The aminolysis of phosphinates; the kinetics and mechanism of the aminolysis of phosphinate esters in acetonitrile

Abstract

. J. Chem. 64, 213 (1986).The aminolysis of aryl diphenylphosphinates, p-nitrophenyl diphenylphosphinothlonate, -phosphinothioate, and -phosphinodithioate by n-butylamine, by the secondary arnines piperidine, pyrrolidine, morpholine, and dipropylamine, as well as by a series of diamines, has been studied in acetonitrile. The general reactivity order is diamines > butylamine > sec-amines.Butylaminolysis follows a two-term rate law, one first order in amine and the other second order in amine. The second order in amine term predominates. sec-Arnines and diamines follow a rate law which is first order in amlne only. Leaving group effects, solvent effects, and activation parameters support a pathway which involves rate-determining collapse of a zwitterionic pentacoordinate intermediate. Operant dans I'acCtonitrile, on a CtudiC l'aminolyse des diphCnylphosphinates d'aryles et des diphCnyl-phosphinothionate, -phosphinothioate et -phosphinodithioate de p-nitro-phCnyle par la n-butylarnine, par les amines secondaires cornrne la pipendine, la pyrrolidine, la morpholine et la dipropylamine ainsi que par une sCrie de diamines. L'ordre de rCactivitC gCnCrale est le suivant: diamines, butylamine, amines secondaires. La butylaminolyse obCit a une Cquation de vitesse impliquant deux termes, un du premier ordre en amine et un autre du deuxieme ordre en amine. Le terme du deuxikme ordre en arnine prCdomine. Les reactions avec les arnines secondaires et avec les diamines obCissent a une Cquation du premier ordre en arnine seulement. Les effets de groupements nuclCofuges et de solvants ainsi que les parametres d'activation sont en accord avec un mCcanisme rCactionnel irnpliquant une Ctape dkterminante au cours de laquelle il y a dCcomposition d'un intermkdiaire zwitteriol~ique pentacoordonnC. Dans le cas de la butylamine, cette dCcomposition est sournise a une catalyse gCnCrale des bases et, pour les diarnines, la rCaction est soumise B une catalyse gCnCrale des bases qui est intramoltculaire.[Traduit par le journal]

Aminolysis of Y-Substituted Phenyl Diphenylphosphinates and Benzoates: Effect of Modification of Electrophilic Center from CO to PO

“…9 In the reaction with n-butylamine, the breakdown of the zwitterionic intermediate has been shown to be general base catalyzed since the reaction follows a two-term rate law, i.e., one first order in amine and the other second order in amine. 9 On the contrary, Lee et al have suggested that reactions of phenyl-substituted phenyl chlorophosphates with pyridines proceed through a concerted mechanism in MeCN, since the Brønsted-type plots obtained are linear with small β nuc values (0.16-0.18). 10a We have performed two series of kinetic studies to investigate the reaction mechanism, i.e., reactions of 1a with seven different alicyclic secondary amines and reactions of piperidine with nine different Y-substituted phenyl diphenylphosphinates (1a-j) in water containing 20 mol % dimethyl sulfoxide (DMSO) at 25.0 ( 0.1 °C.…”

Photoinduced Syntheses and Reactivities of Phosphorus-Containing Interelement Compounds

“…It is expected that the obtained P V –S and P V –Se interelement compounds 19a and 20a will be promising synthetic reagents and intermediates for the syntheses of multifunctionalized organic molecules, − use in living polymerization processes, and trapping of radical species. − Although a number of synthetic methods for 19a , 20a , and their related derivatives have been reported, the majority involve ionic pathways, such as nucleophilic substitution using air- and moisture-sensitive phosphorus sources (e.g., Ph 2 P­(S)–SH, Ph 2 P­(S)–Cl). − Recently, a transition-metal-catalyzed route to synthesis of 19a and its related derivatives has also been reported …”

Aminolysis of 2,4-Dinitrophenyl and 3,4-Dinitrophenyl Diphenylphosphinothioates: Steric Hindrance versus Nucleofugality in Nucleophilic Substitution Reactions

“…This idea is consistent with the conclusion, drawn by Cook et al from analyses of Hammett correlations, solvent effects and activation parameters, that aminolysis of aryl diphenylphosphinates in MeCN proceeds through a stepwise mechanism. 13 However, we have reported that the Yukawa-Tsuno plot for the reactions of 8 different Y-substituted phenyl diphenylphosphinothioates including 6b with piperidine results in excellent linear correlation (R 2 = 0.998) with ρ = 1.91 and r = 0.28. 12b Although the Yukawa-Tsuno equation was derived to account for solvolysis of benzylic system, 14,15 we have shown that the equation is highly effective to elucidate ambiguities in reaction mechanism for nucleophilic substitution reactions of esters with various electrophilic centers (e.g., C=O, C=S, SO 2 , P=O and P=S) [16][17][18] and Michael-type additions of amines to activated acetylenes.…”