Cyanonitrene

Hutchins, M. G. K. et al., Tetrahedron Lett., 1981, 22, 4599-4602 Interaction of sodium hydrogen cyanamide and tert-butyl hypochlorite in methanol at —50°C to ambient temperature forms cyanonitrene. Isolation gave an orange dimeric residue which exploded on two occasions. 

MFor a review of cyanonitrenes, sec Anastassiou Shepclavy Simmons Marsh, in Lwowski, Ref. 177. pp. 305-344. 

Cyanogen azide reacts with cyclooctatetraene (112) at room temperature in ethyl acetate to give alkylidenecyanamide.326 At 78°, a 31% yield of a mixture of the alkylidenecyanamide (113) (68%) and the 1,4-adduct 114 (32%) is obtained. Since cyanogen azide decomposes above 40° and since the alkylidenecyanamide does not rearrange to the 1,4 adduct under the reaction conditions, one may believe that the 1,4 adduct forms directly from cyanonitrene and cyclooctatetraene. This is a case of 1,4 addition studied by Anastassiou.328... 

Anastassiou has provided very strong evidence for collisionally induced relaxation of singlet cyanonitrene to its triplet ground state.67 Thermolysis of cyanogen azide at 40-45° in cis- or trans-1,2-dimethyl-... 

Cyanogen azide, 0541 Cyanogen bromide, 0312 Cyanogen chloride, 0322 Cyanogen fluoride, 0337a Cyanohydrazonoacetyl azide, 1080 5-Cyano-2-methyltetrazole, 1117 Cyanonitrene, 0537... 

Kirmse, and Gaspar and Hammond (1964) have emphasized that the preceding stereochemical criterion is useful but uncertain, because the state of the initial methylene and the probable lifetime of possible intermediates are often unknown. One of the more interesting aspects of this research area is therefore centered on the identification of the state of the reacting species. A state diagram and orbital correlations have been given for cyanonitrene (Anastassiou, 1967). 

For cyanonitrene it was shown that the linear structure is favored over the bent one and the ground state is a triplet... 

In contrast to the carbene chemistry, where addition to a double bond is a very common process, in nitrene chemistry the [1 + 2]-cycloaddition obviously occurs with carbethoxy- and cyanonitrene in an easy way only. There are three main reasons why [1 + 2]-cycloaddition of nitrenes to carbon-carbon double bonds is relatively rare ... 

Cyanogenazide 46 reacts, unlike most organic azides, with strained and unstrained double bonds at room temperature to give alkylidenecyanamides 47 and/or N-cyanoazirines 48 34>91>. These products are also expected from the reaction of cyanonitrene with olefins. 

Table 7. Stereochemistry of the insertion of cyanonitrene into the tertiary C—H bond of cis-and trans-l,2-dimethylcycIohexane as function of the solvent 94>...

Table 9. Stereochemistry of the insertion of photochemically generated cyanonitrene into tertiary C—H bonds of cis-1,2-dimethylcyclohexane 45>...

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