Diazocyclohexanone

Caution 2-Diazocyclohexanone may explode, especially on being heated. The workup and distillation should be carried out in a fume hood behind a safety shield. 

In a 2-1. wide-necked Erlenmeyer flask are mixed 66.2 g. (0.525 mole) of 2-(hydroxymethylene)cyclohexanone (Note 1), 400 ml. of methylene chloride, and 106 g. (1.05 moles) of triethylamine (Note 2). The flask is cooled in an ice-salt bath at —12 to —15°, and 98.0 g. (0.500 mole) of -toluenesulfonyl azide (Note 3) is added with vigorous mechanical stirring over a period of approximately 1 hour, at such a rate that the temperature of the reaction mixture does not rise above —5°. Stirring is continued for an additional 2 hours as the cooling bath melts. A solution of 30.8 g. (0.55 mole) of potassium hydroxide in 400 ml. of water is added, and the mixture is stirred for 15 minutes at room temperature. The resulting emulsion is placed in a 2-1. separatory funnel, the methylene chloride layer is separated after the emulsion has broken, and the aqueous alcoholic layer is 

2-(Hydroxymethylene)cyclohexanone was prepared from cyclohexanone and was freshly distilled before use. 

-Toluenesulfonyl azide was prepared from jj-toluene-sulfonyl chloride and sodium azide. The submitters found that when somewhat less than the stoichiometric quantity of -toluenesulfonyl azide is used, 2-diazocyelohexanone is obtained free of azide the excess 2-(hydroxymethylene)-cyclohexanone is readily removed in the alkaline workup. The crude product obtained by the checkers, however, contained -toluenesulfonyl azide (Note 5). 

The basic aqueous solution on acidification with 6N hydrochloric acid gives N-formyl- -toluenesulfonamide in almost quantitative yield. Crystallization from benzene gave crystals, m.p. 101-102° (lit. 102-103°). 

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Benzoylphenyidiazomethane 2 Butan-l-yl diazoacetate t-Butyl diazoacetate t-Butyl-2-diazoacetoacetate Diazoacetonitrile 2-Diazocyclohexanone Diazocyclopentadiene 1 -Diazoindine... 

DIAZOCYCLOHEXANONE, 51, 86 a-Diazoketones, reaction with trialkylborane, 53, 82 rearrangement, 52, 53 synthesis, 52, 53 >°-Diazoketones, aromatic, from acid chlorides, 53, 37 -Diazoketones, cyclic, alkylation of, 53, 82, 83 Diazomethane, in modified Arndt-... 

Buten-l-yl diazoacetate, 2377 tert-Butyl diazoacetate, 2423 tert-Butyl 2-diazoacetoacetate, 3009 5-tert-Butyl-3-diazo-3//-pyrazole, 2831 Cyanodiazoacetyl azide, 1346 5 -Cy ano-4-diazo-4// -1,2,3 -triazole, 1345 Diazoacetaldehyde, 0710 Diazoacetonitrile, 0675 Diazoacetyl azide, 0679 2-Diazocyclohexanone, 2375 Diazocyclopentadiene, 1832... 

In addition to previously described syntheses4-5 by diazo group transfer with deformylation,6 2-diazocyclohexanone has been prepared by two variants of this method. In one, the reaction of 2-(hydroxymethylene)cyclohexanone with -toluene-sulfonyl azide is carried out in ether/diethylamine, and an enamine is assumed to be formed as an intermediate 7 in the other, the sodium salt of the hydroxymethylene compound was treated with the lithium salt of p-carboxybenzenesulfonyl azide... 

When thiocarbonyl and ot-diazocarbonyl compounds are combined, acyl-substituted thiocarbonyl ylides 158 are generated from a nonisolable 3-acyl-1,2,4-thiadiazoline 157 (Scheme 8.36). In addition to giving acylthiiranes 159 and 1,3-dithiolanes 160, dipoles 158 can also 1,5-cyclize to produce 1,3-oxathioles 161. Acyl-thiocarbonyl ylides derived from diazoketones [e.g., HC(0)C(N2)R, R = Ph, f-Bu (219,220) 2-diazocyclohexanone (221)] produce 1,3-oxathioles [e.g., 162 (220), Scheme 8.36], while those derived from diazoesters (218,222,223) lead to thiiranes by 1,3-cyclization. Ylides derived from a-diazocarboxamides form 1,3-oxathioles (e.g., 163) and thiiranes (e.g., 159, R = f-Bu, R = NMePh, R = R" = Ph), depending on the nature of the substituents (220). A related 1,5-cyclization of an aminomethyl-thiocarbonyl ylide formed from dimethyl 3-anilino-2-diazobutanedioate was also reported (224). 

Diazocyclohexanone, 510 Diazo group transfer, 510 a-Diazoketones, 44-45, 103 Diazomethane, 5, 120-122,455 Dibenz[6,/]azepine, 501 Dibenzobarrelene, 270 Dibenzo-18-crown-6, 142 Dibenzo-l,4-diazepines, 256 Di-2-benzothiazole disulfide, 242 Di-2-benzothiazole sulfide, 242 o-Dibenzoylbenzene, 209... 

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