Synthese und Eigenschaften von N , N ‐Dihalogen‐1,1‐difluoraminen RCF ₂ NXX′

Abstract

Aus der Umsetzung der Nitrile X-CN (la-4a, X = CI, CF3, CC13, CH3) mit Chlor und Brom lassen sich die N,N-Dihalogen-1,l-difluoramine R-CF2-NX2 (R = F, CF?, CC13, CH3; l d -4 d X = C1, le-4e: X = Br) in hohen Ausbeuten darstellen. Synthesewege zu den nicht in reiner Form isolierten Bromchloraminen RCF2NBrC1 (lg-4g) werden aufgezeigt. Im Falle der Ethylverbindungen lassen sich durch Wahl der Stochiometrie die Imine RCF=NX (2b-4b: X = C1; 2c-4c: X = Br) erzeugen. Sowohl Thermolyse als auch Photolyse der Amine fiihrt zu den Diazenen (R-CF,-N=),(lf-40. Synthesis and Properties of N,N-Dihalo-1,l-difluoroamines R -CF2 -NXX'The nitriles X-CN (la-4a, X = C1, CF3, CCl3, CH3) react with chlorine and bromine to form N,N-dihalo-1,l-difluoroamines R-CFz-NXz (R = F, CF3, CC13, CHI; ld-4d: X = CI; le-4e: X = Br) in high yields. Routes are shown for the synthesis of bromochloroamines RCF,NBrCl (lg-4g), which could not be isolated in pure state. For the ethyl derivatives the imines R-CF=NX (2b-4b X = C1; 2c-4c: X = Br) were obtained in good yields by using the appropriate stoichiometry. Both thermolysis and photolysis of the amines give the diazenes (R-CF2-N=)* (If-40.N,N-Dihalogenarnine und N-Halogenimine (Halogen = Chlor oder Brom) besitzen aufgrund der Labilitat der Stickstoff-Halogenbindung grol3e Bedeutung fur die praparative Chemie". Einen Uberblick uber Darstellung und Eigenschaften der bisher bekannten Perhalogenalkyl-N-Halogenverbindungen gibt ein kiirzlich erschienener Gmelin-Band'). RHdCN + C1F +

Halogenation of (CF3)3B·NH3: N,N-Dihaloamino- and Halo-tris(trifluoromethyl)borates [(CF3)3B−NX2]- and [(CF3)3B−X]-, X = F, Cl, Br

“…This reaction proceeds further to yield nitriles when R 1 or R 2 or both are also hydrogen atoms. Consequently, the RNX 2 compounds are particularly stable when the α carbon atom carries no hydrogen substituent (e.g., R = t -Bu or C n F 2 n +1 ). The (CF 3 ) 3 B - anion, which is isoelectronic with the perfluoro- tert -butyl group, also fulfills this criterion, and this analogy offers a rationale for the extraordinary stability of 2 to 4 , of which 3 may well be the most stable RNBr 2 derivative prepared so far.…”