(3R,6R)-1,3,4,6-tetrachlorocyclohexa-1,4-diene

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: (3R,6R)-1,3,4,6-tetrachlorocyclohexa-1,4-diene
• 化学式: C₆H₄Cl₄
• 分子量: 217.9
• InChiKey: HKAJKOBDBFGGIU-AWFVSMACSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (3R,6R)-1,3,4,6-tetrachlorocyclohexa-1,4-diene 生成 三氯苯 、 氯离子 、 氢(+1)阳离子
  参考文献：
  名称：

  γ-六氯环己烷脱盐酸酶LinA的反应机理和立体化学。

  摘要：

  γ-六氯环己烷脱盐酸酶（LinA）催化重要的杀虫剂γ-六氯环己烷（γ-HCH）被土壤细菌Sphingomonas paucimobilis UT26生物转化的初始步骤。通过GC-MS，NMR，CD和分子模型研究了LinA转化γ-六氯环己烷过程中形成的反应产物的立体化学分析。比较了使用酶促脱氯化氢或碱性脱氯化氢从γ-六氯环己烷制得的1,3,4,5,6-五氯环己烯（PCCH）的NMR光谱，发现是相同的。合成的γ-PCCH外消旋物中存在的两种对映体均由LinA转化，每种转化率不同。1,2,4-三氯苯（1,2,4-TCB）被检测为生物合成的γ-PCCH的生物转化的唯一产物。1,2,4-TCB和1,2，3-TCB被确定为外消旋γ-PCCH的脱氯化氢产物。检测到δ-PCCH是δ-HCH脱氯化氢的唯一产物。LinA需要在底物分子上存在1,2-双轴HCl对。LinA对映拓扑学区分存在于γ-HCH上的两个1

  DOI：

  10.1074/jbc.m007452200
• 作为产物：
  描述：

  γ-pentachlorocyclohexene 生成 (3R,6R)-1,3,4,6-tetrachlorocyclohexa-1,4-diene 、 氯离子 、 氢(+1)阳离子
  参考文献：
  名称：

  γ-六氯环己烷脱盐酸酶LinA的反应机理和立体化学。

  摘要：

  γ-六氯环己烷脱盐酸酶（LinA）催化重要的杀虫剂γ-六氯环己烷（γ-HCH）被土壤细菌Sphingomonas paucimobilis UT26生物转化的初始步骤。通过GC-MS，NMR，CD和分子模型研究了LinA转化γ-六氯环己烷过程中形成的反应产物的立体化学分析。比较了使用酶促脱氯化氢或碱性脱氯化氢从γ-六氯环己烷制得的1,3,4,5,6-五氯环己烯（PCCH）的NMR光谱，发现是相同的。合成的γ-PCCH外消旋物中存在的两种对映体均由LinA转化，每种转化率不同。1,2,4-三氯苯（1,2,4-TCB）被检测为生物合成的γ-PCCH的生物转化的唯一产物。1,2,4-TCB和1,2，3-TCB被确定为外消旋γ-PCCH的脱氯化氢产物。检测到δ-PCCH是δ-HCH脱氯化氢的唯一产物。LinA需要在底物分子上存在1,2-双轴HCl对。LinA对映拓扑学区分存在于γ-HCH上的两个1

  DOI：

  10.1074/jbc.m007452200

文献信息

• Cloning and sequencing of a dehalogenase gene encoding an enzyme with hydrolase activity involved in the degradation of gamma-hexachlorocyclohexane in Pseudomonas paucimobilis
  作者：Y Nagata、T Nariya、R Ohtomo、M Fukuda、K Yano、M Takagi

  DOI：10.1128/jb.175.20.6403-6410.1993

  日期：1993.10

  analysis revealed an open reading frame (designated the linB gene) of 885 bp within the region. The deduced amino acid sequence of LinB showed significant similarity to hydrolytic dehalogenase, DhlA (D. B. Janssen, F. Pries, J. van der Ploeg, B. Kazemier, P. Terpstra, and B. Witholt, J. Bacteriol. 171:6791-6799, 1989). The protein product of the linB gene was 32 kDa by sodium dodecyl sulfate-polyacrylamide

