept-5-en-2-one with sulfuric acid.

Preparation

By acid hydrolysis and decarboxylation of the corresponding 4-carbetoxy derivative; by oxidation of 1-methylcyclohex-1-ene with chromium trioxide in acetic acid; by cyclization of 3-carbetoxy-6-chlorohept-5-en-2-one with sulfuric acid.

Synthesis Reference(s)

Journal of the American Chemical Society, 101, p. 494, 1979 DOI: 10.1021/ja00496a044The Journal of Organic Chemistry, 42, p. 1349, 1977 DOI: 10.1021/jo00428a017Tetrahedron Letters, 17, p. 3, 1976

InChI:InChI=1/C7H10O/c1-6-3-2-4-7(8)5-6/h5H,2-4H2,1H3

Upstream product

• 5323-87-5 3-Ethoxycyclohex-2-en-1-one 
• 676-58-4 methylmagnesium chloride 
• 75-16-1 methylmagnesium bromide 
• 591-49-1 1-methylcyclohex-1-ene 
• 89-81-6 piperitone 
• 62269-48-1 3-[(trimethylsilyl)oxy]cyclohex-2-en-1-one 
• 917-54-4 methyllithium 
• 56671-81-9 3-bromo-2-cyclohexen-1-one 
• 141-97-9 ethyl acetoacetate 
• 78-94-4 methyl vinyl ketone 
• 105996-56-3 (3-Ethoxy-3-methyl-cyclohex-1-enyloxy)-trimethyl-silane 
• 76793-92-5 7-methyl-1,4-dithiaspiro[4.5]dec-6-ene 
• 18951-83-2 (-)-trans-(2R)-bromo-(5R)-methylcyclohexanone 
• 74173-18-5 (R)-trimethyl(3-methylcyclohex-1-enyloxy)silane 

Downstream Products

• 43042-60-0 2-methoxy-3-methyl-cyclohex-2-enone 
• 18407-91-5 1-<(triethylsilyl)oxy>-3-methylcyclohex-1-ene 
• 29481-98-9 1,3-dimethyl-2-cyclohexen-1-ol 
• 2979-19-3 3,3-dimethylcyclohexanone 
• 4573-05-1 1,3-dimethyl-1,3-cyclohexadiene 
• 94834-51-2 (3-methyl-cyclohex-2-enyliden)-acetic acid ethyl ester 
• 124648-09-5 cyano-(3-methyl-cyclohex-2-enyliden)-acetic acid ethyl ester 
• 82998-31-0 3-methyl-2-cyclohexenethione 
• 81793-30-8 1-<2-(1,3-dithianyl)>-3,5,5-trimethylcyclohex-2-en-1-ol 
• 145728-43-4 5-Methyl-1-phenyl-spiro[2.5]oct-4-ene 
• 101514-23-2 (+/-)-6-hydroxy-3-methylcyclohex-2-en-1-one 
• 111681-10-8 6-hydroxy-3-methoxymethyl-2-cyclohexenone 
• 100-84-5 1-methoxy-3-methyl-benzene 
• 33426-65-2 3-methylphenol n-propyl ether 

Relevant academic research and scientific papers

Two-phase synthesis of (-)-taxuyunnanine D

The first successful effort to replicate the beginning of the Taxol oxidase phase in the laboratory is reported, culminating in the total synthesis of taxuyunnanine D, itself a natural product. Through a combination of computational modeling, reagent screening, and oxidation sequence analysis, the first three of eight C-H oxidations (at the allylic sites corresponding to C-5, C-10, and C-13) required to reach Taxol from taxadiene were accomplished. This work lays a foundation for an eventual total synthesis of Taxol capable of delivering not only the natural product but also analogs inaccessible via bioengineering.

Dirhodium(II) carboxylate-catalysed oxidation of allylic and benzylic alcohols

Allylic and benzylic alcohols are oxidised to the corresponding carbonyl compounds using tert-butyl hydroperoxide, preferably in stoichiometric amounts, and dirhodium(II) tetraacetate as catalyst (1 mol%) in dichloromethane at ambient temperature.

Vinylcyclopropylacyl Radicals. Intramolecular Ketene Additions leading to Concise Syntheses of Cyclohexenones

Treatment of a range of vinylcyclopropyl selenyl esters with Bu3SnH-AIBN produces cyclohexenone products (50-60%) via 6-exo-dig radical cyclisations involving ketene intermediates.

A convenient one-pot synthesis of cyclohexenic primary amines

The reaction between Grignard reagents prepared from allylic or propargylic halides and the N-phenylsulfenimine derived from the heptane- 2,6-dione affords primary 1-alkenyl (or alkynyl)-3-methylcyclohex-2-enamines in good yields.

