Formation of an Azabicyclopentane Derivative on Photolysis of α‐Azidostyrene

Abstract

+ 2 CzH4 + 3 CZH,OA~(O~CSH,),Experimental 1 mmole each of ( I ) and (2) are dissolved in 10 ml of anhydrous, Nz-saturated benzene and treated with 1.5 mmoles of (3) slowly and with stirring at room temperature. Ethylene is evolved and the color changes within 30 min from green to dark brown. The small amounts of decomposition products that are formed during the reaction are filtered off, and the filtrate is concentrated in a vacuum t o 3-5 ml and treated with 20 ml of ether. The brown crystals of 4-(diphenylphosphinomethyl)-1,l-diethyl-1 -hydrido-2,2,6,6,7,7-hexaphenyl-2,6,7-triphospha-l-cobaltabicyclo(2.2.2]octane (4), which separate within an hour, are filtered off, washed twice with 10 ml of diethyl ether, and dried in a vacuum. Compound ( 4 ) is extremely sensitive t o air, soluble in benzene, acetone, or chloroform, and insoluble in petroleum ether, cyclohexane, or diethyl ether.

Intramolecular cycloaddition reactions of vinyl azides bearing alkenyl and alkynyl groups

“…The conversion of 3 into 7 represents a typical example of azirine formation from a vinyl azide. [5][6][7][8][9][10][11][12][13][14][15][16] The minor component of the reaction mixture was a white crystalline solid, mp 165-166 °C, whose structure is assigned as 9-methylene-9fl-dibenzo[c,e]-i>-triazolo[l,5-a]azepine (8) on the basis of its elemental analysis and spectroscopic data [NMR (60 MHz) r 4.39 (s, 1 ), 4.10 (s, 1 ), 2.20-2.70 (m, 8 H), and 2.08 (s, 1 H)j. This structure was further established by the independent synthesis outlined in Scheme I.…”

Metal atom reactions with fluorocarbons. I. Nonsolvated fluoroorganic zinc compounds

“…cates that these nonsolvated organozinc compounds are much more reactive and less stable than those formed in solution. 4 Fluoroform is an important product when either acetone or pivalaldehyde is used as an additive. The hydrogen uptake by CF3 must be free radical in nature for the following reasons.…”