硫丹醇 | 2157-19-9

• 物质功能分类: 化学农药原药 - 杀虫剂中间体
• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 中文名称: 硫丹醇
• 英文名称: 1,2,3,4,7,7-hexachloro-5,6-bis(hydroxymethyl)bicyclo<2.2.1>hept-2-ene
• 英文别名: 1,2,3,4,7,7-hexachlorobicyclo<2.2.1>hept-2-ene-5,6-bis(methanol)；endosulfan alcohol；endosulfan diol；endosulfandiol；1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2,3-dimethanol；1,4,5,6,7,7-hexachloro-2,3-bis(hydroxymethyl)-bicyclo[2:2:1]hept-5-ene；[1,4,5,6,7,7-hexachloro-3-(hydroxymethyl)-2-bicyclo[2.2.1]hept-5-enyl]methanol
• CAS: 2157-19-9
• 化学式: C₉H₈Cl₆O₂
• 分子量: 360.879
• InChiKey: GTSJHTSVFKEASK-UHFFFAOYSA-N

物化性质

• 熔点：
  207-208℃
• 沸点：
  411.8±40.0 °C(Predicted)
• 密度：
  1.5459 (estimate)
• 闪点：
  100 °C
• 溶解度：
  超声处理轻微溶于甲醇
• 稳定性/保质期：
  硫丹醇是一种固体。

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

安全信息

• 危险品标志：
  N
• 安全说明：
  S60,S61
• 危险类别码：
  R50/53
• WGK Germany：
  2
• 危险品运输编号：
  UN 3077 9/PG 3
• RTECS号：
  DT5300000
• 海关编码：
  2906199090
• 储存条件：
  室温

制备方法与用途

化学性质
硫丹醇为固体。

用途
硫丹醇是有机氯杀虫剂硫丹的中间体。

生产方法
硫丹醇的合成方法有直接法和间接法两种。我国多采用直接法，具体步骤如下：将六氯环戊二烯与溶剂投入反应釜中，搅拌并加热至反应温度后，滴加丁烯二醇。滴加完毕后，在该温度下继续搅拌反应10小时，随后冷却析出硫丹醇结晶。经过滤和溶剂洗涤即可得到硫丹醇。

反应信息

• 作为反应物：
  描述：

  硫丹醇 在 sodium tetrahydroborate 、 cyanocobalamin 作用下， 以 甲醇 、 乙二醇二甲醚 为溶剂， 反应 3.33h， 生成
  参考文献：
  名称：

  Synthesis and structure-activity relationships of a series of insecticidal dioxatricyclododecenes acting as the noncompetitive antagonist of GABAA receptors

  摘要：

  Chlorinated analogues of 5-substituted 2,3:8,7-endo-4,6-dioxatricyclo[7.2.1.0(2,8)]dodec-10-ene (DTD) and 2,3:8,7-endo-4,6-dioxa-5-thiatricyclo[7.1.1.0(2,8)]dodec-10-ene 5-oxide were prepared. With -CH2-, -CH(Me)-, and -S(O)- at the 5 position, the presence of chlorine atoms in the norbornene moiety was important in exerting toxic effects to houseflies, while with -CH(n-Pr)- and -CH(Ph-CN-4)- the introduction of chlorine atoms resulted in a loss of toxic activity. The effect of the presence of chlorine atoms on the potency in inhibiting [S-35]tert-butylbicyclophosphorothionate (TBPS) binding to rat brain membranes was found to be correlated to their insecticidal activity. A good correlation (r=0.807) was obtained between insecticidal activity and the potency in inhibiting [S-35]TBPS binding for 29 compounds, including known noncompetitive antagonists of GABA(A) receptors. The Scatchard analysis indicated that both types of analogues, 1,9,10,11,12,12-hexachloro-DTD and 5-(4-cyanophenyl)-DTD, act competitively at the TBPS binding site in the GABA-gated chloride channel. These two types of analogues, however, appear to interact with slightly different subsites within the TBPS binding site.