  在pseudomonas paucimobilis UT26中，γ-六氯环己烷（gamma-HCH）通过两步脱氯化氢转化为化学上不稳定的中间体1,3,4,6-四氯-1,4-环己二烯（1,4-TCDN），然后通过两步水解脱卤，通过化学不稳定的中间体2,4,5-三氯-2,5代谢成2,5-二氯-2,5-环己二烯-1,4-二醇（2,5-DDOL） -环己二烯-1-醇（2,4,5-DNOL）。为了克隆编码负责化学不稳定中间体1,4-TCDN和2,4,5-DNOL转化的酶的基因，在恶臭假单胞菌PpY101LA中构建了p.paucimobilis UT26的基因组文库，其中装有linA基因由Tn5引入。亚克隆一个粘粒克隆中的一个8kb BglII片段，该片段可将γ-六氯环己烷转化为2,5-DDOL，和随后的删除分析显示，一个ca。1.1kb区域负责该活性。核苷酸序列分析表明该区域内有一个885 bp的开
• Isolation and Characterization of Tn5-Induced Mutants of<i>Pseudomonas paucimobilis</i>UT26 Defective in<i>γ</i>-Hexachlorocyclohexane Dehydrochlorinase (LinA)
  作者：Yuji Nagata、Ryozo Imai、Akira Sakai、Masao Fukuda、Keiji Yano、Masamichi Takagi

  DOI：10.1271/bbb.57.703

  日期：1993.1

  Pseudomonas paucimohilis UT26 grows on y-hexachlorocyclohexane (γ-HCH) as a sole source of carbon and energy. Tn5 mutation was introduced into UT26, and two kinds of mutants defective in γ-HCH degradation were phenotypically isolated; one (UT64) completely lacked the activity to degrade γ-HCH, while the other (UT61) retained a very low level of activity. Tagging and sequencing analysis showed that both mutants had a Tn5 insertion at the same site of the linA (γ-HCH dehydrochlorinase encoding) gene. However, UT61 had an additional rearrangement, which could be the cause of its retaining a low level of activity. An in vitro complementation test with a crude extract from UT64 plus partially purified LinA protein showed that LinA was essential not only for the first-step reaction (γ-HCH to γ-pentachlorocyclohexene; γ-PCCH), but also for the second-step reaction (γ-PCCH to compound B) of γ-HCH degradation in UT26.

  假单胞菌UT26以γ-六氯环己烷（γ-HCH）为碳和能量的唯一来源。Tn5突变被引入UT26，两种在γ-HCH降解中存在缺陷的突变体在表型上被分离出来；其中一种（UT64）完全缺乏降解γ-HCH的活性，而另一种（UT61）保留了非常低的活性水平。标记和测序分析表明，两种突变体在linA（γ-HCH脱氢氯酶编码）基因的相同位点都有Tn5插入。然而，UT61有一个额外的重排，这可能是它保留低水平活性的原因。用UT64的粗提物和部分纯化的LinA蛋白进行的体外互补试验表明，LinA不仅对于γ-HCH降解的第一步反应（γ-HCH到γ-五氯环己烯；γ-PCCH）是必不可少的，而且对于第二步反应（γ-PCCH到化合物B）也是必不可少的。
• Enzymes involved in the biodegradation of hexachlorocyclohexane: A mini review
  作者：Beni Camacho-Pérez、Elvira Ríos-Leal、Noemí Rinderknecht-Seijas、Héctor M. Poggi-Varaldo

