苯硫酚 | 108-98-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚类
• 中文名称: 苯硫酚
• 中文别名: (S)-(+)-3-氯-1,2-丙二醇；硫代苯酚；硫酚；苯硫醇；4-溴-1-氯-2-氟苯；苯基硫醇；巯基苯
• 英文名称: thiophenol
• 英文别名: Benzenethiol；phenylthiol；PhSH
• CAS: 108-98-5
• 化学式: C₆H₆S
• mdl: MFCD00004826
• 分子量: 110.18
• InChiKey: RMVRSNDYEFQCLF-UHFFFAOYSA-N

物化性质

• 稳定性/保质期：
  1. 有毒，可燃，有腐蚀性。对眼睛、黏膜、呼吸道及皮肤有强烈的刺激作用，吸入后可能引起喉、支气管痉挛、水肿及化学性肺炎、肺水肿而导致死亡。大鼠经口LD50值为46.2mg/kg。生产时应严格密闭，并提供充分的局部排风设施；尽可能实现机械化和自动化操作。如有蒸汽接触，应佩戴防毒面具并穿戴防护用具。 2. 稳定性：稳定 3. 禁配物：强氧化剂、强碱 4. 聚合危害：不聚合

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  1

ADMET

代谢

在大鼠中可能产生甲基苯基硫醚；在蟋蟀和蟑螂中产生苯基硫基-β-D-葡萄糖苷；在小鼠中产生苯基硫基-β-D-葡萄糖醛酸苷。/来自表格/

Yields methyl phenyl thioether probably in rats; phenylthio-beta-d-glucoside in crickets & cockroaches; & phenylthio-beta-d-glucuronide in mice. /From table/

来源:Hazardous Substances Data Bank (HSDB)

代谢

硫嘌呤甲基转移酶（TPMT）催化硫嘌呤和硫嘧啶药物的S-甲基化。发现了几种非杂环芳香硫醇化合物，包括硫酚，是硫嘌呤甲基转移酶的底物。这些芳香硫醇化合物的一些表观Km常数在纳摩尔范围内，比以前认为的仅是硫嘌呤甲基转移酶底物的硫嘌呤和硫嘧啶低几个数量级。这些观察结果提示，芳基硫醇甲基转移酶可能是这个酶比硫嘌呤甲基转移酶更好的名称。...

Thiopurine methyltransferase (TPMT) catalyzes the S-methylation of thiopurine and thiopyrimidine drugs. Several nonheterocyclic aromatic thiol compounds, including thiophenol, were discovered to be substrates for thiopurine methyltransferase. Apparent Km constants for some of these aromatic thiol compounds were in the nanomolar range, several orders of magnitude lower than those of the thiopurines & thiopyrimidines previously thought to be the only substrates for thiopurine methyltransferase. These observations suggested that aryl thiol methyltransferase might be a better name than thiopurine methyltransferase for this enzyme. ...

来源:Hazardous Substances Data Bank (HSDB)

代谢

N-乙酰半胱氨酸在吸烟者的尿液中的含量比非吸烟者高。在一项使用（14）C-苯的人体志愿者研究中发现，排出的噻吩酚源自苯代谢物S-苯基-N-乙酰半胱氨酸。人类吸烟者的尿液中噻吩酚水平也有所升高。

N-Acetylcysteine was ... elevated in the urine of smokers compared to nonsmoking humans. ... Studies with ... /a human volunteer/ with (14)C-benzene revealed the thiophenol excreted to be derived from the benzene metabolite S-phenyl-N-acetylcysteine. Human smokers also exhibited elevated urinary thiophenol levels.

来源:Hazardous Substances Data Bank (HSDB)

代谢

在大鼠研究中，接受了已知通过谷胱甘肽结合途径代谢的外源性化学物质，结果显示尿液中总硫醇和苯酚硫醇含量增加。进一步的大鼠研究使用放射性碳(14)标记的苯，揭示了排出的苯酚硫醇来源于苯代谢物S-苯基-N-乙酰半胱氨酸。

Studies with rats receiving xenobiotics known to be metabolized via glutathione conjugation, revealed increases in urinary total thiols and thiophenol. ... Further studies with rats with (14)C benzene revealed the thiophenol excreted to be derived from the benzene metabolite S-phenyl-N-acetylcysteine. ...

