共 21 条
ALKALI-METAL ION-ASSISTED CLEAVAGE OF CROWN-ETHER ANISOLES BY TOLUENETHIOLATE ANION
被引:14
作者:

CACCIAPAGLIA, R
论文数: 0 引用数: 0
h-index: 0
机构: UNIV ROME LA SAPIENZA,CTR CNR,STUDIO MECCAN REAZ,I-00185 ROME,ITALY

MANDOLINI, L
论文数: 0 引用数: 0
h-index: 0
机构: UNIV ROME LA SAPIENZA,CTR CNR,STUDIO MECCAN REAZ,I-00185 ROME,ITALY

ROMOLO, FS
论文数: 0 引用数: 0
h-index: 0
机构: UNIV ROME LA SAPIENZA,CTR CNR,STUDIO MECCAN REAZ,I-00185 ROME,ITALY
机构:
[1] UNIV ROME LA SAPIENZA,CTR CNR,STUDIO MECCAN REAZ,I-00185 ROME,ITALY
[2] UNIV ROME LA SAPIENZA,DIPARTIMENTO CHIM,I-00185 ROME,ITALY
关键词:
D O I:
10.1002/poc.610050806
中图分类号:
O62 [有机化学];
学科分类号:
070303 ;
081704 ;
摘要:
The effect of alkali metal ions (Li+, Na+, K+, Cs+) on the reactivity of toluenethiolate anion in the demethylation of 2-methoxy-1,3-xylyl-18-crown-5, 2-methoxy-1,3-xylyl-24-crown-7 and the model compounds anisole and 2,6-dimethylanisole was investigated in dimethylformamide (+3.3 M water) at 60-degrees-C. It was found that the metal ion effects are markedly influenced by the presence of the polyether chain in the reaction system. Whereas reactions of the model compounds are slightly inhibited by the presence of alkali metal ions, the latter strongly enhance rate of demethylation of the crown ether derivatives, the observed catalytic factors ranging over nearly three orders of magnitude. These remarkable rate-enhancing effects are ascribed to a strong transition-state stabilization by metal ions through cooperation of electrostatic binding with the negative charge developing on the oxygen atom of the methoxy group undergoing nucleophilic attack and coordinative interaction with the polyether chain.
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页码:457 / 460
页数:4
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- [1] MOLECULAR RECEPTORS - SYNTHESIS, X-RAY CRYSTAL-STRUCTURES, AND CHEMICAL-PROPERTIES OF CROWN ETHERS BEARING AN INTRAANNULAR PHENOLIC GROUP[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (09) : 2703 - 2712BROWNE, CM论文数: 0 引用数: 0 h-index: 0机构: UNIV GUELPH,DEPT CHEM,GUELPH N1G 2W1,ONTARIO,CANADAFERGUSON, G论文数: 0 引用数: 0 h-index: 0机构: UNIV GUELPH,DEPT CHEM,GUELPH N1G 2W1,ONTARIO,CANADAMCKERVEY, MA论文数: 0 引用数: 0 h-index: 0机构: UNIV GUELPH,DEPT CHEM,GUELPH N1G 2W1,ONTARIO,CANADAMULHOLLAND, DL论文数: 0 引用数: 0 h-index: 0机构: UNIV GUELPH,DEPT CHEM,GUELPH N1G 2W1,ONTARIO,CANADAOCONNOR, T论文数: 0 引用数: 0 h-index: 0机构: UNIV GUELPH,DEPT CHEM,GUELPH N1G 2W1,ONTARIO,CANADAPARVEZ, M论文数: 0 引用数: 0 h-index: 0机构: UNIV GUELPH,DEPT CHEM,GUELPH N1G 2W1,ONTARIO,CANADA
