Kinetics of Cyclization of Methyl S-(2,4,6-Trinitrophenyl)mercaptoacetate to 2-Methoxycarbonyl-5,7-dinitrobenzo[d]thiazol-3-oxide

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Title:Kinetics of Cyclization of Methyl S-(2,4,6-Trinitrophenyl)mercaptoacetate to 2-Methoxycarbonyl-5,7-dinitrobenzo[d]thiazol-3-oxide
Creators:
Janík, Marek
Macháček, Vladimír
Pytela, Oldřich
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 62, 9, pp. 1429-1445
Uncontrolled Keywords:Reaction mechanism, 2-Methoxycarbonyl-5,7-dinitrobenzo[<i>d</i>]thiazol-3-oxide, Cyclization kinetics

Abstract

The cyclization kinetics of methyl <i>S</i>-(2,4,6-trinitrophenyl)mercaptoacetate to 2-methoxycarbonyl-5,7-dinitrobenzo[<i>d</i>]thiazol-3-oxide have been studied in acetate, methoxyacetate or <i>N</i>-methylmorpholine buffers. In the acetate and methoxyacetate buffers, the cyclization obeys the rate equation <i>v</i> = [SH](<i>k</i>'<sub>MeO</sub>[CH<sub>3</sub>O<sup>-</sup>] + <i>k</i>'<sub>B</sub>[B<sup>-</sup>] + <i>k</i>'<sub>B,MeO</sub>[B<sup>-</sup>][CH<sub>3</sub>O<sup>-</sup>]) and goes by two reaction paths differing in the order of their reaction steps, the splitting off of the proton from C-H group being the rate-limiting step in either path. In the <i>N</i>-methylmorpholine buffers, increasing concentration of the base results in gradual decrease of reaction order in the base and change in the rate-limiting step of cyclization. Methyl <i>S</i>-(2,4-dinitrophenyl)mercaptoacetate undergoes cyclization neither in the given buffers nor in methoxide solution. <p>

Title:Kinetics of Cyclization of Methyl S-(2,4,6-Trinitrophenyl)mercaptoacetate to 2-Methoxycarbonyl-5,7-dinitrobenzo[d]thiazol-3-oxide
Creators:
Janík, Marek
Macháček, Vladimír
Pytela, Oldřich
Uncontrolled Keywords:Reaction mechanism, 2-Methoxycarbonyl-5,7-dinitrobenzo[<i>d</i>]thiazol-3-oxide, Cyclization kinetics
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:62
Number:9
Page Range:pp. 1429-1445
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19971429UNSPECIFIED
ID Code:1219
Item Type:Article
Deposited On:06 Feb 2009 17:07
Last Modified:06 Feb 2009 16:07

Citation

Janík, Marek; Macháček, Vladimír; Pytela, Oldřich (1997) Kinetics of Cyclization of Methyl S-(2,4,6-Trinitrophenyl)mercaptoacetate to 2-Methoxycarbonyl-5,7-dinitrobenzo[d]thiazol-3-oxide. Collection of Czechoslovak Chemical Communications, 62 (9). pp. 1429-1445. ISSN 0010-0765

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