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o ‐Benzochinon‐Addukte, Umlagerungs‐ und Eliminierungs‐Reaktionen von 1,1,3‐Trimethyl‐1,3,2‐diazaphospholidin‐1‐ium‐Salzen [1]
Author(s) -
Becker W.,
Schmutzler R.,
Schiebel H. M.
Publication year - 1992
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19921250407
Subject(s) - chemistry , adduct , medicinal chemistry , thermal decomposition , benzoquinone , halide , acceptor , organic chemistry , physics , condensed matter physics
o ‐Benzoquinone Adducts, Rearrangement and Elimination Reactions of 1,1,3‐Trimethyl‐1,3,2‐diazaphospholidin‐1‐ium Salts The 1,1,3‐Trimethyl‐1,3,2‐diazaphospholidin‐1‐ium Salts X − [ 1 (X = [Br, Y = NEt 2 ), 2 (X = [BPh 4 ], Y = Me), 3 (X = [BPh 4 ], Y = Ph), 4 (X = [BPh 4 ], Y = NEt 2 ), 5 (X = [BPh 4 ], Y = t Bu)] were treated with o ‐benzoquinones. The reaction of 1 with tetrachloro‐ o ‐benzoquinone furnished the spirophosphorane 6 with an intact N → λ 5 P donor‐acceptor interaction. The reaction of 2, 3 , and 4 with 3,5‐di‐ tert ‐butyl‐ o ‐benzoquinone furnished [BPh 4 ] − [ 8 (Y = Me), 9 (Y = Ph), 10 (Y = NEt 2 )]. The reaction of 5 with 3,5‐di‐ tert ‐butyl‐ o ‐benzoquinone yielded 7 which exhibited no significant N →λ 5P donor‐acceptor interaction. The rearrangement product 11 was formed in small amounts during the reaction of 5 with tetrachloro‐ o ‐benzoquinone; 11 was also prepared by an alternative route. Thermolysis of the 1,1,3‐trimethyl‐1,3,2‐diazaphospholidin‐1‐ium salts X − [ 14 (X = Br), 15 (X = I)] in vacuo led, with elimination of methyl halide, to the 1,3,2‐diazaphospholidines 16 (X = Br) and 17 (X = I). The salts were characterized by FAB‐MS.