- [2] ALKALI-METAL ION CATALYSIS IN NUCLEOPHILIC DISPLACEMENT BY ALKOXIDE ION IN PARA-NITROPHENYL DIPHENYLPHOSPHINATE - RATE RETARDATION BY CROWN ETHER AND CRYPTAND COMPLEXING AGENTS[J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1984, (03) : 162 - 163BUNCEL, E论文数: 0 引用数: 0 h-index: 0机构: DEF RES ESTAB,CHEM DEF SECT,OTTAWA K1A 0Z4,ONTARIO,CANADA DEF RES ESTAB,CHEM DEF SECT,OTTAWA K1A 0Z4,ONTARIO,CANADADUNN, EJ论文数: 0 引用数: 0 h-index: 0机构: DEF RES ESTAB,CHEM DEF SECT,OTTAWA K1A 0Z4,ONTARIO,CANADA DEF RES ESTAB,CHEM DEF SECT,OTTAWA K1A 0Z4,ONTARIO,CANADABANNARD, RAB论文数: 0 引用数: 0 h-index: 0机构: DEF RES ESTAB,CHEM DEF SECT,OTTAWA K1A 0Z4,ONTARIO,CANADA DEF RES ESTAB,CHEM DEF SECT,OTTAWA K1A 0Z4,ONTARIO,CANADAPURDON, JG论文数: 0 引用数: 0 h-index: 0机构: DEF RES ESTAB,CHEM DEF SECT,OTTAWA K1A 0Z4,ONTARIO,CANADA DEF RES ESTAB,CHEM DEF SECT,OTTAWA K1A 0Z4,ONTARIO,CANADA
- [3] SOLVENT EFFECT ON GROUND-STATE VERSUS TRANSITION-STATE STABILIZATION BY METAL-IONS - CONTRASTING METAL-ION BEHAVIOR IN TETRAGLYME AND ETHANOL FOR NUCLEOPHILIC DISPLACEMENT AT A PHOSPHORUS CENTER[J]. TETRAHEDRON LETTERS, 1990, 31 (45) : 6513 - 6516BUNCEL, E论文数: 0 引用数: 0 h-index: 0机构: DEF RES ESTAB OTTAWA,SHIRLEY BAY K1A 0Z4,ONTARIO,CANADADUNN, EJ论文数: 0 引用数: 0 h-index: 0机构: DEF RES ESTAB OTTAWA,SHIRLEY BAY K1A 0Z4,ONTARIO,CANADAVANTRUONG, N论文数: 0 引用数: 0 h-index: 0机构: DEF RES ESTAB OTTAWA,SHIRLEY BAY K1A 0Z4,ONTARIO,CANADABANNARD, RAB论文数: 0 引用数: 0 h-index: 0机构: DEF RES ESTAB OTTAWA,SHIRLEY BAY K1A 0Z4,ONTARIO,CANADAPURDON, JG论文数: 0 引用数: 0 h-index: 0机构: DEF RES ESTAB OTTAWA,SHIRLEY BAY K1A 0Z4,ONTARIO,CANADA
- [4] SYNTHESIS OF SULFUR-CONTAINING MACROCYCLES USING CESIUM THIOLATES[J]. JOURNAL OF ORGANIC CHEMISTRY, 1981, 46 (22) : 4481 - 4485BUTER, J论文数: 0 引用数: 0 h-index: 0机构: STATE UNIV GRONINGEN, DEPT ORGAN CHEM, NL-9747 AG GRONINGEN, NETHERLANDS STATE UNIV GRONINGEN, DEPT ORGAN CHEM, NL-9747 AG GRONINGEN, NETHERLANDSKELLOGG, RM论文数: 0 引用数: 0 h-index: 0机构: STATE UNIV GRONINGEN, DEPT ORGAN CHEM, NL-9747 AG GRONINGEN, NETHERLANDS STATE UNIV GRONINGEN, DEPT ORGAN CHEM, NL-9747 AG GRONINGEN, NETHERLANDS
- [5] CATALYSIS BY ALKALI AND ALKALINE-EARTH METAL-IONS IN NUCLEOPHILIC-ATTACK OF METHOXIDE ION ON CROWN ETHERS BEARING AN INTRA-ANNULAR ACETOXY GROUP[J]. TETRAHEDRON, 1989, 45 (16) : 5293 - 5304CACCIAPAGLIA, R论文数: 0 引用数: 0 h-index: 0机构: UNIV ROME LA SAPIENZA,CTR CNR MECCAN REAZ,I-00185 ROME,ITALYLUCENTE, S论文数: 0 引用数: 0 h-index: 0机构: UNIV ROME LA SAPIENZA,CTR CNR MECCAN REAZ,I-00185 