4095-02-7

Usage

Uses

Used in Fragrance Industry:
ETHYL2-CYCLOHEXANONEPROPIONATE is used as an intermediate in the synthesis of Hexahydrocoumarin (H293905), a derivative of Coumarin (C755380) that is used as a fragrance ingredient. Its role in the production of fragrances is crucial, as it helps create unique and complex scents that are used in various personal care and household products.
Used in Chemical Synthesis:
ETHYL2-CYCLOHEXANONEPROPIONATE is also used as a building block in the synthesis of other organic compounds. Its versatile structure allows it to be a valuable component in the creation of various chemical products, including pharmaceuticals, agrochemicals, and other specialty chemicals. Its ability to be modified and incorporated into different molecular structures makes it a valuable asset in the field of organic chemistry.

Synthesis Reference(s)

Tetrahedron, 20, p. 1737, 1964 DOI: 10.1016/S0040-4020(01)99175-6

InChI:InChI=1/C11H18O3/c1-2-14-11(13)8-7-9-5-3-4-6-10(9)12/h9H,2-8H2,1H3

Upstream product

• 1125-99-1 1-(1-Cyclohexen-1-yl)pyrrolidine 
• 140-88-5 ethyl acrylate 
• 77299-75-3 2,2-Dibutyl-3-cyclohex-1-enyl-[1,3,2]oxazastannolidine 
• 2275-26-5 3-(2-oxocyclohexyl)propionic acid 
• 298-06-6 O,O-Diethyl hydrogen phosphorodithioate 
• 108-94-1 cyclohexanone 
• 17448-51-0 2-Hydroxyimino-cyclohexanpropionsaeure-ethylester 
• 97022-10-1 3-(2-Pyrrolidin-1-yl-cyclohex-1-enyl)-propionic acid ethyl ester 
• 823-45-0 2-(hydroxymethylene)cyclohexanone 
• 64-17-5 ethanol 

Downstream Products

• 52890-22-9 ethyl 3-(2-methylidenecyclohexyl)propionate 
• 17448-51-0 2-Hydroxyimino-cyclohexanpropionsaeure-ethylester 
• 94088-21-8 cis-2-<2-(ethoxycarbonyl)ethyl>cyclohexanol 
• 94088-21-8 trans-2-<2-(ethoxycarbonyl)ethyl>cyclohexanol 
• 4430-31-3 trans-octahydro-1-benzopyran-2-one 
• 4430-31-3 (+/-)-(4aR,8aR)-octahydro-2H-chromen-2-one 
• 10333-11-6 3,4,5,6,7,8-hexahydro-2-quinolinone 
• 52890-23-0 2-(3-hydroxypropyl)methylenecyclohexane 
• 107175-53-1 Methanesulfonic acid 3-(2-methylene-cyclohexyl)-propyl ester 
• 153446-20-9 3-(2-methylenecyclohexyl)propyl azide 
• 5164-37-4 1-methyl-4,4a,5,6,7,8-hexahydro-3H-naphthalen-2-one 
• 353460-57-8 (E)-5-(2-Oxo-cyclohexyl)-pent-2-enoic acid ethyl ester 
• 190851-42-4 2-[2-(2-Hexyl-[1,3]dioxolan-2-yl)-ethyl]-cyclohexanone 
• 29927-85-3 hexahydro-indan-1-one 

Relevant academic research and scientific papers

(±)-2-oxocyclohexanepropionic acid: Dual conformational selection and hydrogen bonding in a δ-keto acid, and a two-phase technique for crystallizing acids by contact with aqueous solutions of their salts

The asymmetric unit of the title compound, C9H14O3, consists of two molecules having conformations that differ by 121.7 (4)° in their rotation about the equatorial substituent bond, so that the side chain extends away from

Preparation of Hexahydrocarbazole Derivatives by Reductive Indolization

The reductive indolization is a two-step protocol performed in one flask: First, the acid-mediated Fischer indolization of a cyclic ketone with phenylhydrazine forms an iminium ion which is subsequently reduced by a hydrido borate reagent to the indoline as the final product. We utilized this new strategy for the preparation of hexahydrocarbazole derivatives with a side chain in the quaternary C4a-position. Starting materials were several N1- and aryl-substituted phenylhydrazines and a cyclic ketone with propanoic ester moiety, which is the product of the conjugated addition of cyclohexanone to ethyl acrylate. Furthermore, benzannulated congeners as well as a pyrido[4,3-b]indole derivative were accessed. The hexahydrocarbazole defines a molecular scaffold with two points of diversification. Therefore, several derivatives at N9 and at the C4a-side chain were prepared.

Microwave promoted regeneration of carbonyl compounds from oximes using N, N-dichloro poly(styrene-co-divinylbenzene)sulphonamide resin

An efficient, economically viable and operationally simple method was developed for deoximation of oximes (of ketones and aldehydes) to their corresponding carbonyl compounds using polymer beads of N, N-dichloro poly(styrene-co-divinylbenzene)sulphonamide resin. Polymeric reagent offered speedy conversion and substantial yields of products under mild condition and is recyclable. Deoximation was monitored by the use of 13C NMR.

Efficient carboazidation of alkenes using a radical desulfonylative azide transfer process

The radical-mediated carboazidation of terminal alkenes using electrophilic alkanesulfonyl azides is reported. A single reagent delivers the necessary electrophilic alkyl radical as well as the azido group, and good yields are obtained by using a moderate excess of the carboazidating reagent (1.5-2 equiv). Interestingly, in addition to the starting sulfonyl azide, this method requires only the use of a radical initiator, di-tert-butyldiazene. In terms of atom economy, this azide transfer reaction is close to ideal, as SO2 (1 equiv) is the only side product. The synthetic potential of this process has been demonstrated by a formal synthesis of the alkaloid lepadiformine C.

