γ-pentachlorocyclohexene

• 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: γ-pentachlorocyclohexene
• 英文别名: (3R,4S,5S,6R)-1,3,4,5,6-pentachlorocyclohexene
• 化学式: C₆H₅Cl₅
• 分子量: 254.371
• InChiKey: MQYAVRUCONBHOR-JSTMLOLSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  γ-pentachlorocyclohexene 在 lithium aluminium tetrahydride 、 lithium hydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.0h， 以31%的产率得到(34/5)-1,3,4,5-tetrachlorocyclohexene
  参考文献：
  名称：

  Kurihara, Norio; Kohsaka, Hideo; Nakajima, Minoru, Agricultural and Biological Chemistry, 1981, vol. 45, # l2, p. 2883 - 2886

  摘要：

  DOI：
• 作为产物：
  描述：

  lindane 在 sodium hydroxide 、 sodium nitrate 作用下， 以 甲醇 为溶剂， 生成 γ-pentachlorocyclohexene
  参考文献：
  名称：

  吸附对溶解的腐殖质的影响对水中疏水性有机化合物转化反应的影响。第二部分：水解反应。

  摘要：

  研究了溶解的腐殖酸（HA）对两种类型的水解反应的影响：（I）γ-六氯环己烷（HCH）和1,1,2,2-四氯乙烷（TeCA）的脱氯化氢反应涉及氢氧离子（OH） （-））和（II）在施加的pH值（pH 4.5）下由H（+）催化的乙酸1-辛酯（OA）水解。在pH 10（k'= 0.33 h（-1））下添加2 gl（-1）的HA不会影响TeCA水解的速率，但HCH的水解受到显着抑制（k'= 4.6 x 10（-3）没有HA的h（-1）和在2 gl（-1）HA时为2.8 x 10（-3）h（-1））。在此HA浓度下，六氯环己烷的吸附率为51％，而TeCA的吸附量微不足道。由于OH（-）被HA分子的净负电荷静电排斥，有效地保护了被吸附的HCH分子。相反，OA在pH 4.5（k'= 1）下水解。加入2 gl（-1）HA（k'= 1.1 x 10（-3）h（-1））后，急剧加速了6 x 10（-5）h（-

  DOI：

  10.1016/j.chemosphere.2007.12.001

文献信息

• 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。
• 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
• New Metabolites in the Degradation of α- and γ-Hexachlorocyclohexane (HCH): Pentachlorocyclohexenes Are Hydroxylated to Cyclohexenols and Cyclohexenediols by the Haloalkane Dehalogenase LinB from Sphingobium indicum B90A
  作者：Vishakha Raina、Daniel Rentsch、Thomas Geiger、Poonam Sharma、Hans Rudolf Buser、Christof Holliger、Rup Lal、Hans-Peter E. Kohler

  DOI：10.1021/jf800465q

  日期：2008.8.1

  Technical hexachlorocyclohexane (HCH) and lindane are obsolete pesticides whose former production and use led to widespread contaminations posing serious and lasting health and environmental risks. Out of nine possible stereoisomers, alpha-, beta-, gamma-, and delta-HCH are usually present at contaminated sites, and research for a better understanding of their biodegradation has become essential for the development of appropriate remediation technologies. Because haloalkane dehalogenase LinB was recently found responsible for the hydroxylation of beta-HCH, delta-HCH, and delta-pentachlorocyclohexene (delta-PCCH), we decided to examine whether beta- and gamma-PCCH, which can be formed by LinA from alpha- and gamma-HCH, respectively, were also converted by LinB. Incubation of such substrates with Escherichia coli BL21 expressing functional LinB originating from Sphingobium indicum B90A showed that both beta-PCCH and gamma-PCCH were direct substrates of LinB. Furthermore, we identified the main metabolites as 3,4,5,6-tetrachloro-2-cyclohexene-1-ols and 2,5,6-trichloro-2-cyclohexene-1,4-diols by nuclear magnetic resonance spectroscopy and gas chromatography-mass spectrometry. In contrast to alpha-HCH, gamma-HCH was not a substrate for LinB. On the basis of our data, we propose a modified gamma-HCH degradation pathway in which gamma-PCCH is converted to 2,5-cyclohexadiene-1,4-diol via 3,4,5,6-tetrachloro-2-cyclohexene-1-ol and 2,5,6-trichloro-2-cyclohexene-1,4-diol.
• Hughes et al., Journal of the Chemical Society, 1953, p. 3827,3829
  作者：Hughes et al.

  DOI：——

  日期：——
• The Partial Additive Chlorination of the Benzene Ring. III. Pentachlorccyclohexene and Hexachlorocyclohexene
  作者：Alfred J. Kolka、Harold D. Orloff、Margaret E. Griffing

  DOI：10.1021/ja01634a012

  日期：1954.3