ROME,ITALYMANDOLINI, L论文数: 0 引用数: 0 h-index: 0机构: UNIV ROME LA SAPIENZA,CTR CNR MECCAN REAZ,I-00185 ROME,ITALYVANDOORN, AR论文数: 0 引用数: 0 h-index: 0机构: UNIV ROME LA SAPIENZA,CTR CNR MECCAN REAZ,I-00185 ROME,ITALYREINHOUDT, DN论文数: 0 引用数: 0 h-index: 0机构: UNIV ROME LA SAPIENZA,CTR CNR MECCAN REAZ,I-00185 ROME,ITALYVERBOOM, W论文数: 0 引用数: 0 h-index: 0机构: UNIV ROME LA SAPIENZA,CTR CNR MECCAN REAZ,I-00185 ROME,ITALY
- [6] ION-PAIRING AND REACTIVITY OF THE ALKALI-METAL AND ALKALINE-EARTH-METAL DERIVATIVES OF ETHYL (5-BROMOPENTYL)ACETOACETATE[J]. JOURNAL OF ORGANIC CHEMISTRY, 1988, 53 (11) : 2579 - 2582CACCIAPAGLIA, R论文数: 0 引用数: 0 h-index: 0机构: UNIV LA SAPIENZA,DIPARTIMENTO CHIM,I-00185 ROMA,ITALYMANDOLINI, L论文数: 0 引用数: 0 h-index: 0机构: UNIV LA SAPIENZA,DIPARTIMENTO CHIM,I-00185 ROMA,ITALY
- [7] METAL-ION EFFECTS ON THE RATE OF INTRAMOLECULAR O-ALKYLATION OF THE ANION OF ETHYL(3-CHLOROPROPYL)ACETOACETATE[J]. TETRAHEDRON, 1990, 46 (04) : 1353 - 1366CACCIAPAGLIA, R论文数: 0 引用数: 0 h-index: 0机构: UNIV ROMA LA SAPIENZA,CNR,CTR STUDI MECCAN REAZ,I-00185 ROME,ITALYMANDOLINI, L论文数: 0 引用数: 0 h-index: 0机构: UNIV ROMA LA SAPIENZA,CNR,CTR STUDI MECCAN REAZ,I-00185 ROME,ITALY
- [8] DIFFERENTIAL METAL-ION STABILIZATION OF REACTANTS AND TRANSITION-STATES IN THE TRANSACYLATION OF CROWN-ETHER ARYL ACETATES[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (07) : 2611 - 2617CACCIAPAGLIA, R论文数: 0 引用数: 0 h-index: 0机构: UNIV ROME LA SAPIENZA,CARDIAC SURG,CTR MECCANISMI REAZ,I-00185 ROME,ITALYVANDOORN, AR论文数: 0 引用数: 0 h-index: 0机构: UNIV ROME LA SAPIENZA,CARDIAC SURG,CTR MECCANISMI REAZ,I-00185 ROME,ITALYMANDOLINI, L论文数: 0 引用数: 0 h-index: 0机构: UNIV ROME LA SAPIENZA,CARDIAC SURG,CTR MECCANISMI REAZ,I-00185 ROME,ITALYREINHOUDT, DN论文数: 0 引用数: 0 h-index: 0机构: UNIV ROME LA SAPIENZA,CARDIAC SURG,CTR MECCANISMI REAZ,I-00185 ROME,ITALYVERBOOM, W论文数: 0 引用数: 0 h-index: 0机构: UNIV ROME LA SAPIENZA,CARDIAC SURG,CTR MECCANISMI REAZ,I-00185 ROME,ITALY
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- [10] STRUCTURE AND REACTIVITY OF LITHIUM AND SODIUM ARYLOXIDES IN DIMETHYLFORMAMIDE - IONS, ION-PAIRS, AND ION TRIPLETS[J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1986, (07) : 551 - 553CRESCENZI, M论文数: 0 引用数: 0 h-index: 0机构: UNIV LA SAPIENZA ROMA,CNR,CTR STUDIO MECCANISMI REAZ,I-00185 ROMA,ITALYGALLI, C论文数: 0 引用数: 0 h-index: 0机构: UNIV LA SAPIENZA ROMA,CNR,CTR STUDIO MECCANISMI REAZ,I-00185 ROMA,ITALYMANDOLINI, L论文数: 0 引用数: 0 h-index: 0机构: UNIV LA SAPIENZA ROMA,CNR,CTR STUDIO MECCANISMI REAZ,I-00185 ROMA,ITALY