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Bis[bis(dimethylamino)phosphino]acetylene (2a) and two molecules of dimethyl- and diethyl-acetylenedicarboxylate (1a /1b ) react in a criss-cross-cycloaddition to yield 1λ 5  ,4λ 5 - diphosphapentalenes (3), which react further with 1 to yield a 1λ 5  ,4λ 5 -diphosphaazulenes (5). A mechanism of both reactions is proposed. The reaction of 1λ 5 ,4λ 5 -diphosphaazulene with 1a at high pressure yields 1,1,4,4-tetrakis(dimethylamino)-3,5,6,7,8 -pentakis(methoxycarbonyl)- 2-[1,2,2tris(methoxycarbonyl)ethenyl]-1λ 5 ,4λ 5  -diphosphaazulene (7). The reaction of bis(diphenylphosphino) acetylene (2c) with 1a yields 1,5a-dihydro-1-methoxy-(1-methoxycarbonylethinyl)- 3,3,7,7-tetraphenyl)-2-oxa-3λ 5 ,7λ 5  -diphosphacyclopenta[1,2,3-c,d]azulene- 4,5,5a,6,8,9-hexakis(methoxycarbonyl) (9) and 4-(diphenylphosphoryl)-5-[1,2-bis-(methoxycarbonyl)- ethylidene]-1λ 5 -phosphol-2,3-bis(methoxycarbonyl) (10)

zeitschrift für naturforschung b

Synthese und Untersuchung neuer 1λ 5 , 4λ 5 -Diphosphapentalen- und 1λ 5 ,4λ 5  - sowie 1λ 5 ,5λ 5 -Diphosphaazulen-Systeme / Synthesis of New 1λ 5 ,4λ 5 -Diphosphapentalene- and 1λ 5 ,5λ 5 -Diphosphaazulene Systems