Microbial oxidation of 4-chloroaniline.
Microbial oxidation of 4-chloroaniline.
复制标题
4-氯苯胺的微生物氧化。
DOI：
10.1021/jf60185a028
复制
发表时间：
1973
影响因子：
6.1
通讯作者：
U. I. Klingebiel
中科院分区：
文献类型：
--
作者：
D. D. Kaufman;J. Plimmer;U. I. Klingebiel
4-土壤真菌尖孢镰刀菌至少通过两条代谢途径降解氯苯胺。4-氯苯胺代谢的主要机制是芳香胺的氧化，但也有芳香胺的酰化。分离出4-氯苯胺的代谢产物4-氯苯羟胺、4-氯亚硝基苯、4-氯硝基苯、4，4 '-二氯偶氮苯、4，4'-二氯偶氮苯和4 '-氯乙酰苯胺。通过与合成样品比较其化学和物理性质，确定了其中几种代谢物的鉴别。4，4 ′-二氯氧化偶氮苯可能是由两个分子的4-氯苯羟胺氧化缩合或由4-氯苯羟胺与4-氯亚硝基苯缩合而成。4，4 ′-二氯偶氮苯既可由4-氯苯胺与4-氯亚硝基苯缩合生成，也可由4，4 ′-二氯氧化偶氮苯还原生成。4-氯苯胺及其产物被进一步氧化为酚类代谢物，并释放出CK。苯胺部分构成了许多农药的基本部分。这些农药在环境中几乎全部降解，最终释放出游离的苯胺。该部分的后续降解尚不清楚。氯代苯胺在土壤和化学体系中的转化机理已被许多研究者研究。降解反应和合成反应都有报道。接受14 C-苯基标记的3 '，4'-二氯丙酰苯胺（敌稗）的土壤中少量14 CO2的演变表明苯胺部分发生了一些降解（Chisaka和Kear-ney，1970）。已经报道了导致形成对称和不对称偶氮苯的缩合反应（Bartha和Pramer，1967; Bartha，1969; Kearney等人，1969; Plimmer等人，1970年）。还报道了三个3，4-二氯苯胺分子缩合形成4-（3，4-二氯苯胺基）-3，3，4 ′-四氯偶氮苯（Rosenet al.，1969年）。我们报道了在土壤真菌尖孢镰刀菌Schlecht代谢3，4-二氯苯胺期间形成3，3 '，4，4'-四氯偶氮苯（考夫曼等人，1971，
4-Chloroaniline was degraded through at least two metabolic pathways by the soil fungus Fusarium oxysporum Schlecht. Oxidation of the aro-matic amine group was the major mechanism of 4-chloroaniline metabolism, but acylation of the aromatic amine group also occurred. 4-Chlorophenylhydroxylamine, 4-chloronitrosobenzene, 4-chloronitrobenzene, 4, 4'-dichloroazobenzene, 4, 4'-dichloroazoxybenzene, and 4'-chloroacetanilide were isolated as metabolites of 4-chloroaniline. The identity of several of these metabolites was established by comparison of their chemical and physical properties with synthetic samples. It is probable that 4, 4'-dichloroazoxybenzene was formed by oxidative condensation of two mole-cules of4-chlorophenylhydroxylamine or by the condensation of 4-chlorophenylhydroxylamine with 4-chloronitrosobenzene. 4, 4'-Dichloroazo-benzene could be formed by either the condensa-tion of 4-chloroaniline with 4-chloronitrosoben-zene or by reduction of 4, 4'-dichloroazoxyben-zene. Further oxidation of 4-chloroaniline and its products to phenolic metabolites and the liberation of CK were also observed.The aniline moiety constitutes a basic part of numerous pesticides. These pesticides are nearly all degraded in the environment, with the ultimate liberation of the aniline as a free entity. Subsequent degradation of this moiety is not well understood. Mechanisms of chloroaniline transformation in soil and chemical systems havebeen examined by numerous investigators. Both degradative and synthetic reactions have been reported. Evolution of small amounts of 14C02 from soils receiving 14C-phényl-labeled 3', 4'-dichloropropionanilide (propanil) suggests that some deg-radation of the aniline moiety occurs(Chisaka and Kear-ney, 1970). Condensation reactionsresulting in the formation of both symmetrical and asymmetrical azobenzenes have been reported (Bartha and Pramer, 1967; Bartha, 1969; Kearney et ai, 1969; Plimmer et al., 1970). The condensation of three molecules of 3, 4-dichloroaniline to form 4-(3, 4-dichloroanilino)-3, 3,, 4'-tetrachloroazobenzene has also been reported (Rosenet al., 1969). We reported the formation of 3, 3', 4, 4'-tetrachloroazoxybenzene during the metabolism of 3, 4-dichloroaniline by the soil fungus Fusarium oxysporum Schlecht (Kaufman et ai, 1971,