Oxidation of benzyl radicals by Fe(CN)(6)(3-)

被引:20
作者
Merga, G
Schuchmann, HP
Rao, BSM
vonSonntag, C
机构
[1] MAX PLANCK INST STRAHLENCHEM,D-45470 MULHEIM,GERMANY
[2] UNIV PUNE,DEPT CHEM,POONA 411007,MAHARASHTRA,INDIA
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 1996年 / 04期
关键词
D O I
10.1039/p29960000551
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Hydroxyl radicals and their anions [O-.- radicals, pK(a)((OH)-O-.) = 11.9] have been generated radiolytically in N2O-saturated aqueous solution and reacted with 4-chlorotoluene. While the (OH)-O-. radical mainly produces hydroxycyclohexadienyl-type radicals, the O-.- radical practically only abstracts H atoms from the methyl group yielding 4-chlorobenzyl radicals (k = 1.9 x 10(9) dm(3) mol(-1) s(-1); determined by pulse radiolysis). The radicals formed by (OH)-O-. radical attack at pH 7 (mainly hydroxycyclohexadienyl-type radicals) are oxidized by Fe(CN)(6)(3-) k = 1.8 x 10(7) dm(3) mol(-1) s(-1)) giving rise to the following products (G values in units of 10(-7) mol J(-1) are given in parentheses): 4-chloro-2-hydroxytoluene (2.9), 4-chloro-3-hydroxytoluene (2.4), 4-chlorobenzyl alcohol (0.05), 4-chlorobenzaldehyde (0.1) and 4-chloro-2-hydroxybenzaldehyde (0.15). The 4-chlorobenzyl radical is the main species formed at pH 13.7 and is oxidized by Fe(CN)(6)(3-) with a similar rate constant (k = 4.2 x 10(7) dm(3) mol(-1) s(-1)), the major products being 4-chlorobenzaldehyde (3.7), 4-chloro-2-hydroxybenzaldehyde (0.65) and 4-chlorobenzyl alcohol (0.5). From (OH)-O-. radical attack (ca. 10% at this pH), 4-chloro-2-hydroxytoluene (0.4) and 4-chloro-3-hydroxytoluene (0.3) are also formed. It is suggested that the oxidation of the Li-chlorobenzyl radical by Fe(CN)(6)(3-) yields in the first step a carbocation which cyclizes by deprotonation. The resulting cyclohexadienyl-type radical undergoes beta-fragmentation yielding the 4-chlorobenzyloxyl radical. A 1,2-H shift and subsequent oxidation leads to 4-chlorobenzaldehyde. The unsubstituted benzyl radical is also oxidized by Fe(CN)(6)(3-) yielding benzaldehyde in high yields.
引用
收藏
页码:551 / 556
页数:6
相关论文
共 28 条
[1]   PULSE RADIOLYSIS STUDIES ON OXIDATION OF ORGANIC RADICALS IN AQUEOUS SOLUTION [J].
ADAMS, GE ;
WILLSON, RL .
TRANSACTIONS OF THE FARADAY SOCIETY, 1969, 65 (563P) :2981-&
[2]  
Berdnikov V.M., 1972, KINET CATAL+, V13, P986
[3]  
BHATIA K, 1974, J PHYS CHEM-US, V78, P2335
[4]   CRITICAL-REVIEW OF RATE CONSTANTS FOR REACTIONS OF HYDRATED ELECTRONS, HYDROGEN-ATOMS AND HYDROXYL RADICALS (.OH/.O-) IN AQUEOUS-SOLUTION [J].
BUXTON, GV ;
GREENSTOCK, CL ;
HELMAN, WP ;
ROSS, AB .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1988, 17 (02) :513-886
[5]   AROMATIC HYDROXYLATION .8. A RADIATION CHEMICAL STUDY OF THE OXIDATION OF HYDROXYCYCLOHEXADIENYL RADICALS [J].
BUXTON, GV ;
LANGAN, JR ;
SMITH, JRL .
JOURNAL OF PHYSICAL CHEMISTRY, 1986, 90 (23) :6309-6313
[6]   FORMATION OF BENZYL RADICALS BY PULSE-RADIOLYSIS OF TOLUENE IN AQUEOUS-SOLUTIONS [J].
CHRISTENSEN, HC ;
SEHESTED, K ;
HART, EJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1973, 77 (08) :983-987
[7]   RADIOLYSIS OF AQUEOUS TOLUENE SOLUTIONS [J].
CHRISTENSEN, HC ;
GUSTAFSS.R .
ACTA CHEMICA SCANDINAVICA, 1972, 26 (03) :937-+
[8]   RADIATION-INDUCED HOMOLYTIC AROMATIC-SUBSTITUTION .5. EFFECT OF METAL-IONS ON HYDROXYLATION OF TOLUENE [J].
EBERHARDT, MK ;
IVELISSEMARTINEZ, M .
JOURNAL OF PHYSICAL CHEMISTRY, 1975, 79 (18) :1917-1920
[9]  
FANG X, IN PRESS ULTRASONICS
[10]  
Gilbert B.C., 1977, J CHEM RES S, P1