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

识别和使用：硫酚是一种无色透明的液体或棱柱状晶体，具有类似大蒜的刺鼻、穿透性气味，尤其是当它不纯时。它主要用作蚊幼虫杀虫剂和农药、药物以及琥珀色染料的化学中间体。人类暴露和毒性：硫酚会导致人类红细胞中的氧合血红蛋白转化为高铁血红蛋白，并引起剂量依赖性的氧化应激。动物研究：在兔眼上滴用硫酚会导致严重的刺激、中等程度的发红、结膜的水肿和3-4天的排出物。角膜出现混浊，在2-3周内逐渐加重，变得乳白色，遮盖了瞳孔和虹膜的细节。然而，在2个月内眼睛会恢复。在大鼠妊娠期间给予硫酚会增加着床后损失，减少活产仔数，降低胎儿体重/窝，高剂量组还会增加外部畸形的发生率。总之，在高剂量水平（50 mg/kg/天）观察到母体毒性，表现为母体死亡率、持续的身体重量和体重增加减少，以及治疗期间食物消耗量减少。在给药期间，所有硫酚组都观察到挖掘行为，表明对给药配方有厌恶感。挖掘行为随着剂量的增加和剂量的提前开始而呈剂量相关增加。基于妊娠第6-9天母体体重增加和食物消耗的轻微、暂时性减少，母体毒性的最低观察到有害效应水平（LOAEL）为20 mg/kg/天。在另一项Sprague Dawley大鼠的实验中，F0和F1代的肝脏和肾脏重量随着硫酚剂量的增加而增加，并与中心小叶肝细胞肥大和肾小管变性相关。在给予18和35 mg/kg的Sprague Dawley F0大鼠中观察到精子运动能力下降了5-6%。在所有处理的F1雄性中观察到精子生成抑制，但在F0雄性中没有观察到。在兔子的发育研究中，发育毒性的NOAEL为大于或等于40 mg/kg/天；母体毒性的NOAEL为10 mg/kg/天。硫酚在沙门氏菌鼠伤寒测试菌株TA100和TA98中，无论是否进行代谢激活，都显示出相对的诱变反应。

IDENTIFICATION AND USE: Thiophenol is a water-white liquid or prism-like crystal with a repulsive, penetrating odor similar to garlic, especially when impure. It is primarily used as a mosquito larvicide and chemical intermediate for pesticides, pharmaceuticals and amber dyes. HUMAN EXPOSURE AND TOXICITY: Thiophenols causes conversion of oxyhemoglobin to methemoglobin in human red blood cells and dose-dependent oxidative stress. ANIMAL STUDIES: Application of a drop to rabbit eyes caused severe irritation, moderate redness, chemosis of the conjunctiva with discharge for 3-4 days. Corneas developed opacities which gradually increased during 2-3 wk, becoming opalescent and obscuring details of pupil and iris. However, in 2 months the eyes recovered. Thiophenol administration in rats during gestation increased postimplantation loss, decreased the live litter size, decreased fetal body weight/litter, and increased the incidence of external malformations in the high dose group. In summary, maternal toxicity, observed as maternal mortality, a persistent decrease in body weight and weight gain, and decreased in food consumption during the treatment period occurred at the high dose level of 50 mg/kg/day. Rooting behavior was observed in all thiophenol groups during the dosing period indicating an aversion to the dosing formulation. Rooting behavior showed a dose-related increase and an earlier onset with increasing dose. The lowest observed-adverse-effect-level (LOAEL) was 20 mg/kg/day for maternal toxicity based upon minor, transient decreases in maternal weight gain & food consumption on gestation day 6-9. In another experiment in Sprague Dawley rats, F0 and F1 liver and kidney weights increased with increasing dose of thiophenol and were associated with centrilobular hepatocellular hypertrophy and renal tubule degeneration. Decreased (5-6%) sperm motility was observed in Sprague Dawley F0 rats administered 18 and 35 mg/kg. Inhibited spermiation was observed in all treated F1 males but not the F0 males. In developmental study in rabbits NOAEL for developmental toxicity was > or = 40 mg/kg/day; The NOAEL for maternal toxicity was 10 mg/kg/day. Thiophenol, in Salmonella typhimurium tester strains TA100 and TA98, showed relative mutagenic response with and without metabolic activation.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 暴露途径

这种物质可以通过吸入、皮肤接触和摄入被身体吸收。

The substance can be absorbed into the body by inhalation, through the skin and by ingestion.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 暴露途径

吸入，皮肤吸收，吞食，皮肤和/或眼睛接触

inhalation, skin absorption, ingestion, skin and/or eye contact

来源:The National Institute for Occupational Safety and Health (NIOSH)

毒理性

• 症状

眼睛、皮肤、呼吸系统刺激；皮炎；发绀；咳嗽、喘息、呼吸困难（呼吸困难）、肺水肿、肺炎；头痛、眩晕、中枢神经系统抑制；恶心、呕吐；肾脏、肝脏、脾脏损伤

irritation eyes, skin, respiratory system; dermatitis; cyanosis; cough, wheezing, dyspnea (breathing difficulty), pulmonary edema, pneumonitis; headache, dizziness, central nervous system depression; nausea, vomiting; kidney, liver, spleen damage

来源:The National Institute for Occupational Safety and Health (NIOSH)

