Cyclodecanone

Alkoxyall l Hydroperoxides. These compounds (1, X = OR , R = H) have been prepared by the ozonization of certain unsaturated compounds in alcohol solvents (10,125,126). 2-Methoxy-2-hydroperoxypropane [10027-74 ] (1, X = OR , R" = methyl), has been generated in methanol solution and spectral data obtained (127). A rapid exothermic decomposition upon concentration of this peroxide in a methylene chloride—methanol solution at 0°C has been reported (128). 2-Bromo-l-methoxy-l-methylethylhydroperoxide [98821-14-8]has been distilled (bp 60°C (bath temp.), 0.013 kPa) (129). Two cycHc alkoxyaLkyl hydroperoxides from cyclodecanone have been reported (1, where X = OR R, R = 5-oxo-l, 9-nonanediyl) with mp 94—95°C (R" = methyl) and mp 66—68°C (R" = ethyl) (130). Like other hydroperoxides, alkoxyaLkyl hydroperoxides can be acylated or alkylated (130,131). 

The reaction temperature is important. At temperatures below 75° some sebacoin remains unreduced, while at temperatures above 80° considerable cyclodecane is formed. The submitters report that the reaction run at the reflux temperature gives cyclodecanone in 27% yield and cyclodecane in 32% yield. 

The product should be isolated and distilled as quickly as possible inasmuch as the imreacted sebacoin is readily oxidized to sebacil, which cannot be separated from the cyclodecanone by simple distillation. 

For efficient separation of cyclodecanone from cyclodecane, a 60-cm. column of the simple Podbielniak type may be used. Removal of sebacil cannot be accomplished readily by fractional distillation, since cyclodecanone and sebacil have virtually identical boiling points. 

The procedure described is a modification of the directions of Prelog, Frenkiel, Kobelt, and Barman. Cyclodecanone has been prepared by the dehydration of sebacoin followed by catalytic hydrogenation, by the pyrolysis of the thorium or yttrium salt of nonane-1,9-dicarboxylie acid, and by the ring enlargement of cyclononanone, as well as by the reduction of sebacoin. ... 

Cupric oxide [Copper oxide (CuO)], 10 Cyclodecanone, 111 Cyclododecanone, 108 Cyclododecanone, 2,12-dibromo-, 107 1 -Cy cloheptene, 1 -bromo-7 -acety loxy-[2-Cyclohepten-l-ol, 2-bromo-, acetate], 34... 

Regio- and stereospecific 1,3-cycloaddition of di-tert-butylated acyl nitrone (548), generated in situ from (547), with Z-2-cyclodecanone and subsequent aromatization is the key step in the synthesis of biomimetic pyridomacrolidin... 

Cyclodecanone has been obtained together with other products in the pyrolysis of the thorium or yttrium salts of nonanedioic acid.3 4 It has also been prepared by reduction of sebacoin with zinc and hydrochloric acid,6, 6 by dehydration of sebacoin fol-... 

Cyclobutanecarboxylic acid, reaction with hydrazoic add, 47, 28 Cyclobutene, 1,2,3,4-tetramethyl-3,-4-oichloro-, 46, 34 reactions of, 46, 36 Cyclobutylamine, 47,28 Cvclobutyl isocyanide, 46, 77 Cyclodecanone, 48, 56 Cyclododecanone, conversion to cyclo-tetradecanone, 48, 58 Cyclohcptanone, 45, 31 conversion to cyclononanone, 48, 58 1, 3-Cyclohexadiene, 47, 31... 

The overall yield of cyclodecanone is comparable to the overall yield obtained by conversion of dimethyl sebacate to sebacoin 11 and subsequent reduction to cyclodecanone.6 In addition, the present procedure does not require the use of a high-speed stirrer, the rigorous exclusion of air, and the high dilution that are necessary in preparing sebacoin. 

Imines derived from macrocyclic ketones (C10 to C 15 ) and (- )-(S)-a-(methoxymcthyl)benzene-ethanamine are successfully deprotonated using LDA ( —25 JC. THF. 1 h)9. In contrast to azaenolates of C0- to C8-membered cyclic ketones, which show only E geometry, Z-isomers are observed with macrocyclic imines. As evident from H-NMR data, azaenolates of cyclodecanone imines generated under these conditions are a mixture of E- and Z-isomers (33 66), whereas azaenolates of cyclododecanone and cyclopenladecanone imines arc formed as the pure. E-isomers (see Table 3). Upon heating the solutions of metalated imines to reflux for 1 hour, complete isomerization to the thermodynamically more stable Z-isomers occurs. 

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