METAL-ION CATALYSIS IN NUCLEOPHILIC-SUBSTITUTION REACTIONS PROMOTED BY COMPLEXES OF POLYETHER LIGANDS WITH ALKALI-METAL SALTS

被引：27

作者：

GOBBI, A

LANDINI, D

MAIA, A

SECCI, D

机构：

[1] UNIV MILAN,CTR CNR,I-20133 MILAN,ITALY

[2] UNIV MILAN,DIPARTIMENTO CHIM ORGAN & IND,I-20133 MILAN,ITALY

[3] UNIV CAGLIARI,DIPARTIMENTO FARM CHIM TECNOL,I-09124 CAGLIARI,ITALY

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1995年 / 60卷 / 18期

关键词：

D O I：

10.1021/jo00123a036

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Metal ion effects have been revealed on nucleophilic substitution reactions of n-octyl sulfonates 1-3 promoted by complexes of polyether ligands (PEGs, crown ethers, cryptands) with alkali metal salts MY (M = Li, Na, K; Y = I, Br) in low polarity solvents (chlorobenzene, o-dichlorobenzene, toluene) at 60 degrees C. Rate constants increase, in the order K+ < Na+ <Li+, with the complexes of crown ethers 5 and 6 and PEG 4, whereas they are independent of the cation in the case of cryptates of 7. In the series of sulfonic esters 1-3 these effects progressively diminish with increasing nucleofugality of the leaving group. These results are interpreted on the basis of a transition state where the complexed cation (Lig superset of M(+)) assists the departure of the leaving group (''electrophilic catalysis'').

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页码：5954 / 5957

页数：4

相关论文

共 27 条

[1]

CASSASCHI A, 1993, J AM CHEM SOC, V115, P8002

[2] COMPLEXATION OF ALKALI-METAL IONS BY THE CRYPTAND 4,7,13,16-TETRAOXA-1,10-DIAZABICYCLO[8.8.5]TRICOSANE IN SEVERAL SOLVENTS [J].

DHILLON, R ;

LINCOLN, SF .

AUSTRALIAN JOURNAL OF CHEMISTRY, 1994, 47 (01) :123-130

[3] METAL-ION CATALYSIS IN NUCLEOPHILIC DISPLACEMENT-REACTIONS AT CARBON, PHOSPHORUS, AND SULFUR CENTERS .1. CATALYSIS BY METAL-IONS IN THE REACTION OF PARA-NITROPHENYL DIPHENYLPHOSPHINATE WITH ETHOXIDE [J].

DUNN, EJ ;

BUNCEL, E .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1989, 67 (09) :1440-1448

[4] METAL-ION CATALYSIS IN NUCLEOPHILIC DISPLACEMENT-REACTIONS AT CARBON, PHOSPHORUS, AND SULFUR CENTERS .2. METAL-ION CATALYSIS IN THE REACTION OF PARA-NITROPHENYL DIPHENYLPHOSPHINATE WITH ALKALI-METAL PHENOXIDES IN ETHANOL [J].

DUNN, EJ ;

MOIR, RY ;

BUNCEL, E ;

PURDON, JG ;

BANNARD, RAB .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1990, 68 (10) :1837-1845

[5] THE EFFECTS OF MG-2+, HYDROGEN-BONDING, AND STERIC FACTORS ON RATE AND EQUILIBRIUM-CONSTANTS FOR PHOSPHORYL TRANSFER BETWEEN CARBOXYLATE IONS AND PYRIDINES [J].

HERSCHLAG, D ;

JENCKS, WP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (05) :1942-1950

[6] RATE OF DISPLACEMENT OF TOLUENE-P-SULPHONATE RELATIVE TO BROMIDE ION . A NEW MECHANISTIC CRITERION [J].

HOFFMANN, HM .

JOURNAL OF THE CHEMICAL SOCIETY, 1965, (DEC) :6753-+

[7] SYNTHESIS OF SUBSTITUTED CROWN ETHERS FROM OLIGOETHYLENE GLYCOLS [J].

IKEDA, I ;

YAMAMURA, S ;

NAKATSUJI, Y ;

OKAHARA, M .

JOURNAL OF ORGANIC CHEMISTRY, 1980, 45 (26) :5355-5358

[8] FACILITATION OF DIPHOSPHATE GROUP ELIMINATION FROM GERANYL DIPHOSPHATE BY MAGNESIUM-ION CHELATION IN CYCLIC MONOTERPENOID BIOSYNTHESIS [J].

ITO, DI ;

IZUMI, S ;

HIRATA, T ;

SUGA, T .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1992, (01) :37-39

[9] PHASE-TRANSFER REACTIONS CATALYZED BY LIPOPHILIC [2.2.2]CRYPTANDS AND DICYCLOHEXANO-18-CROWN-6 - DEHYDRATING EFFECT OF CONCENTRATED AQUEOUS ALKALINE-SOLUTIONS [J].

LANDINI, D ;

MAIA, A ;

MONTANARI, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (10) :2917-2923

[10] MECHANISM AND ANION ACTIVATION IN SOLID LIQUID PHASE-TRANSFER REACTIONS CATALYZED BY CYCLOPHOSPHAZENIC POLYPODANDS - COMPARISON WITH CYCLIC ANALOG CROWN ETHERS [J].

LANDINI, D ;

MAIA, A ;

PODDA, G ;

SECCI, D ;

YAN, YM .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1992, (10) :1721-1724