毒理性

• 吸入症状

咳嗽。头痛。恶心。喉咙痛。

Cough. Headache. Nausea. Sore throat.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

制备方法与用途

制备方法

将苯磺酸或苯磺酰氯用硫酸和锌进行还原，或采用电解还原，可制得苯硫酚。另一种方法是以氯苯为原料，与硫化氢反应。具体操作是将氯苯与硫化氢按摩尔比1:2混合，在580-600℃下反应，转化率在30%以上时，苯硫酚的收率超过70%。

合成制备方法

同样地，可以将苯磺酸或苯磺酰氯用硫酸和锌进行还原，或采用电解还原来制得苯硫酚。另一种方法是以氯苯为原料，与硫化氢反应。具体操作是将氯苯与硫化氢按摩尔比1:2混合，在580-600℃下反应，转化率在30%以上时，苯硫酚的收率超过70%。

用途简介

苯硫酚用作染料、医药、农药、阻聚剂、抗氧剂等精细化学品的中间体，例如用于生产药物甲砜霉素、杀菌剂、克瘟散等。

用途

1. 苯硫酚可作为染料、医药、农药、阻聚剂、抗氧剂等精细化学品的中间体，如用于生产药物甲砜霉素、杀菌剂、克瘟散等。
2. 它能够使烯烃从Z一式转化为E一式。其钠盐碱性比甲醇钠或乙醇钠弱，具有较强的亲核性，能选择性地脱去季铁盐的甲基或苄基。
3. 用于有机合成、制药工业以及作为分析试剂。

反应信息

• 作为反应物：
  描述：

  苯硫酚 在 sodium azide 、 氯-(4-甲基苯基)磺酰基亚胺钠 、 四丁基氯化铵 、 水 作用下， 以 乙腈 为溶剂， 反应 1.5h， 生成 苯磺酰基叠氮化物
  参考文献：
  名称：

  使用氯胺-T从硫醇一锅法合成磺酰胺和磺酰叠氮

  摘要：

  描述了由硫醇方便地合成磺酰胺和磺酰叠氮化物。通过用氯胺-T（= N-氯代甲苯磺酰胺= N-氯--4-甲基苯磺酰胺），四丁基氯化铵（Bu 4 NCl）和H 2 O氧化，可以完成从硫醇中磺酰氯的原位制备。在同一锅中与过量的胺或NaN 3反应。

  DOI：

  10.1002/hlca.201200648
• 作为产物：
  描述：

  苯基氯硫代甲酸酯 以 乙醇 为溶剂， 生成 苯硫酚
  参考文献：
  名称：

  Dual Pathways in the Solvolyses of Phenyl Chlorothioformate

  摘要：

  DOI：

  10.1021/jo970657b
• 作为试剂：
  描述：

  tert-butyl (S)-(3-(isoquinolin-6-ylamino)-3-oxo-2-phenylpropyl)(2-((2-nitrophenyl)sulfonyl)-5,8,11-trioxa-2-azatridecan-13-yl)carbamate 在 potassium carbonate 、 苯硫酚 、 potassium iodide 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 20.0h， 生成 tert-butyl (2R,5R)-4-(2-(6-(4-fluorobenzyl)-5-(14-((S)-3-(isoquinolin-6-ylamino)-3-oxo-2-phenylpropyl)-2,17,17-trimethyl-15-oxo-5,8,11,16-tetraoxa-2,14-diazaoctadecyl)-3,3-dimethyl-2,3-dihydro-1H-pyrrolo[3,2-b]pyridin-1-yl)-2-oxoethyl)-5-(methoxymethyl)-2-methylpiperazine-1-carboxylate
  参考文献：
  名称：

  WO2024071371A1

  摘要：

  公开号：

文献信息

• Copper-Mediated Direct Sulfenylation of 4-Hydroxyquinolinones and 4-Hydroxypyridones with Aryl Thiols via a C−H Functionalization Process
  作者：Tao Guo、Hongyan Wang

  DOI：10.1055/s-0036-1588829

  日期：2017.9

  An efficient approach for the direct sulfanylation of 4-hydroxyquinolinones and 4-hydroxypyridones with aryl thiols in the presence of CuI/DMSO has been developed. The substrate scope is broad, allowing facile synthesis of a range of structurally diverse 3-sulfanyl-4-hydroxyquinolinones and 3-sulfanyl-4-hydroxypyridones in good efficiency.

