An efficient synthesis and crystal structure of novel 1‐oxo‐2‐propyl‐4‐(substituted)phenylimino‐1,2,3,4,5,6,7,8‐octahydro[1,4,3]thiazaphosphorino[4,3‐a][1,3,2]benzodiazaphosphorine 3‐oxides |
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Authors: | Junmin Huang Hui Chen Ruyu Chen |
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Abstract: | A series of 1‐oxo‐2‐propyl‐4‐(substituted)phenylimino‐1,2,3,4,5,6,7,8‐octahydro‐1,4,3]thiazaphosphorino4,3‐a]1,3,2]benzodiazaphosphorine 3‐oxides ( 5a–g ) has been synthesized in excellent yields via the reaction of 1‐(2‐bromoethyl)‐2,3‐dihydro‐3‐propyl‐1,3,2‐benzodiazaphosphorin‐4(1H)‐one 2‐oxide with (substituted) phenyl isothiocyanates, which contain the proximate imino and phosphoryl groups in the fused heterocycle. The structures of all of the new compounds were confirmed by spectroscopic methods and microanalyses. The results from X‐ray crystallography analysis of 5a showed that the proximate imino and phosphoryl groups are not coplanar due to their being jointly located in the fused heterocycle, thus having ring tension, and this then destroys the conjugation between the C?N and the P?O moieties. As a result, the length of the P? C bond, measured as 1.8285(18) Å, is just the same as that of a P? C bond not involved in conjugation (1.80–1.85 Å). Also, the C(1), C(2), S(1), C(3), P(1), and N(2) atoms of the 1,4,3]thiazaphosphorino moiety exist preferably in the boat conformation. The coplanar C(1), N(2), C(3), and S(1) atoms, within an average deviation of 0.0564 Å, form the ground floor of the boat conformation, whereas, the P(1) and C(2) atoms are on the same side of the coplanar structure with the distance of 0.7729 Å and 0.7621 Å, respectively. On the other hand, around the C?N double bond, the P(1)? C(3) bond and the N(1)? C(11) bond are in a trans relationship because of the repulsive action of the n‐propyl group in the 2‐position of the title compound. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:599–610, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10041 |
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