Solvent effects on the steric course of the solvolysis of tertiary acyclic derivatives

被引：26

作者：

Müller, P ^{[1
]}

Rossier, JC ^{[1
]}

机构：

[1] Univ Geneva, Dept Organ Chem, CH-1211 Geneva 4, Switzerland

来源：

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 2000年 / 11期

关键词：

D O I：

10.1039/b004884o

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The solvolysis of (R)-3-chloro-3,7-dimethyloctane (2), of the corresponding hydrogen phthalate (S)-4g, and of the p-nitrobenzoate (S)-4h proceeds with up to 87% inversion of configuration in solvents such as methanol or ethanol. The degree of inversion decreases in more dissociating solvents. In 2,2,2-trifluoroethanol (TFE), up to 40% retention of configuration occurs.

引用

页码：2232 / 2237

页数：6

共 47 条

[31]

MULLER P, 2000, IN PRESS J PHYS ORG, V13

[32] DIE ABSOLUTE KONFIGURATION DES LINALOOLS DURCH VERKNUPFUNG MIT DEM PINANSYSTEM [J].

OHLOFF, G ;

KLEIN, E .

TETRAHEDRON, 1962, 18 (JAN) :37-&

[33] RETENTIVE SOLVOLYSIS .11. RETENTIVE PHENOLYSES OF OPTICALLY-ACTIVE SECONDARY AND TERTIARY SYSTEMS WITHOUT A GROUP IMPOSING CONFIGURATIONAL RESTRICTION [J].

OKAMOTO, K ;

KINOSHITA, T ;

OSHIDA, T ;

YAMAMOTO, T ;

ITO, Y ;

DOHI, M .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1976, (14) :1617-1627

[34] PHENOLYSIS OF TETRAHYDROLINALYL AND 2-OCTYL SYSTEMS - RATES, STERIC COURSES, AND PRODUCT DISTRIBUTIONS [J].

OKAMOTO, K ;

KINOSHIT.T .

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1972, 45 (09) :2802-+

[35] STABILITY-SELECTIVITY RELATIONSHIP FOR PHENOLYSES OF ALKYL CHLORIDES AND P-NITROBENZOATES [J].

OKAMOTO, K ;

KINOSHIT.T .

CHEMISTRY LETTERS, 1974, (09) :1037-1040

[36] SOLVENT MOLECULES AND CARBOCATION INTERMEDIATES IN SOLVOLYSES [J].

OKAMOTO, K .

PURE AND APPLIED CHEMISTRY, 1984, 56 (12) :1797-1808

[37] SN2-SN1 SPECTRUM .2. QUANTITATIVE TREATMENTS OF NUCLEOPHILIC SOLVENT ASSISTANCE - SCALE OF SOLVENT NUCLEOPHILICITIES [J].

SCHADT, FL ;

BENTLEY, TW ;

SCHLEYER, PV .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (24) :7667-7674

[38] ALPHA-DEUTERIUM EFFECTS ON RATES OF SOLVOLYSIS OF A 2-ADAMANTYL SULFONATE ESTER [J].

SHINER, VJ ;

FISHER, RD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1971, 93 (10) :2553-&

[39]

STEVENS PG, 1939, J AM CHEM SOC, V61, P1296

[40]

Takeuchi K, 1997, J PHYS ORG CHEM, V10, P717, DOI 10.1002/(SICI)1099-1395(199710)10:10<717::AID-POC941>3.0.CO

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