2,3,5,6-Tetrakis-(β-hydroxy-ethylmercapto)-hydrochinon | 92373-11-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2,3,5,6-Tetrakis-(β-hydroxy-ethylmercapto)-hydrochinon
• 英文别名: 2,3,5,6-tetrakis[(2-hydroxyethyl)thio]hydroquinone；1,4-dihydroxy-2,3,5,6-tetra-(2'hydroxyethyl-thio) benzene；2,3,5,6-Tetrakis(2-hydroxyethylsulfanyl)benzene-1,4-diol
• CAS: 92373-11-0
• 化学式: C₁₄H₂₂O₆S₄
• 分子量: 414.589
• InChiKey: TVWFLXROQJHXHN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  24
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  223
• 氢给体数：
  6
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,3,5,6-Tetrakis-(β-hydroxy-ethylmercapto)-hydrochinon 生成 2,3,5,6-Tetrakis-(β-chlor-ethylmercapto)-hydrochinon
  参考文献：
  名称：

  REACTIONS OF 2,3,5,6-TETRAKIS(β-HYDROXYETHYLMERCAPTO)-1,4-HYDROQUINONE AND RELATED COMPOUNDS

  摘要：

  氯醌（I）与碱和2-巯基乙醇的处理不仅导致氯原子的取代，还导致还原形成2,3,5,6-四(β-羟乙基巯基)-1,4-氢醌（II）。从II制备2,3,5,6-四(β-氯乙基巯基)-1,4-氢醌（III）的条件与从II制备较低熔点化合物（IV）的条件有所不同，需要精确控制温度和浓度，以避免制备过程中的不稳定行为。通过分析和环化反应，已确定较低熔点化合物的结构为2,3-二氢-5,7,8-三(β-氯乙基巯基)-6-羟基-1,4-苯并噻嗪（IV）。将2,3-二氯-1,4-萘醌（VIII）与2-巯基乙醇处理得到2,3-双(β-羟乙基巯基)-1,4-萘醌（IX），而不像氯醌那样生成醌醇。醌（IX）无法通过氯化氢处理转化为2,3-双(β-氯乙基巯基)-1,4-萘醌，因为在这些条件下只形成了1,4-氧硫-5,10-蒽醌（X）。描述了涉及分子内加成、消除和环化的X形成机制。

  DOI：

  10.1139/v62-191
• 作为产物：
  描述：

  2,3,5,6-四氯酚 在 Sphingobium chlorophenolicum hexahistidine-tagged pentachlorophenol hydroxylase 、 抗坏血酸 、 还原型辅酶II(NADPH)四钠盐 作用下， 反应 0.02h， 生成 2,3,5,6-Tetrakis-(β-hydroxy-ethylmercapto)-hydrochinon
  参考文献：
  名称：

  Pentachlorophenol Hydroxylase, a Poorly Functioning Enzyme Required for Degradation of Pentachlorophenol by Sphingobium chlorophenolicum

  摘要：

  Several strains of Sphingobium chlorophenolicum have been isolated from soil that was heavily contaminated with pentachlorophenol (PCP), a toxic pesticide introduced in the 1930s. S. chlorophenolicum appears to have assembled a poorly functioning pathway for degradation of PCP by patching enzymes recruited via two independent horizontal gene transfer events into an existing metabolic pathway. Flux through the pathway is limited by PCP hydroxylase. PCP hydroxylase is a dimeric protein that belongs to the family of flavin-dependent phenol hydroxylases. In the presence of NADPH, PCP hydroxylase converts PCP to tetrachlorobenzoquinone (TCBQ). The k(cat) for PCP (0.024 s(-1)) is very low, suggesting that the enzyme is not well evolved for turnover of this substrate. Structure-activity studies reveal that substrate binding and activity are enhanced by a low pK(a) for the phenolic proton, increased hydrophobicity, and the presence of a substituent ortho to the hydroxyl group of the phenol. PCP hydroxylase exhibits substantial uncoupling; the C4a-hydroxyflavin intermediate, instead of hydroxylating the substrate, can decompose to produce H2O2 in a futile cycle that consumes NADPH. The extent of uncoupling varies from 0 to 100% with different substrates. The extent of uncoupling is increased by the presence of bulky substituents at position 3, 4, or 5 and decreased by the presence of a chlorine in the ortho position. The effectiveness of PCP hydroxylase is additionally hindered by its promiscuous activity with tetrachlorohydroquinone (TCHQ), a downstream metabolite in the degradation pathway. The conversion of TCHQ to TCBQ reverses flux through the pathway. Substantial uncoupling also occurs during the reaction with TCHQ, Photo used with permission from Johannes Rudolph.

