A rationalization of the solvent effect on the Diels-Alder reaction in ionic liquids using multiparameter linear solvation energy relationships

被引：120

作者：

Bini, Riccardo ^{[1
]}

Chiappe, Cinzia ^{[1
]}

Mestre, Veronica Llopsis ^{[2
]}

Pomelli, Christian Silvio ^{[3
]}

Welton, Thomas ^{[2
]}

机构：

[1] Univ Pisa, Dipartimento Chim Bioorgan & Biofarm, I-56100 Pisa, Italy

[2] Univ London Imperial Coll Sci Technol & Med, London SW7 2AZ, England

[3] Dipartimento Chim & Chim Ind, I-56100 Pisa, Italy

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2008年 / 6卷 / 14期

基金：

英国工程与自然科学研究理事会;

关键词：

D O I：

10.1039/b802194e

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The Diels-Alder reaction between cyclopentadiene and three dienophiles (acrolein, methyl acrylate and acrylonitrile) having different hydrogen bond acceptor abilities has been carried out in several ionic liquids and molecular solvents in order to obtain information about the factors affecting reactivity and selectivity. The solvent effects on these reactions are examined using multiparameter linear solvation energy relationships. The collected data provide evidence that the solvent effects are a function of both the solvent and the solute. For a solvent effect to be seen, the solute must have a complimentary character; selectivities and rates are determined by the solvent hydrogen bond donation ability (a) in the reactions of acrolein and methyl acrylate, but not of acrylonitrile.

引用

页码：2522 / 2529

页数：8

共 30 条

[1] The role of hydrogen bonding in controlling the selectivity of Diels-Alder reactions in room-temperature ionic liquids [J].

Aggarwal, A ;

Lancaster, NL ;

Sethi, AR ;

Welton, T .

GREEN CHEMISTRY, 2002, 4 (05) :517-520

[2] Determination of the polarities of some ionic liquids using 2-nitrocyclohexanone as the probe [J].

Angelini, G ;

Chiappe, C ;

De Maria, P ;

Fontana, A ;

Gasparrini, F ;

Pieraccini, D ;

Pierini, M ;

Siani, G .

JOURNAL OF ORGANIC CHEMISTRY, 2005, 70 (20) :8193-8196

[3] IMPORTANCE OF ELECTRONIC AND NUCLEAR-POLARIZATION ENERGY ON DIASTEREOFACIAL SELECTIVITY OF DIELS-ALDER REACTIONS IN AQUEOUS-SOLUTION [J].

ASSFELD, X ;

RUIZLOPEZ, MF ;

GARCIA, JI ;

MAYORAL, JA ;

SALVATELLA, L .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1995, (13) :1371-1372

[4]

Barton AF., 2017, CRC handbook of solubility parameters and other cohesion parameters

[5] CORRELATION OF SOLVENT EFFECTS ON STEREOSELECTIVITIES OF DIELS-ALDER REACTIONS BY MEANS OF LINEAR FREE ENERGY RELATIONSHIPS - A NEW EMPIRICAL MEASURE OF SOLVENT POLARITY [J].

BERSON, JA ;

MUELLER, WA ;

HAMLET, Z .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1962, 84 (02) :297-&

[6] DIELS-ALDER REACTIONS IN NONAQUEOUS POLAR-SOLVENTS - KINETIC EFFECTS OF CHAOTROPIC AND ANTICHAOTROPIC AGENTS AND OF BETA-CYCLODEXTRIN [J].

BRESLOW, R ;

GUO, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (17) :5613-5617

[7] ON THE ORIGIN OF PRODUCT SELECTIVITY IN AQUEOUS DIELS-ALDER REACTIONS [J].

BRESLOW, R ;

MAITRA, U .

TETRAHEDRON LETTERS, 1984, 25 (12) :1239-1240

[8] SELECTIVE DIELS-ALDER REACTIONS IN AQUEOUS-SOLUTIONS AND SUSPENSIONS [J].

BRESLOW, R ;

MAITRA, U ;

RIDEOUT, D .

TETRAHEDRON LETTERS, 1983, 24 (18) :1901-1904

[9] SOLVENT EFFECTS ON ENDO/EXO-SELECTIVITIES AND REGIO-SELECTIVITIES OF DIELS-ALDER REACTIONS OF CARBONYL-CONTAINING DIENOPHILES [J].

CATIVIELA, C ;

GARCIA, JI ;

MAYORAL, JA ;

SALVATELLA, L .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1994, (04) :847-851

[10] Solvent effects on Diels-Alder reactions. The use of aqueous mixtures of fluorinated alcohols and the study of reactions of acrylonitrile [J].

Cativiela, C ;

Garcia, JI ;

Gil, J ;

Martinez, RM ;

Mayoral, JA ;

Salvatella, L ;

Urieta, JS ;

Mainar, AM ;

Abraham, MH .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1997, (03) :653-660

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