HYDROLYSIS OF PHOSPHONOFORMATE TRIESTERS - RATE ACCELERATION OF A MILLIONFOLD IN NUCLEOPHILIC-SUBSTITUTION AT PHOSPHORUS

被引：20

作者：

KROL, ES ^{[1
]}

THATCHER, GRJ ^{[1
]}

机构：

[1] QUEENS UNIV, DEPT CHEM, KINGSTON K7L 3N6, ONTARIO, CANADA

来源：

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 1993年 / 05期

关键词：

D O I：

10.1039/p29930000793

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The base-catalysed hydrolysis of triesters of phosphonoformic acid via P-O bond cleavage proceeds at rates at least 10(4) times greater than diethyl difluoromethylphosphonate and 10(6) times greater than diphenyl methylphosphonate. Buffer catalysis and isotope labelling studies suggest the mechanism of rate acceleration by the ethoxycarbonyl group to involve either intramolecular nucleophilic catalyses via a three-membered ring or stereoelectronic assistance, both of which are unprecedented.

引用

页码：793 / 794

页数：2

共 26 条

[1] REACTIONS OF AROYL HALIDES WITH PHOSPHITES . ESTERS OF AROYLPHOSPHONIC ACIDS [J].

BERLIN, KD ;

TAYLOR, HA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (18) :3862-&

[2]

BURNS P, 1972, TETRAHEDRON LETT, P925

[3] MECHANISMS OF NUCLEOPHILIC SUBSTITUTION IN PHOSPHATE ESTERS [J].

COX, JR ;

RAMSAY, OB .

CHEMICAL REVIEWS, 1964, 64 (04) :317-&

[4] EVIDENCE FOR CYCLIC AZAPHOSPHIRIDINE OXIDE INTERMEDIATES IN THE METHOXIDE-INDUCED REARRANGEMENTS OF N-ALKYL ALPHA-CHLOROPHOSPHONAMIDATES - FORMATION OF PHOSPHORAMIDATES AS WELL AS ALPHA-AMINOPHOSPHONATES [J].

HARGER, MJP ;

WILLIAMS, A .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1989, (03) :563-569

[5] MECHANISM OF REACTION OF PHENYLPROPARGYLALDEHYDE WITH AQUEOUS SODIUM HYDROXIDE TO GIVE PHENYLACETYLENE AND SODIUM FORMATE [J].

HINE, J ;

KOSER, GF .

JOURNAL OF ORGANIC CHEMISTRY, 1971, 36 (10) :1348-+

[6] KINETICS AND MECHANISM OF REACTION OF DIMETHYL ACETYLPHOSPHONATE WITH WATER - EXPULSION OF A PHOSPHONATE ESTER FROM A CARBONYL HYDRATE [J].

KLUGER, R ;

PIKE, DC ;

CHIN, J .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1978, 56 (13) :1792-1795

[7] RATES OF FORMATION AND DECOMPOSITION OF TETRAHEDRAL INTERMEDIATES IN HYDROLYSIS OF DIMETHYL AROYLPHOSPHONATES - SUBSTITUENT EFFECTS ON A MODEL FOR CARBOXYLATE ESTER HYDROLYSIS [J].

KLUGER, R ;

CHIN, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (23) :7382-7388

[8] HYDROLYSIS OF PHOSPHONOFORMATE ESTERS - PRODUCT DISTRIBUTION AND REACTIVITY PATTERNS [J].

KROL, ES ;

DAVIS, JM ;

THATCHER, GRJ .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1991, (02) :118-119

[9]

KROL ES, 1991, 74TH ANN CAN CHEM C

[10] DETERMINATION OF POLAR SUBSTITUENT CONSTANTS FOR DIALKOXY-AND DIARYLPHOSPHONO AND TRIALKYL-AND TRIARYLPHOSPHONIUM GROUPS [J].

MARTIN, DJ ;

GRIFFIN, CE .

JOURNAL OF ORGANIC CHEMISTRY, 1965, 30 (12) :4034-&

← 1 2 3 →