Reactions of phosphorus(III) thioa amides with proton-donor nucleophilic reagents

Journal Article · Thu Mar 20 04:00:00 EST 1986 · J. Gen. Chem. USSR (Engl. Transl.); (United States)

OSTI ID:5571246

Kostin, V P; Sinyashin, O G; Karelov, A A; Batyeva, E S; Pudovik, A N

Depending on the reaction conditions, the butanolysis of dialkyl phosphoramidoditrhioites goes with the formation of tributyl phosphite and the corresponding phosphorotrithioite or the product of the replacement of the amino group on the tervalent-phosphorus atom: a mixed phosphorodithioite O,S-ester. Phosphoramidodithioites and phosphorodiaminothioites react with ethylene glycol and with pyrocatechol with the replacement of both the amino and the alkylthio groups, leading respectively to 1,4,6,9-tetraoxa-5lambda/sup 5/-phosphaspiro(4.4)nonane and diethylammonium tris(o-phenylenedioxy)phosphate. The phenolysis, alkanethiolysis, and arenethiolysis of phosphoramidodithioites go with the breakage of the P-N bond and the formation of the corresponding phosphorodithious O,S-esters and phosphorotrithioites. According to the results of quantum-chemical calculation, the determining influence on the relative reactivities of P(III) amide esters and thio amide esters in reactions with alcohols and phenol is shown by the charge factor, but in reactions with alkane- and arene-thiols by orbital factors.

• Research Organization: A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan', USSR
• OSTI ID: 5571246
• Journal Information: J. Gen. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Gen. Chem. USSR (Engl. Transl.); (United States) Vol. 55:10; ISSN JGCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ALCOHOLS
AMIDES
AROMATICS
ATOMIC MODELS
BUTANOLS
CATALYTIC EFFECTS
CHARGE DISTRIBUTION
CHEMICAL REACTION KINETICS
CHEMICAL SHIFT
COUPLING
COUPLING CONSTANTS
DEVELOPERS
GLYCOLS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
INTERMEDIATE COUPLING
ISOMERS
ISOTOPES
J-J COUPLING
KINETICS
LIGHT NUCLEI
LYSIS
MATHEMATICAL MODELS
MECHANICS
NMR SPECTRA
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXYGEN COMPOUNDS
PHENOLS
PHOSPHORUS 31
PHOSPHORUS ISOTOPES
POLYPHENOLS
PYROCATECHOL
QUANTUM MECHANICS
REACTION KINETICS
SPECTRA
STABLE ISOTOPES
STEREOCHEMISTRY
THIOLS
WATER