Cyclohexanone 3-acetyl

Reference has also already been made (Chapter 2, Section A.7) to the reaction which takes place between cyclohexanone and PhPCl2, and through which (1-chlorocyclo-hexyl)phenylphosphinic acid was obtained as an illustration of this synthetic route to a (1-chloroalkyl)phosphinic acid. Mixtures of the same reactants which also contain water or an alcohol or a mixture of cyclohexanone, acetyl chloride and phenylphosphonous acid yield the isomeric (l-hydroxycyclohexyl)phenylphosphinic chloride 230 ". The same compound was also formed when a 1 1 mixture of phenylphosphonous dichloride and phenylphosphonous acid (phenylphosphinic acid) was allowed to interact with cyclohexanone, no addition occurring between the acid and the ketone in the absence of the PhPCl2. The formation of230 was therefore depicted as the addition of the cyclohexanone... 

Cyclohexanon Mesityloxid I - Acetyl-cyclohexen 3-Oxo- l-phenyl-buten-( 1)... 

The stereoselective intramolecular Henry reactions have been reported by Seebach. The Michael addition of doubly deprotonated acetyl acetaldehyde to l-methylenedioxyphenyl-2-nitroethene followed by subsequent intramolecular nitro-aldol cyclization leads to the diastereomerically pure cyclohexanone derivative, where the nitro and OH groups are cis as shown in Eq. 3.73.114 This reaction is applied to the synthesis of l-desoxy-2-lycorinone as shown in Eq. 3.74.115... 

Compound 197 has been treated with carbonyl-containing derivatives such as cyclohexanone and 3-methyl-l-phenylpyrazol-5-one, in refluxing ethanol containing some drops of piperidine as catalyst, in order to promote Michael additions leading to spiro derivatives 198 and 199, where an acetyl group has been eliminated during the process (Scheme 8) <2000FES641>. 

It is a hygroscopic solid and is recommended for the acetylation of a ketone, such as cyclohexanone. 

Apart from the reaction of cyclohexanecarboxylic acid with methyllithium, cyclohexyl methyl ketone has been prepared by the reaction of cyclohexylmagnesium halides with acetyl chloride or acetic anhydride and by the reaction of methylmagnesium iodide with cyclohexanecarboxylic acid chloride. Other preparative methods include the aluminum chloride-catalyzed acetylation of cyclohexene in the presence of cyclohexane, the oxidation of cyclohexylmethylcarbinol, " the decarboxylation and rearrangement of the glycidic ester derived from cyclohexanone and M)utyl a-chloroj)ropionate, and the catalytic hydrogenation of 1-acetylcycIohexene. "... 

Biological. Microbial degradation products reported include cyclohexanol (Dugan, 1972 Verschueren, 1983), l-oxa-2-oxocycloheptane, 6-hydroxyheptanoate, 6-oxohexanoate, adipic acid, acetyl-CoA, succinyl-CoA (quoted, Verschueren, 1983), and cyclohexanone (Dugan, 1972 Keck et al 1989). 

A similar acetylation procedure (without p-toluenesulfonic acid) has been employed to prepare other /3-diketones.5 As examples, cyclohexanone was converted to 2-acetylcyclohex-anone (73%) cyclopentanone yielded 2-acetylcyclopentanone (80%) 3-pentanone yielded 3-methyl-2,4-hexanedione (81%) dibenzyl ketone yielded l,3-diphenyl-2,4-pentanedione (72%), and acetophenone gave benzoylacetone (70%). 

Treatment of acetone with uranium(VI) fluoride in the vapor phase at room temperature gives13 some acetyl fluoride, along with much polymeric material. Under the same conditions, cyclohexanone also produces an unidentified acid fluoride initially, but this is then consumed to give polymeric material. 

Walther et al. improved the Na0Ph/C02 system by tuning the role of the solvent, such that the carboxylation of acetone was carried out selectively by sodium phenoxide with N-methyl-caprolactam under 0.1 MPa C02 to afford 3-ketoglutaric acid in 65% yield [34]. The same authors reported the conversion of acetyl-naphthalene (acetonaphthone) to acetyl-naphthalene carboxylic acid with 84% yield, and of cyclohexanone to cyclohexane-2,6-dicarboxylic acid in 56% yield. 

During the isolation of denudatine, Gotz and Wiesner (135) also isolated a new alkaloid, designated as delnudine (149), from the seeds of D. denudation. Preliminary spectral data revealed the presence of two hydroxyls, a cyclohexanone, and an exocyclic double bond in proximity with the ketone. The presence of the tertiary carbinolamine moiety was demonstrated by the formation of a basic diacetate (150) and a neutral 0,JV-diacetate (151) on acetylation with acetic anhydride in pyridine. They demonstrated that one of the ketones in compound 151 was derived from the carbinolamine moiety. Finally, the structure of delnudine was established as 149 by a single-crystal... 

This microflow processing was also demonstrated using other P-keto esters such as ethyl 2-chloro-3-oxobutanoate [309,273] or ethyl 2-methyl-3-oxobutanoate [273]. Five-and six-ring P-ketoester derivatives such as 3-acetyl-3,4,5-trihydrofuran-2-one (1) [273], 2-acetyl cyclohexanone [273] and ethyl 2-oxocydohexane carboxylate (2) [273] were directly fluorinated as well. 

On successive treatment with trimethyloxonium tetrafluoroborate, triethylamine and aqueous acid, oxime acetate 83 prepared from cyclohexanone oxime and Ac20 yields a-acetoxy ketone 87 (Scheme 7). A similar result is obtained with other symmetric ketones including 4-heptanone, deoxybenzoin and dibenzyl ketone. 87 can also be formed by the reaction of cyclohexanone and O-acetyl-Af-methylhydroxylamine hydrochloride upon hydrolysis. If the reaction time is prolonged prior to hydrolysis, ketoamide 89 is isolated as the main product. The key step of the reaction is the [l,3]-acetoxy shift of 7V-acetoxyenamine 85 to the a-acetoxyimine 86. The formation of 89 provides support for the intermediacy of acetoxyimine 86 in the reaction sequence. The evidence available suggests that the [l,3]-acetoxy migration proceeds via a Claisen-type rearrangement (Scheme 7)78. 

Moreover, it has been shown102 that under conditions of electrophilic catalysis by acetyl cations the addition of ketones to nitriles proceeds more rapidly than the self-condensation of ketones shown in equations 34-36. Thus, cyclohexanone reacts with both benzonitrile and acetonitrile in the presence of perchloric acid/acetic anhydride mixture to form Af-acyliminium salts 186 which are then converted to the Af-acylimines 187. The /Lacylaminoketones 9773 did not form the salts 186 in a control experiment... 

Besides formyl compounds, 2-acetyl,92 2-benzoyl,93 and 2-ethox-alyl94-96 cyclohexanones have been cyclized with hydroxylamine, to give 3-methyl-, 3-phenyl-, and 3-ethoxycarbonyl-4,5,6,7-tetrahydro-indoxazenes, respectively. In some cases the simultaneous formation... 

Nitration of enol acetates a-nitro ketones. This reagent is more useful than acetyl nitrate (AciO/HNOj) for nitration of enol acetates of cyclohexanones, particularly those of 2-alkyIcyclohexanones, which can undergo ring cleavage. However, yields are low unless the 2-substituent is a primary alkyl group. 

Lead tetraacetate oxidizes oximes to various products. For exanqrle, the oxime of cyclohexanone gives a-acetoxynitrosocyclohexane in 35% yield.Aldoximes react with lead tetraacetate to give nitrile oxides which then yield acetyl hydroxamates 1 reaction with acetic acid. ... 

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