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Reaktive E = C(p—p)π‐Systeme, XXXI Erste Vertreter aminosubstituierter 1,2,4‐Diazaphosphole
Author(s) -
Grobe Joseph,
Van Due Le,
Hegemann Marianne,
Krebs Bernt,
Läge Mechtild
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.19921250219
Subject(s) - chemistry , diazomethane , cycloaddition , yield (engineering) , medicinal chemistry , stereochemistry , structural isomer , crystallography , organic chemistry , catalysis , materials science , metallurgy
Reactive E = C(p—p)π Systems, XXXII [1] . — First Representatives of Amino‐Substituted 1,2,4‐Diazaphospholes (Diisopropylamino)phosphaethyne i Pr 2 N—C≡P reacts at 20° C in a [3 + 2] cycloaddition with (trifluoromethyl)diazomethane ( 2a ) or methyl diazoacetate ( 2b ) to yield a mixture of the corresponding regioisomers 1 H ‐1,2,4‐diazaphospholes ( 5a or 5b ) and 1 H ‐1,2,3‐diazaphospholes ( 6a or 6b ) in quantitative yields (isomer ratio: 5a/6a = 2:1; 5b/6b = 4:1). X‐ray diffraction studies on 5a and 5b indicate a delicate charge balance in the bonding system of 1 H ‐1,2,4,σ 2 ‐diazaphospholes under the influence of the exocyclic push/pull substituents i Pr 2 N and CF 3 or CO 2 Me, respectively.