  一种在CuI/DMSO存在下，利用芳基硫醇直接对4-羟基喹啉酮和4-羟基吡啶酮进行砜化的高效方法已经开发出来。底物范围广泛，能够轻松合成一系列结构多样的3-砜基-4-羟基喹啉酮和3-砜基-4-羟基吡啶酮，效率良好。
• Synthesis of Sulfonylhydrazine-1,2-dicarboxylates from Thiols and Dialkyl Azodicarboxylates
  作者：Jiaxi Xu、Bingnan Zhou、Xiao Yang

  DOI：10.1055/s-0036-1588108

  日期：——

  thiols/thiophenols to dialkyl azodicarboxylates and subsequent oxidation with MCPBA. The protocol represents the first application of sulfenylhydrazines as precursors to sulfonylhydrazine derivatives, leading to a novel and effective method for the synthesis of sulfonylhydrazines. 1-Sulfonylhydrazine-1,2-dicarboxylates are efficiently prepared via nucleophilic addition of thiols/thiophenols to dialkyl azodicarboxylates

  摘要 通过将硫醇/硫酚亲核加成到偶氮二羧酸二烷基酯并随后用MCPBA氧化，可以有效地制备1-磺酰基肼-1,2-二羧酸酯。该协议代表了磺酰肼作为磺酰肼衍生物的前体的首次应用，从而导致了一种新颖而有效的合成磺酰肼的方法。 通过将硫醇/硫酚亲核加成到偶氮二羧酸二烷基酯并随后用MCPBA氧化，可以有效地制备1-磺酰基肼-1,2-二羧酸酯。该协议代表了磺酰肼作为磺酰肼衍生物的前体的首次应用，从而导致了一种新颖而有效的合成磺酰肼的方法。
• [EN] BENZAMIDE OR BENZAMINE COMPOUNDS USEFUL AS ANTICANCER AGENTS FOR THE TREATMENT OF HUMAN CANCERS<br/>[FR] COMPOSÉS BENZAMIDE OU BENZAMINE À UTILISER EN TANT QU'ANTICANCÉREUX POUR LE TRAITEMENT DE CANCERS HUMAINS
  申请人：UNIV TEXAS

  公开号：WO2017007634A1

  公开（公告）日：2017-01-12

  The described invention provides small molecule anti-cancer compounds for treating tumors that respond to cholesterol biosynthesis inhibition. The compounds selectively inhibit the cholesterol biosynthetic pathway in tumor-derived cancer cells, but do not affect normally dividing cells.

  所描述的发明提供了用于治疗对胆固醇生物合成抑制作出反应的肿瘤的小分子抗癌化合物。这些化合物选择性地抑制肿瘤来源的癌细胞中的胆固醇生物合成途径，但不影响正常分裂的细胞。
• Expanding the Scope of Hypervalent Iodine Reagents for Perfluoroalkylation: From Trifluoromethyl to Functionalized Perfluoroethyl
  作者：Václav Matoušek、Jiří Václavík、Peter Hájek、Julie Charpentier、Zsófia E. Blastik、Ewa Pietrasiak、Alena Budinská、Antonio Togni、Petr Beier

  DOI：10.1002/chem.201503531

  日期：2016.1.4

  A series of new hypervalent iodine reagents based on the 1,3‐dihydro‐3,3‐dimethyl‐1,2‐benziodoxole and 1,2‐benziodoxol‐3‐(1H)‐one scaffolds, which contain a functionalized tetrafluoroethyl group, have been prepared, characterized, and used in synthetic applications. Their corresponding electrophilic fluoroalkylation reactions with various sulfur, oxygen, phosphorus, and carbon‐centered nucleophiles

  基于1,3-二氢-3,3-二甲基-2-1,2-苯并恶唑和1,2-苯并恶唑-3-（1 H）-one骨架的一系列新的高价碘试剂，它们含有功能化的四氟乙基已经制备，表征并用于合成应用。它们与各种硫，氧，磷和以碳为中心的亲核试剂进行相应的亲电氟烷基化反应，可得到具有连接两个功能部分的四氟乙烯单元的产物。一个相关的λ 3含有荧光团的碘已显示在温和条件下与半胱氨酸衍生物反应，生成硫醇标记的产物，该产物在存在过量硫醇的情况下是稳定的。因此，这些新试剂作为快速，不可逆和选择性硫醇生物结合的工具，在化学生物学中显示出巨大的潜力。
• [EN] HYPERVALENT IODINE CF2CF2X REAGENTS AND THEIR USE<br/>[FR] RÉACTIFS CF2CF2X À BASE D'IODE HYPERVALENT ET LEUR UTILISATION
  申请人：ETH ZUERICH

  公开号：WO2016019475A1

  公开（公告）日：2016-02-11

  A hypervalent iodine of formula (I) or formula (II) wherein R is a nucleophile and a method for their production is described. Such compounds can be used for fluoroethylation of compounds carrying a reactive group. A preferred compound carrying a reactive group is cystein in any environment such as peptide targets.

  一种具有化学式（I）或化学式（II）的高价碘，其中R是亲核试剂，并描述了它们的生产方法。这类化合物可用于对携带反应基团的化合物进行氟乙基化。携带反应基团的优选化合物是半胱氨酸，可存在于任何环境中，如肽靶标。

表征谱图