Role of Amine Modifiers in the Epoxidation of Allylic Alcohols with a TiO2-SiO2 Aerogel

A detailed study of the epoxidation of 3-methyl-2-cyclohexen-1-ol with tert-butylhydroperoxide revealed that the poor performance of a 20 wt% TiO2-80 wt% SiO2 aerogel was due to nonoxidative consumption of the allylic alcohol. Epoxide selectivities could be improved remarkably and acid-catalyzed side reactions suppressed by addition of small amounts of aliphatic, cycloaliphatic, or aromatic amines. The best modifier was N, N-dimethylbutylamine. Amine (1 mol%) enhanced the epoxide selectivities, related to the reactant or peroxide, from 3 to 99% and 35 to 100%, respectively. Kinetic investigations uncovered how the chemical structure and the amount of various amines influence the complex network of redox- and acid-catalyzed reactions during allylic alcohol epoxidations. The stability of amines was studied under oxidizing reaction conditions. The method of amine addition was applied also to the epoxidation of other linear and cyclic allylic alcohols and 2-hexene. The scope of this method seems to be limited to epoxidation of allylic alcohols. A model for the interaction of allylic alcohol, amine, and peroxide with the Ti active site is proposed, which can interpret the enhanced selectivity and suppressed activity in the presence of amines or other bases.

Vinylsilane-terminated cycloacylation: A general synthetic approach to four- to six-membered cyclic ketones and its regiochemical features

Intramolecular acylations of m-trimethylsilyl-m-alkenoyl chlorides (m = 4 and 5) are described which afford the expected α-alkylidenecycloalkanone and/or the unexpected cycloalkenone, depending markeldy upon the substitution pattern on the vinylsilane moiety and/or the chain length (m).

Resolution of Allylic Alcohols by Cholesterol Oxidase Isolated from Rhodococcus erythropolis

The oxidation of non-steroidal compounds by cholesterol oxidase isolated from Rhodococcus erythropolis is reported for the first time.It was regio-, stereo- and enantio-selective.The enzyme oxidized preferentially the 2-cyclohexenyl-1-alcohols whose configuration is (S) at the reaction center.

BIOTRANSFORMATION OF LIMONENE AND RELATED COMPOUNDS BY ASPERGILLUS CELLULOSAE

The biotransformation of (+)-, (-)- and (+/-)-limones by Aspergillus cellulosae M-77 has been investigated. (+)-Limonene was transformed mainly to (+)-isopiperperitenone, (+)-limonene-1,2-trans-diol, (+)-cis-carveol and (+)-perilly alcohol, along with the minor formation of isopiperitenol and α-terpineol, whereas (-)-limonene was transformed to (-)-perillyl alcohol, (-)-limonene-1,2-trans-diol and (+)-neodihydrocarveol as the major products, along with the minor products such as (-)-isopiperitenone.In the case of the DL-form, perillyl alcohol, limonene-trans-1,2-diol, isopiperitenone and α-terpineol were also formed. 1-Methylcyclohexene and cyclohexene were also transformed to 3-methyl-2-cyclohexenone and 2-cyclohexenone via the corresponding alcohols, respectively.Key Word Index: Aspergillus cellulosae; biotransformation; (+)-, (-)- and (+/-)-limones; isoperitenone; limonene-1,2-trans-diol; cis-carveol; α-terpineol; 1-methylcyclohexene; cyclohexene; 3-methyl-2-cyclohexenone; 2-cyclohexenone.

INTRAMOLECULAR ACYLATION OF VINYLIC SILANES. A NOVEL, GENERAL APPROACH FOR THE SYNTHESIS OF FOUR- TO SIX-MEMBERED CARBOCYCLIC SYSTEMS AND ITS REGIOCHEMICAL FEATURES

Intramolecular acylations of m-trimethylsilyl-m-alkenoyl chlorides (m = 4 and 5) are described which afford the expected α-alkylidenecycloalkanone and/or the unexpected cycloalkenone, depending upon the substrate struture.

Integrated Electro-Biocatalysis for Amine Alkylation with Alcohols

The integration of electro and bio-catalysis offers new ways of making molecules under very mild, environmentally benign conditions. We show that TEMPO mediated electro-catalytic oxidation of alcohols can be adapted to work in aqueous buffers, with minimal organic co-solvent, enabling integration with biocatalytic reductive amination using the AdRedAm enzyme. The combined process offers a new approach to amine alkylation with native alcohols, a key bond formation in the chemical economy that is currently achieved via precious metal-catalyzed hydrogen-borrowing technologies. The electrobio transformation is effective for primary and secondary alcohols undergoing coupling with allyl, propargyl, benzyl, and cyclopropyl amines, and has been adapted for use with solid-supported AdRedAm for ease of operation.