Cyclohexyl azide

Kwart and Khan investigated the copper-catalyzed decomposition of benzenesulphonyl azide both in methanol 33) and in cyclohexene 34>. No reaction occurs between benzenesulphonyl azide and cyclohexene at 100 °C but the addition of copper powder causes a smooth decomposition to take place yielding an impressive array of products 34>. The major ones are benzenesulphonamide 18 (37%), the aziridine 19 (15%) and the lV-(l-cyclohexenyl)benzenesulphonamide 20 (17%) (Scheme 2). Some traces of cyclohexyl azide were also found but the addition of hydro-quinone eliminated its formation. 

Other ring cleavages involve the reduction of the triazolotriazole (11), which gives 4-phenyltriazole, and the reaction of the mesoionic oxatriazolone (12) with diphenylacetylene, giving 1-cyclohexyl-4,5-diphenyltriazole, possibly through cyclohexyl azide as an intermediate... 

Azidocyclohexane. See Cyclohexyl Azide under Cyclohexane and J.H.Boyer et al,... 

Cyclohexane and derivs 3 C595 cyclohexyl azide 3 C595 1,2-dinitrocyclohexane 3 C595 mononitrocyclohexane 3 C595... 

Photolysis of (102) in the presence of water yielded cyclohexanone (27%) which was suggested to be formed via cyclohexyl azide and the antiaromatic, unknown triazirine... 

An additional example of diastereoselectivity is provided by the cyclization of a dienyl-substi-tuted cyclohexyl azide 13, a model cyclization for gephyrotoxin 148,149, Other groups in place of the ketal functionality produced mixtures of diastereomers. 

Stereospecific synthesis of secondary amines. Phenyidichloroborane (I) reacts with an azide, for example cyclohexyl azide (2). in benzene solution, first at 20" and... 

The reaction is stereospecific. Thus trans-2-methylcyclopentyldichloroborane (4) reacts with cyclohexyl azide (2) to give N-(tram-2-methylcyclopentyl)cyclohexyl-ainine (5). 

Additional support for the postulate of these two reaction paths comes from the thermolysis of cyclohexyl azide in ethyl benzoate and indene, where = 47.5 and 34.6 kcal.mole", and AS = 32.2 and 17.4 eu, respectively ". (The enormously high value of 32.2 eu may be due to some experimental error.) Ring enlargement has been observed in the thermolysis of phenyl azide in aniline solutions " " . 

The heats of formation of various azides were determined firom their heats of combustion and decomposition (some of the data are collected in reference 1). The heats of formation of HN3, cyclopentyl azide and cyclohexyl azide were compared with those calculated for the canoni-... 

Decomposition of aUcyl azides with aluminium chloride in benzene at 50° gave products which corresponded to the formation of a carbonium ion (loss of N3 ) and to an electron-deficient nitrogen (loss of N2) . For example, cyclohexyl azide gave phenylcyclohexane (30%), cyclohexanone imine (90) (15%) and the ring-expanded imine (91) (30-40%). The same workers reported the first example of an aUcyl nitrenium ion being trapped by benzene in reasonable yieldIn the presence of three equivalents of aluminium chloride in benzene, azidoacetone (92) gave the aromatic substitution product (93) in 35%... 

Walker and Waters considered the effects of various solvents on the rates of decomposition of phenyl, /(-methoxyphenyl and cyclohexyl azides and on the nature of the products obtained. Some of their results are summarized in Table 4. The decompositions could... 

The copper-catalysed decomposition of benzenesulphonyl azide in cyclohexene gave a variety of products (equation 182) . In the presence of hydroquinone, cyclohexyl azide was not observed. It was assumed that cyclohexanone came from the hydrolysis of the imine (405). The copper-catalysed decomposition of 2-biphenylylsulphonyl... 

Cyclohexene-l-ol, 90 2-Cyclohexenone, 262,484, 511 Cyclohex-2-enyl acetate, 318 Cyclohexylamine, 300 N-Cyclohexylaniline, 377 Cyclohexyl azide, 377 Cyclohexyl bromide, 126 Cyclohexylcarbinol, 192 Cyclohexylcaiboxalhyde, 192 l Cyclohexylcyclohexanol, 52 Cyclohexyldichloroborane, 371 Cyclohexyldimethylamine, 245 N-Cyclohexylhydroxylamine, 80... 

Alkyl isocyanates, like n-butyl isocyanate, do not react with different alkyl azides and aryl azides respectively. In contrast, aryl isocyanates 131 react with alkyl azides 130 like n-butyl azide or cyclohexyl azide to yield 1-alkyl-4-aryl-A -tetrazoline-5-ones 132, however, aryl isocyanates do not react with aryl azides. The reactions take place within some hours and up to several days at elevated temperatures, ranging from 55 to 130 °C, and are performed in benzene or without solvent (Scheme 29A). The addition of aryl azides to acyl isocyanates, such as benzoyl isocyanate or carboalkoxy isocyanates like chloroacetyl isocyanate and trichloroacetyl isocyanate, was unsuccessfully attempted at different reaction conditions [107]. 

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