  DOI：

  10.1021/jf00035a059
• 作为产物：
  描述：

  氯菌酸 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 硫丹醇
  参考文献：
  名称：

  Zur Chemie von Polyhalocyclopentadienen, 22. Mitt.: �ber die Herstellung von 1,4,5,6,7,7-Hexachlorbicyclo[2.2.1]hepten-(5)-bishydroxymethylen-(2,3)

  摘要：

  DOI：

  10.1007/bf00924776

文献信息

• Isolation of endosulfan sulfate-degrading Rhodococcus koreensis strain S1-1 from endosulfan contaminated soil and identification of a novel metabolite, endosulfan diol monosulfate
  作者：Koji Ito、Fujimasa Kawashima、Kazuhiro Takagi、Ryota Kataoka、Masaaki Kotake、Hiromasa Kiyota、Kenichi Yamazaki、Futa Sakakibara、Sanae Okada

  DOI：10.1016/j.bbrc.2016.04.021

  日期：2016.5

  S1-1, was isolated from soil to which endosulfan had been applied annually for more than 10 years until 2008. The strain isolated in this work reduced the concentration of endosulfan sulfate (2) from 12.25 μM to 2.11 μM during 14 d at 30 °C. Using ultra performance liquid chromatography-electrospray ionization-mass spectroscopy (UPLC-ESI-MS), a new highly water-soluble metabolite possessing six chlorine

  从每年施用硫丹的土壤中分离出好氧降解硫酸硫的细菌Rhodococcus koreensis S1-1菌株，直到2008年为止。这项工作分离出的菌株降低了硫丹硫酸盐（2）的浓度。在30°C下14 d期间为12.25μM至2.11μM。使用超高效液相色谱-电喷雾电离质谱（UPLC-ESI-MS），发现一种新的具有六个氯原子的高度水溶性代谢物是硫丹二醇单硫酸盐（6），由环状硫酸盐的水解反应从2衍生而来。酯环。通过候选衍生物的化学合成以及HR-MS和UPLC-MS分析阐明了6的结构。因此，建议菌株S1-1具有新的代谢途径2。
• [EN] NUCLEOPHILIC ENHANCEMENT OF BETA-ENDOSULFAN IN AN ENDOSULFAN MIX<br/>[FR] AMELIORATION NUCLEOPHILE DE BETA-ENDOSULFAN DANS UN MELANGE D'ENDOSULFANS
  申请人：CROP CARE AUSTRALASIA PTY LTD

  公开号：WO2004103989A1

  公开（公告）日：2004-12-02

  The invention relates to a process for the preparation of endosulfan enriched in the ß-isomer thereof (ß-endosulfan). The invention also provides a process for enriching the ß-isomer content of a mixture of a- and ß-endosulfan, and to processes for obtaining ß-endosulfan in substantially pure form.

  本发明涉及一种制备富含ß-内吸砒的过程（ß-内吸砒）。本发明还提供了一种富集a-和ß-内吸砒混合物中ß-异构体含量的过程，以及获取ß-内吸砒的过程，其形式基本纯净。
• Comparative studies of various iron-mediated oxidative systems for the photochemical degradation of endosulfan in aqueous solution
  作者：Noor S. Shah、Xuexiang He、Javed Ali Khan、Hasan M. Khan、Dominic L. Boccelli、Dionysios D. Dionysiou

  DOI：10.1016/j.jphotochem.2015.03.014

  日期：2015.6

  This study investigated iron-mediated oxidative processes for the photochemical degradation of endosulfan, a chlorinated insecticide and central nervous system disruptor. At UV fluence of 360 mJ/cm2, 52.4% and 32.0% removal of 2.45 μM initial endosulfan was observed by UV/Fe3+ and UV/Fe2+ processes, respectively, at an initial concentration of 17.8 μM iron. The degradation of endosulfan by UV/Fe3+