Total synthesis of the marine alkaloid (±)-lepadiformine via a radical carboazidation

The total synthesis of lepadiformine has been achieved in 10 steps and 15% overall yield from cyclohexanone. The amino-substituted quaternary carbon center is created through a radical carboazidation reaction. The tricyclic core of lepadiformine is built via an efficient hydrogenation process, involving reduction of the azide and intramolecular reductive amination of a ketone, followed by lactamization of the intermediate γ-aminoester. The hydroxymethyl side chain is introduced according to a modified Takahata procedure after conversion of the lactam into a thiolactam.

Construction of fused cyclooctanoid ring systems via seven-membered ring carbonyl ylides

A series of α-diazo carbonyl compounds tethered to cyclopentanone/cyclohexanone/1-tetralone units have been synthesized using a diazomethane solution to construct various fused cyclooctane ring systems via rhodium-generated carbonyl ylides. The reaction of rhodium(II) acetate dimer with various α-diazo carbonyl compounds generated transient cyclic seven-membered ring carbonyl ylides, which underwent facile 1,3-dipolar cycloadditions with dipolarophiles, like N-phenylmaleimide, p-benzoquinone, and DMAD to furnish a variety of fused epoxy-bridged cyclooctane ring systems in a tandem manner. Interestingly, an oxepine ring system was generated via an intramolecular proton transfer of a seven-membered ring carbonyl ylide. A tri-oxa polycyclic compound was obtained in the case of p-benzoquinone as dipolarophile. A single-crystal X-ray analysis of a fused cyclootanoid derivative is reported to decisively establish the structure and stereochemistry of the fused epoxy-bridged cyclooctane ring systems; a further analysis revealed the existence of a unique intermolecular C-H ···π interaction motif in the solid-state architecture.

Efficient and scaleable methods for ω-functionalized nonanoic acids: Development of a novel process for azelaic and 9-aminononanoic acids (nylon-6,9 and nylon-9 precursors)

A new, convergent synthesis and process of the title open-chain C-9 compounds, valuable monomers for preparation of polyamides with specific properties, are discussed. Starting from relatively inexpensive raw materials, for example, cyclohexanone and activated C-3 olefins, the method provides polymer grade co-functionalized nonanoic acids. An improved protocol for cyanoethylation or carbalkoxyethylation of cyclohexanone in the presence of a catalytic amount of primary or secondary amines gave 3-(2-oxo-cyclohexane) propanecarboxylic acid derivatives 1 in high yield. Cyclohexaneperoxycarboxylic acid (CHPCA) is introduced as highly efficient reagent in Baeyer-Villiger rearrangement of 1. Pyrolysis of 2 (EWG = CN) afforded under optimized conditions 3 in high yield and regioisomeric purity, otherwise a mixture of three unsaturated isomeric ω-cyano nonenoic acids is obtained. Partial hydrogenation of unsaturated acids 3 allowed isolation of saturated long-chain difunctionalized acids 4. Hydrolysis of 4 led to 1,9-nonanedicarboxylic acid (azelaic acid) 5, whereas its hydrogenation at elevated pressure gave 9-aminononanoic acid 6. Alternatively, a practical four-step syntehsis of 5 via isolable 7-substituted oxepan-2-one (EWG = COOMe) 2 has been designed and experimentated. The versatile position of 3-(2-oxo-cyclohexane) propanecarboxylic acid derivatives 1 as raw materials for Fine Chemicals is also discussed.

Efficient synthesis of ω-functionalized nonanoic acids

Starting from cyclohexanone and acrylonitrile, a four-step synthesis of the title open-chain C9 compounds is reported. An improved protocol for cyanoethylation of cyclohexanone in the presence of a catalytic amount of cyclohexylamine afforded 3-(2-oxocyclohexyl)propanenitrile (1) in 92% yield. Cyclohexaneperoxycarboxylic acid (CHPCA) is introduced as a highly efficient reagent in the Baeyer-Villiger rearrangement of 1, yielding over 90% of 2. Pyrolysis of 2 afforded under optimized conditions 3 in 92% yield and 99% regioisomeric purity, otherwise a mixture of three unsaturated isomeric ω-cyano nonenoic acids 3, 10 and 11 is obtained. Partial hydrogenation of 3 allowed the isolation of 4 in 90% yield. Hydrogenation of 4 at elevated hydrogen pressure gave 9-aminononanoic acid (5), whereas hydrolysis of 4 led to 1,9-nonanedioic acid (azelaic acid, 6). Both, 5 and 6 are valuable C9 monomers for the preparation of polyamides with specific properties.

THIONATION OF 3-(2-OXOCYCLOHEXYL)PROPIONIC ACID AND ITS DERIVATIVES

The reactions of the δ-keto acid 3-(2-oxocyclohexyl)propionic acid, its methyl ester, and its N-morpholide with phosphorus pentasulfide, O,O-diethyl dithiophosphate, and Lawesson's reagent were studied under various conditions. It was established that these reactions give mixtures of the acyclic and cyclic thionation products, the most important of which are cyclohexa-3,4-dihydro-2H-thiin-2-one, cyclohexa-3,4-dihydro-2H-pyran-2-one, and cyclohexa-3,4-dihydro-2H-thiin-2-thione; the latter readily undergoes spontaneous oxidation to cyclohexa-2H-thiin-2-thione.