Selectivity in photolysis of benzyl acetate and benzyl hexanoate upon cyclodextrin complexation

被引：3

作者：

Annalakshmi, Subramanian ^{[1
]}

Pitchumani, Kasi ^{[1
]}

机构：

[1] Madurai Kamaraj Univ, Sch Chem, Madurai 625021, Tamil Nadu, India

来源：

JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY | 2006年 / 184卷 / 1-2期

关键词：

cyclodextrin; photolysis; benzyl esters; homolytic and heterolytic mechanisms;

D O I：

10.1016/j.jphotochem.2006.03.017

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Irradiation of benzyl acetate (1) and benzyl hexanoate (2) in methanol yields products from both heterolytic and homolytic pathways. However, in presence of cyclodextrin, photolysis of 1 in aqueous solution and in solid state produces benzyl alcohol as the predominant product and this is attributed to the stabilization of benzylcarbonium ion by secondary hydroxyl groups present at the rim of the cyclodextrin cavity. However, photolysis of 2, in presence of cyclodextrin, produces hexylbenzene as the predominant product via a homolytic pathway and the change in selectivity is explained by the coinclusion of spacer group inside the cyclodextrin cavity. (c) 2006 Elsevier B. V. All rights reserved.

引用

页码：34 / 43

页数：10

共 32 条

[21] Photochemistry of arylmethyl esters in nucleophilic solvents: Radical pair and ion pair intermediates [J].

Pincock, JA .

ACCOUNTS OF CHEMICAL RESEARCH, 1997, 30 (01) :43-49

[22]

PONCE A, 1993, J PHYS CHEM-US, V97, P97

[23] MODIFICATION OF PHOTOCHEMISTRY BY CYCLODEXTRIN COMPLEXATION - COMPETITIVE NORRISH TYPE-I AND TYPE-II REACTIONS OF BENZOIN ALKYL ETHERS [J].

REDDY, GD ;

USHA, G ;

RAMANATHAN, KV ;

RAMAMURTHY, V .

JOURNAL OF ORGANIC CHEMISTRY, 1986, 51 (16) :3085-3093

[24] SPECIFIC INCLUSION CATALYSIS BY BETA-CYCLODEXTRIN IN THE ONE-STEP PREPARATION OF VITAMIN-K1 OR K2 ANALOGS [J].

TABUSHI, I ;

YAMAMURA, K ;

FUJITA, K ;

KAWAKUBO, H .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (04) :1019-1026

[25] Organic reactions mediated by cyclodextrins [J].

Takahashi, K .

CHEMICAL REVIEWS, 1998, 98 (05) :2013-2033

[26] CHAIN-LENGTH EFFECTS IN THE CLEAVAGE OF ARYL ESTERS BY CYCLODEXTRINS - DIFFERENT TRANSITION-STATES FOR META-NITROPHENYL AND PARA-NITROPHENYL ALKANOATES [J].

TEE, OS ;

MAZZA, C ;

DU, XX .

JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (11) :3603-3609

[27] A novel mode of inclusion for pyrene in β-cyclodestrin compounds:: The crystal structures of β-cyclodextrin with cyclohexanol and pyrene, and with n-octanol and pyrene [J].

Udachin, KA ;

Ripmeester, JA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (05) :1080-1081

[28]

VOGEL AI, 1989, TXB PRACTICAL ORGANI, P700

[29]

Zhang Y, 2001, B KOR CHEM SOC, V22, P1397

[30] Meta-ortho effect in organic photochemistry: Mechanistic and exploratory organic photochemistry [J].

Zimmerman, HE .

JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (28) :5616-5621

← 1 2 3 4 →