  DOI：

  10.1021/bi300261p

文献信息

• Ester von 3-tert.Butyl- bzw. 3-tert.-Butyl-5-alkyl-4-hydroxyphenyl-(alkan-)-carbonsäuren mit Oxethylaten von Polythiolen, Verfahren zu ihrer Herstellung und ihre Verwendung als Stabilisatoren
  申请人：HÜLS AKTIENGESELLSCHAFT

  公开号：EP0268039A2

  公开（公告）日：1988-05-25

  Ester von 3-tert.Butyl-bzw. 3-tert.Butyl-5-alkyi-4-hydroxy-phenyl-(alkan-)carbonsäuren der Formel I mit Oxethylaten von Polythiolaromaten der allgemeinen Formeln II und III, vorzugsweise der Formel II, mit 2 bis 6 Thiolgruppen sowie mit Oxethylaten von Dithiolcycloalkanen der allgemeinen Formel IV, die maximal 6 Alkylenoxideinheiten enthalten, mit X = (CH2)mSH X' = (CH2)rSH X" = (CH2)sSH, wobei m,r,s = 0 oder 1 sein können, R,R',R" = H, Alkyl,Halogen, Hydroxyl, R3 = H,C1-bis C4-Alkyl, R4,R5 = Cz-bis C4-Alkylen, q = 0 bis 7, vorzugweise 1, n = 2 bis 6 für z bzw. z' = 0 n = 1 bis 5 für z bzw. z' ≠0 o + p = n und wobei 0 ≤ a,z ≤ a + z ≤ 6-n (in Formel II) bzw. 0 ≤ b,c,z' ≤ 4 ≤ 8-n (in Formel III) sein können. Zur Herstellung dieser Ester werden die 3-tert.Butyl-bzw. 3-tert.-Butyl-5-alkyl-4-hydroxyphenyl-(alkan)-carbonsäuren bzw. deren Derivate mit Oxethylaten von Polythiolaromaten und Dithiolcycloalkanen in Gegenwart von an sich bekannten Katalysatoren verestert oder umgeestert. Die erfindungsgemäßen Ester verwendet man zur Stabilisierung von Polymeren.

  式 I 的 3-叔丁基-或 3-叔丁基-5-烷基-4-羟基苯基-（烷基）羧酸的酯类 与通式 II 和 III 的聚硫代芳香族化合物（最好是通式 II 的聚硫代芳香族化合物）的氧化乙酸酯，其中含有 2 至 6 个硫醇基团 以及通式 IV 的二硫醇环烷氧化物（最多含有 6 个氧化亚烷基单元）、 其中 X = (CH2)mSH X' = (CH2)rSH X" = (CH2)sSH，其中 m,r,s = 0 或 1、 R,R',R"=H、烷基、卤素、羟基、 R3 = H、C1 至 C4 烷基、 R4、R5 = Cz 至 C4 亚烷基、 q = 0 至 7，最好为 1、 对于 z 或 z' = 0，n = 2 至 6 当 z 或 z' ≠0 时，n = 1 至 5 o + p = n 其中 0 ≤ a,z ≤ a + z ≤ 6-n （式 II）或 0 ≤ b,c,z' 可以是 ≤ 4 ≤ 8-n （式 III）。 为了制备这些酯，3-叔丁基或 3-叔丁基-5-烷基-4-羟基苯基-(烷)-羧酸或其衍生物在本身已知的催化剂存在下，与多硫芳烃和二硫环烷的氧乙酸酯进行酯化或酯交换反应。 本发明的酯类可用于稳定聚合物。
• US4906775A
  申请人：——

  公开号：US4906775A

  公开（公告）日：1990-03-06
• Pentachlorophenol Hydroxylase, a Poorly Functioning Enzyme Required for Degradation of Pentachlorophenol by <i>Sphingobium chlorophenolicum</i>
  作者：Klara Hlouchova、Johannes Rudolph、Jaana M. H. Pietari、Linda S. Behlen、Shelley D. Copley

