Mass and microwave spectroscopic studies of pyrolysates and pyrolysis mechanism of 1,1,2-trichloronitrosoethane

• Published in: Journal of analytical and applied pyrolysis Vol. 53; no. 2; pp. 177 - 184
• Main Authors: Sakaizumi, Takeshi, Sekiya, Ryo, Kuze, Nobuhiko, Ohashi, Osamu
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.02.2000
• Subjects: 1,1-Dichloroethene; Chloroacetylene; Cyanogen chloride; Formaldehyde; Microwave spectroscopy; Nitrosyl chloride; Pyrolysis mechanism; Microwave spectroscopy; Pyrolysis mechanism; 1,1-Dichloroethene; Chloroacetylene; Cyanogen chloride; Formaldehyde; Nitrosyl chloride
• ISSN: 0165-2370; 1873-250X
• DOI: 10.1016/S0165-2370(99)00065-0

The pyrolysates of 1,1,2-trichloronitrosoethane (CH 2ClCCl 2NO) have been investigated by pyrolysis–mass spectrometry and microwave spectroscopy (Py–MS/MW). The five pyrolysates were identified to be 1,1-dichloroethene 1, nitrosyl chloride 2, chloroacetylene 3, formaldehyde 6 and cyanogen chloride 7 by microwave spectroscopy. The generation of 3 was verified by the direct reaction of 1 with NO* and Cl* radicals inside a Stark cell. Two radicals were generated by pyrolysis of 2. The observed ionic peaks m/ z at 91 and 93 (C 2H 2ClNO) having the relative intensity of 3:1 were tentatively assigned to 1-chloronitrosoethene ( 4 or 4′) produced by elimination of Cl 2 of the precursor. Two pyrolysis mechanisms of 1,1,2-trichloronitrosoethane were elucidated by judging from these pyrolysates identified. One is that 1 is generated by elimination of 2, and 3 is furthermore produced by reaction of 1 with NO and Cl radicals. The other is that 4 may be generated by elimination of Cl 2 of the precursor and 6 and 7 may be produced by cleavage of four-membered ring molecule 5 produced by intramolecular cyclization of 4.