Addition derivatives, startg

A soln. of l-pyrrolidino-cw-3,5-dimethylcyclohexene and the startg. nitrone in dimethylformamide stirred 48 hrs. at room temp. 4-pyrrolidinoisoxazolidine deriv. Y 66%. Y. Nomura, F. Furusaki, and Y. Takeudii, Bull. Chem. Soc. Japan 43, 1913 (1970) normal addition cf. Synth. Meth. 22, 709. 

Carbohydrate derivatives. A soln. of D-mannose diethyl mercaptal in aq. 70%-ethanol treated portionwise with a slurry of Raney-Ni W 2 in ethanol, the composition of the mixture checked 15 min. after each addition, and the products isolated when the startg. m. has disappeared 4.31 g. crude 1-deoxy-1-ethylmercapto-D-mannitol and 0.98 g. 1-deoxy-D-mannitol. F. e. s. B. Lindberg and L. Norden, Acta Ghem. Scand. 15, 958 (1961). 

Ca-hypochlorite-soln. protected by a surface layer of mineral oil added dropwise under CO2 during 0.5 hr. to an aq. suspension of the startg. allene deriv., and stirring continued 15 min. -> product. Y 85%. - Addition of the chlorine atom occurs almost exclusively at the central C-atom. F. e. s. J.-P. Biandiini and M. Co-cordano, Tetrahedron 26, 3401 (1970). 

A 5%-soln. of the startg. olefinic benzocyclobutene deriv. in toluene heated 16 hrs. at 190° in an autoclave -> product. Y 85%. F. e., also addition to carbon-carbon triple bonds, stereo- and regio-specificity, s. W. Oppolzer and K. Keller, Am. Soc. 95, 3833-3836 (1971). 

Nitromethane added at 15 to a soln. of 1.1 g. of the startg. diformyl compound in anhydrous methanol followed by the addition with gentle stirring during 5 min. of a soln. of Na-meth-oxide cooled to 10, the cooling bath removed, and the mixture stirred 4 hrs. 1 g. nitrobenzene derivative. 

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