Reactions of Trichlorophosphazo-N-Sulfurylchloride and its Derivatives I. Synthesis of a New Heterocycle Containing P,N,S,and C Atoms in its Six-membered Ring. Crystal Structures of (CH 3 ) 3 SiN(H)P(Cl 2 )NS(O 2 )Cl,(CH 3 ) 3 SiN(CH 3 )P(Cl 2 )NS(O 2 )C1,and P(Cl 2 )NS(O 2 )N(H)C(CH 3 )N at 150 K

Abstract

Trichlorophosphazo-N-sulfurylchloride Cl₃PNS(O₂)- C1 (1) reacts with [(CH₃)₃Si]₂NR, R = H, CH₃ to give its N-trimethylsilyl derivatives (CH₃)₃SiN(H)P(Cl₂)NS(O₂)Cl (2) and (CH₃)₃SiN(CH₃)P(Cl₂)NS(O₂)Cl (3). At elevated temperatures (2) reacts with CH₃CN under an intramolecular elimination of (CH₃)₃SiCl and a formation of 3,3-dichloro-5-methyl-6H-l,2,4,6,3-thiatriazaphosphinine-1,1-dioxide P(Cl₂)NS(O₂)N(H)C(CH₃)N. All compounds were characterized by their ³¹P-NMR spectra and chemical analysis and their identity was established by their crystal structure determination. (2): Orthorhombic, S.G. P2₁2₁2₁, with a = 9.425(2), b = 10.507(3), c = 12.803(5) Å,D_X= 1.591 g/cm³, Z = 4, reflections collected 1796, final R = 0.0392; (3): Orthorhombic, S.G. P2₁2₁2₁, with a = 6.275(2), b = 12.638(3), c = 16.759(7) Å, D_X = 1.587 g/cm³, Z = 4, reflections collected 1816, final R = 0.0370; (4): Orthorhombic, S.G. Pna2₁, with a = 7.784 (2), b = 13.911(3), c = 7.413(1) Å, D_X = 1.953 g/cm³, Z = 4, reflections collected 2558, final R = 0.0265.