  DOI：10.1021/bi300261p

  日期：2012.5.8

  Several strains of Sphingobium chlorophenolicum have been isolated from soil that was heavily contaminated with pentachlorophenol (PCP), a toxic pesticide introduced in the 1930s. S. chlorophenolicum appears to have assembled a poorly functioning pathway for degradation of PCP by patching enzymes recruited via two independent horizontal gene transfer events into an existing metabolic pathway. Flux through the pathway is limited by PCP hydroxylase. PCP hydroxylase is a dimeric protein that belongs to the family of flavin-dependent phenol hydroxylases. In the presence of NADPH, PCP hydroxylase converts PCP to tetrachlorobenzoquinone (TCBQ). The k(cat) for PCP (0.024 s(-1)) is very low, suggesting that the enzyme is not well evolved for turnover of this substrate. Structure-activity studies reveal that substrate binding and activity are enhanced by a low pK(a) for the phenolic proton, increased hydrophobicity, and the presence of a substituent ortho to the hydroxyl group of the phenol. PCP hydroxylase exhibits substantial uncoupling; the C4a-hydroxyflavin intermediate, instead of hydroxylating the substrate, can decompose to produce H2O2 in a futile cycle that consumes NADPH. The extent of uncoupling varies from 0 to 100% with different substrates. The extent of uncoupling is increased by the presence of bulky substituents at position 3, 4, or 5 and decreased by the presence of a chlorine in the ortho position. The effectiveness of PCP hydroxylase is additionally hindered by its promiscuous activity with tetrachlorohydroquinone (TCHQ), a downstream metabolite in the degradation pathway. The conversion of TCHQ to TCBQ reverses flux through the pathway. Substantial uncoupling also occurs during the reaction with TCHQ, Photo used with permission from Johannes Rudolph.
• REACTIONS OF 2,3,5,6-TETRAKIS(β-HYDROXYETHYLMERCAPTO)-1,4-HYDROQUINONE AND RELATED COMPOUNDS
  作者：Marshall Kulka

  DOI：10.1139/v62-191

  日期：1962.7.1

  The treatment of chloranil (I) with alkali and 2-mercaptoethanol resulted not only in replacement of the chlorine atoms but also in reduction to form 2,3,5,6-tetrakis(β-hydroxyethylmercapto)-1,4-hydroquinone (II). The conditions for the preparation of 2,3,5,6-tetrakis(β-chloroethylmercapto)-1,4-hydroquinone (III) from II differed from those required for the preparation of a lower-melting compound (IV) from II by such a narrow margin that exact control of temperature and concentration were necessary in order to avoid erratic behavior in the preparation. The structure of the lower-melting compound has been established as 2,3-dihydro-5,7,8-tris(β-chloroethylmercapto)-6-hydroxy-1,4-benzoxathiin (IV) by analyses and cyclization reactions. The treatment of 2,3-dichloro-1,4-naphthoquinone (VIII) with 2-mercaptoethanol yielded 2,3-bis(β-hydroxyethylmercapto)-1,4-naphthoquinone (IX) and not the quinol as was the case with chloranil. The quinone (IX) could not be converted to 2,3-bis(β-chloroethylmercapto)-1,4-naphthoquinone by treatment with hydrogen chloride because under these conditions only 1,4-oxathio-5,10-anthraquinone (X) was formed. A mechanism for the formation of X which involves intramolecular addition, elimination, and cyclization is described.

  氯醌（I）与碱和2-巯基乙醇的处理不仅导致氯原子的取代，还导致还原形成2,3,5,6-四(β-羟乙基巯基)-1,4-氢醌（II）。从II制备2,3,5,6-四(β-氯乙基巯基)-1,4-氢醌（III）的条件与从II制备较低熔点化合物（IV）的条件有所不同，需要精确控制温度和浓度，以避免制备过程中的不稳定行为。通过分析和环化反应，已确定较低熔点化合物的结构为2,3-二氢-5,7,8-三(β-氯乙基巯基)-6-羟基-1,4-苯并噻嗪（IV）。将2,3-二氯-1,4-萘醌（VIII）与2-巯基乙醇处理得到2,3-双(β-羟乙基巯基)-1,4-萘醌（IX），而不像氯醌那样生成醌醇。醌（IX）无法通过氯化氢处理转化为2,3-双(β-氯乙基巯基)-1,4-萘醌，因为在这些条件下只形成了1,4-氧硫-5,10-蒽醌（X）。描述了涉及分子内加成、消除和环化的X形成机制。