  这项研究调查了铁介导的氧化过程，以光化学降解硫丹，一种氯化杀虫剂和中枢神经系统干扰物。在UV能量通量为360 mJ / cm 2时，在铁的初始浓度为17.8μM时，分别通过UV / Fe 3+和UV / Fe 2+工艺观察到了2.45μM初始硫丹的52.4％和32.0％去除。通过添加过氧化物（例如，H 2 O 2，S 2 O 8 2-或HSO 5 -），UV / Fe 3+或UV / Fe 2+对硫丹的降解作用显着增强。）。之间的UV /过氧化物/ Fe的过程中，在UV通量的99.0％的最高效率的降解360毫焦耳/厘米2通过UV / HSO观察5 - /铁2+与2.45μM[硫丹] 0，17.8μM的[Fe 2 + ] 0，并且49.0μM[HSO 5 - ] 0。通过增加[Fe 2+ ] 0和/或[过氧化物] 0或通过降低[硫丹] 0可以提高硫丹的降解速率常数，而硫丹的初始降解速率随[Fe
• Endosulfan formulation and methods of use thereof
  申请人：——

  公开号：US20040054010A1

  公开（公告）日：2004-03-18

  The present inventors have found that the contrasting chemical, physical and environmental characteristics of alpha and beta endosulfan provide an opportunity to formulate an effective endosulfan formulation with lower risk to the environment. Accordingly, the present invention provides a method for controlling or reducing pest numbers in an area affected or likely to be affected by pests, the method comprising applying to the area an endosulfan formulation, the formulation comprising beta endosulfan and alpha endosulfan, wherein the ratio of beta to alpha endosulfan in the formulation is at least 3.5:6.5 w/w.

  本发明者发现，α硫丹和β硫丹的化学、物理和环境特性截然不同，这为配制对环境风险较低的有效硫丹制剂提供了机会。因此，本发明提供了一种在受害虫影响或可能受害虫影响的地区控制或减少害虫数量的方法，该方法包括向该地区施用硫丹制剂，该制剂包括β硫丹和α硫丹，其中制剂中β硫丹和α硫丹的重量比至少为3.5:6.5。
• Process for the stereoselective preparation of insecticide 6,7,8,9,10-10-hexahalo-1, 5, 5a, 6, 9, 9a-hexadro-6, 9-methano-2, 4, 3-benzodioxathiepin-3-oxide
  申请人：——

  公开号：US20040092751A1

  公开（公告）日：2004-05-13

  A process for the stereoselective preparation of insecticide 6,7,8,9,10,10-hexahalo-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin-3-oxide of the general formula 1: 1 wherein X is a halogen such as fluorine, chlorine or bromine. The process comprises reacting 1,4,5,6,7,7-hexahalo-5-norbornene-2,3-dimethanol of the general formula IV: 2 wherein X is as defined above, with a cyclic sulfite ring forming reagent optionally in an inert organic solvent at ambient to 139° C., wherein the reaction is carried out in the presence of a stereo isomer directing agent comprising an isomer of the compound of the formula I different from the desired isomer. The molar ratio of the stereoisomer directing agent to the dimethanol compound of the formula IV is a least 0.07.

  一种立体选择性制备通式 1 的杀虫剂 6,7,8,9,10,10-六卤-1,5,5a,6,9,9a-六氢-6,9-甲桥-2,4,3-苯并二氧硫杂卓-3-氧化物的工艺： 1 其中 X 为卤素，如氟、氯或溴。该工艺包括将通式 IV 的 1,4,5,6,7,7-六卤-5-降冰片烯-2,3-二甲醇与通式 IV 的 1,4,5,6,7,7-六卤-5-降冰片烯-2,3-二甲醇反应： 2 其中 X 如上文所定义，与环状亚硫酸盐成环试剂可选在惰性有机溶剂中于常温至 139 摄氏度下反应，反应在立体异构体引导剂存在下进行，立体异构体引导剂包括与所需异构体不同的式 I 化合物异构体。立体异构体引导剂与式 IV 的二甲醇化合物的摩尔比至少为 0.07。