Kinetics and Mechanism of Anilinolyses of Aryl Methyl and Aryl Propyl Chlorothiophosphates in Acetonitrile† 


Vol. 35,  No. 9, pp. 2797-2802, Sep.  2014
10.5012/bkcs.2014.35.9.2797


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  Abstract

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 oC. 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 for 10 based on the positive ρXY (= +0.68) value. The deuterium kinetic isotope effects (DKIEs; kH/kD) are 0.89-1.28 and 0.62-1.20 with 8 and 10, respectively. Primary normal and secondary inverse DKIEs are rationalized by a frontside attack involving hydrogen bonded, four-center-type transition state and backside attack involving in-line-type transition state, respectively.

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  Cite this article

[IEEE Style]

H. R. Barai and H. W. Lee, "Kinetics and Mechanism of Anilinolyses of Aryl Methyl and Aryl Propyl Chlorothiophosphates in Acetonitrile†," Bulletin of the Korean Chemical Society, vol. 35, no. 9, pp. 2797-2802, 2014. DOI: 10.5012/bkcs.2014.35.9.2797.

[ACM Style]

Hasi Rani Barai and Hai Whang Lee. 2014. Kinetics and Mechanism of Anilinolyses of Aryl Methyl and Aryl Propyl Chlorothiophosphates in Acetonitrile†. Bulletin of the Korean Chemical Society, 35, 9, (2014), 2797-2802. DOI: 10.5012/bkcs.2014.35.9.2797.

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ISSN(Print) 0253-2964
ISSN(Online) 1229-5949