Methylenethioxophosphorane (thiophosphene) intermediates in the reactions of diphenylmethylphosphonamidothioic chlorides with amines. Differences between the elimination–addition mechanisms of nucleophilic substitution for PS and PO substrates

Harger, Martin J. P.

doi:10.1039/b109944m

Cited by 3 publications

(1 citation statement)

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“…It has been reported that nucleophilic substitution at a (thio)phosphoryl (P=S/O) center generally proceeds either through stepwise mechanism with a trigonal bipyramidal pentacoordinated (TBP-5C) intermediate (upper route) or an S N 2 mechanism with TBP-5C transition state (TS) (lower route), Scheme 1. (Skoog and Jencks 1984, Thatcher and Kluger 1989, Hosfield et al 1999, Guha et al 2000, Williams 2000, Chapados et al 2001, Harger 2002, Hengge 2002, 2005, Humphry et al 2004, Swamy and Kumar 2006, Um and Kumar. 2006…”

Section: Introductionmentioning

confidence: 99%

Effect of substituents on reactivity and reaction mechanism observed in Sn reaction of some organophosphorus compounds: based on Physical organic methodologies

Lumbiny

2013

J. Asiat. Soc. Bangladesh, Sci.

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Section: Introductionmentioning

confidence: 99%

Effect of substituents on reactivity and reaction mechanism observed in Sn reaction of some organophosphorus compounds: based on Physical organic methodologies

Lumbiny

2013

J. Asiat. Soc. Bangladesh, Sci.

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Kinetics and Mechanism of the Aminolysis of Aryl Phenyl Chlorothiophosphates with Anilines

et al. 2007

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Kinetic studies of the reactions of aryl phenyl chlorothiophosphates (1) and aryl 4-chlorophenyl chlorothiophosphates (2) with substituted anilines in acetonitrile at 55.0 degrees C are reported. The negative values of the cross-interaction constant rhoXY (rhoXY = -0.22 and -0.50 for 1 and 2, respectively) between substituents in the nucleophile (X) and substrate (Y) indicate that the reactions proceed by concerted SN2 mechanism. The primary kinetic isotope effects (kH/kD = 1.11-1.13 and 1.10-1.46 for 1 and 2, respectively) involving deuterated aniline nucleophiles are obtained. Front- and back-side nucleophilic attack on the substrates is proposed mainly on the basis of the primary kinetic isotope effects. A hydrogen-bonded, four-center-type transition state is suggested for a front-side attack, while the trigonal bipyramidal pentacoordinate transition state is suggested for a back-side attack. The MO theoretical calculations of the model reactions of dimethyl chlorothiophosphate (1') and dimethyl chlorophosphate (3') with ammonia are carried out. Considering the specific solvation effect, the front-side nucleophilic attack can occur competitively with the back-side attack in the reaction of 1'.

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1,3-Digermacyclobutanes with exocyclic CP and CPS double bonds

et al. 2007

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Methylenethioxophosphorane (thiophosphene) intermediates in the reactions of diphenylmethylphosphonamidothioic chlorides with amines. Differences between the elimination–addition mechanisms of nucleophilic substitution for PS and PO substrates

Cited by 3 publications

References 17 publications

Effect of substituents on reactivity and reaction mechanism observed in Sn reaction of some organophosphorus compounds: based on Physical organic methodologies

Effect of substituents on reactivity and reaction mechanism observed in Sn reaction of some organophosphorus compounds: based on Physical organic methodologies

Kinetics and Mechanism of the Aminolysis of Aryl Phenyl Chlorothiophosphates with Anilines

1,3-Digermacyclobutanes with exocyclic CP and CPS double bonds

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