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Issue 10, 2005
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Addition products of a P(III)-isothiocyanate to dialkyl acetylenedicarboxylates: a spirocyclic phosphinimine and a triphosphorus heterocycle with tetra- and penta-coordinate phosphorus

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Abstract

Treatment of the P(III) isothiocyanate CH2[6-t-Bu-4-Me-C6H2O]2PNCS (1) with dimethyl acetylenedicarboxylate (DMAD) or diethyl acetylenedicarboxylate (DEAD) yields the spirocyclic phosphinimines CH2[6-t-Bu-4-Me-C6H2O]2P[NC(S)C(CO2R)C(CO2R)] [R = Me (2), Et (3)], in a reaction unlike those of organic isocyanates. From the reaction of 1 with DEAD, a second product, the triphosphorus compound 5, with the composition [2×1 + 3] but with a completely reorganized structure {CH2[6-t-Bu-4-Me-C6H2O]2P[double bond, length as m-dash]C(CO2Et)C(CO2Et)[double bond, length as m-dash]CN–}{CH2[6-t-Bu-4-Me-C6H2O]2P(NCS)}–SC[double bond, length as m-dash]N–P(S)[(OC6H2-6-t-Bu-4-Me)2CH2] with tetra- and penta-coordinate phosphorus, is also isolated. Structure and reactivity of these compounds are discussed. Addition of 2,2,2-trifluoroethanol to 2 or 3 leads to the pentacoordinate phosphorus compounds [CH2(6-t-Bu-4-Me-C6H2O)2P(OCH2CF3){C(CO2R)C(CO2R)–C(S)–NH–}] [R = Me (6), Et (7)]. The phosphonate [CH2(6-t-Bu-4-Me-C6H2O)2P(O)C(CO2Et)[double bond, length as m-dash]C(CO2Et)–C(S)–NH2] (8) is obtained by evaporating a solution of 7 in open air.

Graphical abstract: Addition products of a P(iii)-isothiocyanate to dialkyl acetylenedicarboxylates: a spirocyclic phosphinimine and a triphosphorus heterocycle with tetra- and penta-coordinate phosphorus

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Publication details

The article was received on 16 Feb 2005, accepted on 13 Apr 2005 and first published on 25 Apr 2005


Article type: Paper
DOI: 10.1039/B502358K
Dalton Trans., 2005, 1847-1851

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    Addition products of a P(III)-isothiocyanate to dialkyl acetylenedicarboxylates: a spirocyclic phosphinimine and a triphosphorus heterocycle with tetra- and penta-coordinate phosphorus

    S. Kumaraswamy, K. S. Kumar, N. S. Kumar and K. C. K. Swamy, Dalton Trans., 2005, 1847
    DOI: 10.1039/B502358K

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