Kinetics and Mechanism of the Aminolysis of O-Methyl S-Aryl Thiocarbonates in Acetonitrile
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چکیده
منابع مشابه
Kinetics and mechanism of the aminolysis of aryl N-ethyl thiocarbamates in acetonitrile.
The aminolysis of aryl N-ethyl thiocarbamates (EtNHC(=O)SC(6)H(4)Z) with benzylamines (XC(6)H(4)CN(2)NH(2)) in acetonitrile at 30.0 degrees C is investigated. The rates are faster than the corresponding values for aryl N-phenyl thiocarbamates (PhNHC(=O)SC(6)H(4)Z), reflecting a stronger push to expel the leaving group by EtNH than the PhNH nonleaving group in a concerted process. The negative r...
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Nucleophilic substitution reactions of Y-aryl methyl (8) and Y-aryl propyl (10) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 55.0 C. A concerted mechanism is proposed for 8 based on the negative ρXY (= –0.23) value, while a stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed f...
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The aminolysis reactions of thioesters and thiocarbonates, in either aqueous solution or in 44 wt % aqueous ethanol at 25 °C, are subjected to a kinetic investigation. The Brønsted-type plots (lg kN vs. amine pKa, where kN is the nucleophilic rate constant) obtained for these reactions can be grouped in three categories: linear plots with slopes 0.8–1, biphasic plots (two linear portions and a ...
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Kinetic studies on the pyridinolysis of aryl dithiocyclopentanecarboxyaltes 2 were carried out at 60.0 C in acetonitrile. In the aminolysis of 2, the βX values were 0.5 0.8 with anilines, and there was no breakpoint. However, in the pyridinolysis of 2, biphasic Brönsted plots were obtained, with a change in slope from a large value (βX ≅ 0.7) to a small value (βX ≅ 0.4) at pKa = 5.2. This was a...
متن کاملKinetics and mechanism of the aminolysis of aryl ethyl chloro and chlorothio phosphates with anilines.
The reactions of ethyl Y-phenyl chloro (1) and chlorothio (2) phosphates with X-anilines in acetonitrile at 55.0 degrees C are studied kinetically and theoretically. Kinetic results yield the primary kinetic isotope effects (k(H)/k(D) = 1.07-1.80 and 1.06-1.27 for 1 and 2, respectively) with deuterated aniline (XC(6)H(4)ND(2)) nucleophiles, and the cross-interaction constants rho(XY) = -0.60 an...
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ژورنال
عنوان ژورنال: Bulletin of the Korean Chemical Society
سال: 2011
ISSN: 0253-2964
DOI: 10.5012/bkcs.2011.32.5.1539