STEREOSPECIFIC FORMATION OF A 1,2λ3 -AZAPHOSPETANE IN THE THERMOLYSIS OF BIS[BIS(DIISOPROPYLAMINO)PHOSPHANYL] DIAZOMETHANE |
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Authors: | Marie-Joëlle Menu Yves Dartiguenave Michèle Dartiguenave Antoine Baceiredo Guy Bertrand |
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Institution: | Laboratorie de Chimie de Coordination du CNRS, U8241 205 , route de Narbonne, 31 077 , Toulouse , Cédex , France |
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Abstract: | Abstract Heating of bisbis(diisopropylamino)phosphanyl]diazomethane 7. in refluxing benzene for 48 hours, quantitatively led to the corresponding 1.2λ3-azaphosphetane 9 as only one diastereoisomer. This result is explained in terms of carbene insertion into a methin-CH bond of an isopropyl substituent. The regiospecificity and the stereospecificity of the ring closure is discussed. Treatment of 9 with elemental sulfur afforded the corresponding 1.2.2λ3-azathiophosphetane 10 which has been characterized b X ray crystallo raphy: C25H56N4P2S2, space group P2(l)/n, a = 13.628 (3) Å, 6 = 19.369 (5) Å, c 112.485 (4) Å, V = 3073 (3) Å3. |
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Keywords: | Thermolysis carbene insertion azaphosphetane X-ray crystallography of azathiophosphetane |
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