  DOI：10.1016/j.jenvman.2011.06.047

  日期：2012.3

  The scope of this paper encompasses the following subjects: (i) aerobic and anaerobic degradation pathways of gamma-hexachlorocyclohexane (HCH); (ii) important genes and enzymes involved in the metabolic pathways of gamma-HCH degradation; (iii) the instrumental methods for identifying and quantifying intermediate metabolites, such as gas chromatography coupled to mass spectrometry (GC MS) and other techniques.It can be concluded that typical anaerobic and aerobic pathways of gamma-HCH are well known for a few selected microbial strains, although less is known for anaerobic consortia where the possibility of synergism, antagonism, and mutualism can lead to more particular routes and more effective degradation of gamma-HCH. Conversion and removals in the range 39%-100% and 47%-100% have been reported for aerobic and anaerobic cultures, respectively. Most common metabolites reported for aerobic degradation of lindane are gamma-pentachlorocyclohexene (gamma-PCCH), 2,5-dichlorobenzoquinone (DCBQ), Chlorohydroquinone (CHQ), chlorophenol, and phenol, whereas PCCH, isomers of trichlorobenzene (TCB), chlorobenzene, and benzene are the most typical metabolites found in anaerobic pathways. Enzyme and genetic characterization of the involved molecular mechanisms are in their early infancy; more work is needed to elucidate them in the future.Advances have been made on identification of enzymes of Sphingomonas paucimobilis where the gene LinB codifies for the enzyme haloalkane dehalogenase that acts on 1,3,4,6-tetrachloro 1,4-cyclohexadiene, thus debottlenecking the pathway. Other more common enzymes such as phenol hydroxylase, catechol 1,2-dioxygenase, catechol 2,3-dioxygenase are also involved since they attack intermediate metabolites of lindane such as catechol and less substituted chlorophenols. Chromatography coupled to mass spectrometric detector, especially GC-MS, is the most used technique for resolving for gamma-HCH metabolites, although there is an increased participation of HPLC-MS methods. Scintillation methods are very useful to assess final degradation of gamma-HCH. (C) 2011 Elsevier Ltd. All rights reserved.
• Reaction Mechanism and Stereochemistry of γ-Hexachlorocyclohexane Dehydrochlorinase LinA
  作者：Lukáš Trantı́rek、Kamila Hynková、Yuji Nagata、Alexey Murzin、Alena Ansorgová、Vladimı́r Sklenář、Jiřı́ Damborský

  DOI：10.1074/jbc.m007452200

  日期：2001.3

  the initial steps in the biotransformation of the important insecticide gamma-hexachlorocyclohexane (gamma-HCH) by the soil bacterium Sphingomonas paucimobilis UT26. Stereochemical analysis of the reaction products formed during conversion of gamma-HCH by LinA was investigated by GC-MS, NMR, CD, and molecular modeling. The NMR spectra of 1,3,4,5,6-pentachlorocyclohexene (PCCH) produced from gamma-HCH

  γ-六氯环己烷脱盐酸酶（LinA）催化重要的杀虫剂γ-六氯环己烷（γ-HCH）被土壤细菌Sphingomonas paucimobilis UT26生物转化的初始步骤。通过GC-MS，NMR，CD和分子模型研究了LinA转化γ-六氯环己烷过程中形成的反应产物的立体化学分析。比较了使用酶促脱氯化氢或碱性脱氯化氢从γ-六氯环己烷制得的1,3,4,5,6-五氯环己烯（PCCH）的NMR光谱，发现是相同的。合成的γ-PCCH外消旋物中存在的两种对映体均由LinA转化，每种转化率不同。1,2,4-三氯苯（1,2,4-TCB）被检测为生物合成的γ-PCCH的生物转化的唯一产物。1,2,4-TCB和1,2，3-TCB被确定为外消旋γ-PCCH的脱氯化氢产物。检测到δ-PCCH是δ-HCH脱氯化氢的唯一产物。LinA需要在底物分子上存在1,2-双轴HCl对。LinA对映拓扑学区分存在于γ-HCH上的两个1