Cycloheptanone 2-phenyl

The stereospecific C-alkylation of a range of benzylic ketones, such as tetralones, 2-phenylcyclohexanones and cycloheptanones, and 2-phenyl-y-lactones, has also been described [8]. For example, Af-(4-trifiuoromethylbenzyl)cinchonidinium bromide catalyses the reaction of 1,5-dibromopentane with 7-methoxy-l-methyl-2-tetralone to yield the (R)-l-(5-bromopentyl) derivative (75% yield with 60% ee). 

The procedure reported here provides a convenient method for the a-hydroxylation of ketones which form enolates under the reaction conditions. The reaction has been applied successfully to a series of para-substituted acetophenones, 1-phenyl-1-propanone, 3-pentanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclododecanone, 2-methyl cyclohexanone, 2-norbornanone and benzalacetone. In the case of a steroidal example it was shown that a carbon-carbon double bond and a secondary hydroxyl group are not oxidized. A primary amino function, as in the case of p-aminoacetophenone, is not affected.5 Similarly, a tertiary amino ketone such as tropinone undergoes the a-hydroxy at ion reaction.5... 

This reaction has been made with various carbonyl compounds, e.g., cyclopentanone,27 cyclohexanone,20 cycloheptanone,27 cycloocta-none,27 1-tetralone,21 2-tetralone,28 variously substituted acetophenones,29 phenyl benzyl ketone,29 dibenzyl ketone,29 dibenzoyl-methane,18, 30 ethyl benzoylacetate,18 ethyl malonate,30 malon-anilide,30 and 2-(bisalkylthio)methylenecyclopentanones and cyclohexanones.27... 

Presumably, the methyl sulfoxide was chosen here because it worked better—it is more usual to use a phenyl sulfoxide, and PhS groups can be introduced in the same way (by reacting enolates with PhSSPh or PhSCl). The cycloheptanone derivative used in our first elimination example was made from cycloheptanone in this way. 

Willstatter s method (Volume I, pp. 278 285-286) to a-methyltropidine, i.e. (+ )-5-dimethylamino-l,3-cycloheptadiene (LXXXIV). Resolution of the latter with dibenzoyltartaric acid followed by (a) isomerization of each antimer into )3-methyltropidines (LXXXV), (b) hydrolysis, (c) partial hydrogenation of the cycloheptenone, and (d) Grignard reaction with the cycloheptanones (LXXXVI) gave the phenyl-, and p-chlorophenyl-l-cycloheptenes (LXXXVII). The product of oxidation, arising from (+ )-LXXXI V, contained the whole radioactivity, while the benzoic and p-chlorobenzoic acids from the levorotatory form were radioinactive. This proved that the whole label from ornithine-a-i C was either in C-1 or in C-5 in hyoscyamine (80, 81). 

The procedure reported here provides a convenient method for the a-hydroxylation of ketones which form enolates under the reaction conditions. The reaction has been applied successfully to a series of para-substituted acetophenones, 1-phenyl-1-propanone, 3-pentanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclododecannne, 2-methyl cyclohexanone, 2-... 

A new synthesis of furans from a-hydroxyketones has been reported, e.g. (326) was prepared from sebacoin. Treatment of phenyl hydrazones of cyclic ketones with arsenic trichloride gave arsadiazoles, e.g. (327) was obtained from cycloheptanone. Novel 1,5-benzodiazepines, e.g. (328), were obtained when cyclic ketones were condensed with o-phenylenediamine or its 4-chloro-derivative in the presence of boron trifluoride etherate. "... 

The reaction of geminal dibromides and carbonyl compounds in the presence of butyl-lithium or lithium metal can provide a general route to a wide range of oxirans. Stevens and Pillai have used a Darzens cyclization reaction to form the first example of an isolable epoxy-amine (121). 2-(l-Aziridinyl)-2-phenyl-l-oxaspiro[2,5]octane (121) was relatively stable and rearranged to the corresponding cycloheptanone (122) only after... 

Dinitrophenylhydrazones of ketones including cycloheptanone are cleaved by aqueous solutions of TiCla." Only cis-cycloheptene was obtained by alkyl-lithium induced decomposition of cycloheptanone tosylbydrazone. Tosylhydrazones of a-halogenoketones react with phenyl copper at — 60 °C to give a-phenyl ketones after hydrolysis, thus a-chlorocycloheptanone was converted into a-phenylcyclohept-anone. ... 

The reaction of cycloheptanone with hexamethylphosphoramide gives (325) in low yield condensations of the ketone with 6-amino-2,4,5-triphenyl-resorcinol to give (326) and with the dianion of methyl- or phenyl-succinic acid monoesters to give (327 R = H or Me) are reported. 

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