The effect of additives on the reactions of ethyl azidoformate with cyclohexane

.alpha. Elimination of N-chloro-N-sodiourethane in ethers and in hydrocarbons

“…As for the decomposition of 4, where the singlet nitrene was generated, the effect of the additives such as nitrobenzene and sulfur led to the increased yield of the insertion products and to the decreased yield of the abstraction product. 10 The influence of copper on the present reaction was not so great as that on the reaction of chloramine-T, where the copper-nitrene complex had been proposed. This difference can be explained as follows.…”

“…Ethers and in Hydrocarbons Noboru Torimoto,* Tadao Shingaki,1 and Toshikazu Nagai1 Science Education Institute of Osaka Prefecture, Karita-cho, Sumiyoshi-ku, Osaka 558, Japan Received July 10,1978 We reported that, in the presence of copper, the reactions of N-chloroand , -dichlorourethanes with several substrates such as hydrocarbons and ethers proceeded via a copper-radical complex involving no nitrene.2 Furthermore, Carr et al reported that the reaction of chloramine-T with dioxane gave the N-substituted sulfonamide in the presence of copper, suggesting that a copper-sulfonylnitrene complex was formed as an intermediate. 3 In these reactions, the presence of copper gave the C-H insertion products, while it was found that the reaction of N-chloro-N-sodiourethane gave the C-H insertion product in spite of the absence of copper.…”

Thermal reactions of sulfonyl azides

“…Decomposition of Azides in Cumene. Pressure bottles containing (a) 0.75 g of 1-pentanesulfonyl azide in 12.5 ml of cumene, (b) 1.5 g of n-octadecyl azidoformate1 2 in 25 ml of cumene, (c) 1.0 g of p-toluenesulfonyl azide in 17 ml of cumene, and (d) 25 ml of cumene were flushed with nitrogen and then heated at 150°o vernight. The contents of the bottles were analyzed by gas chromatography for dicumyl with the following results: a, 0.89 pg/µ ; b, 1.31 µg/µl•, c, none detected; d, <0.01 µg/µl.…”

A study of the photolysis of O-methyl podocarpinitrile oxide

“…Step 1. Preparation of Methyl 0-methyl podocarpate(S, 31 ) [21] Podocarpic acid [8] (Table XVII). (Table XVII).…”

“…(Table XVII). [20] to methyl 0-methyl podocarpate [2]], reduction of ester [21] to 0-methyl podocarpinol [22], oxidation of alcohol [22] to 0-methyl podocarpinal [23], conversion to 0-methyl podocarpaldoxime [24], and then oxidation to 0-methyl podocarpinitrile oxide [l] in an overall yield of 41%. (Figure 1.)…”