UMSETZUNGEN VON 4-CHLOR-1,3,5,7-TETRAMETHYL-1,3,5,7-TETRAAZA-4λ⁵- PHOSPHASPIRO[3,3]HEPTAN-2,6-DION, BIS(TRIMETHYLSILYL)- TRIMETHYLBIURET UND BIS(2-CHLORETHYL)- AMINOPHOSPHORSÄUREDICHLORID MIT Me₂NCH₂CH₂N(Me)SiMe₃; STUDIUM INTRAMOLEKULARER P-N-WECHSELWIRKUNGEN

Abstract

A study of possible donor-acceptor interactions in N,N′,N′-trimethylethylenediamine-substituted phosphorus compounds has been conducted. Neither the trimethylethylenediamine-substituted λ⁵P-spirophosphorane 3 nor compound 6, a λ³P-trimethylethylenediamine-substituted derivative of trimethylbiuret, showed any evidence for intramolecular interaction (¹H n.m.r. spectroscopy). In the case of the bis(2-chloroethyl)amino-substituted compounds 9 and 10 dynamic behaviour was observed by n.m.r. spectroscopy. By ³¹P n.m.r. spectroscopy three isomers (a-c) were established. The dimerization of isomer a with formation of two dioxaphosphetidine structures (b and c) is suggested to occur, as are cis and trans isomers, b and c. No reaction occurred between N,N′-dimethylanthranilic acid amide and bis(2-chloroethyl)aminophosphoric acid dichloride, in contrast to the analogous reaction with methylphosphonic acid dichloride. Electronic reasons are thought to be responsible for the lack of reactivity of bis(2-chloro)aminophosphoric acid dichloride.

Key Words:

• N,N′,N′-trimethylethylenediamine
• P-N-interaction
• cis/trans-Isomerization
• Bis(2-chloroethyl) amino substituent.