甲硫醇 | 74-93-1

• 物质功能分类: 香精与香料 - 合成香料 - 硫醇类香料
• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醇
• 中文名称: 甲硫醇
• 中文别名: 硫氢甲烷；甲硫醇；巯基甲烷；硫氢甲烷
• 英文名称: methylthiol
• 英文别名: Methanethiol；methyl mercaptan
• CAS: 74-93-1
• 化学式: CH₄S
• 分子量: 48.1088
• InChiKey: LSDPWZHWYPCBBB-UHFFFAOYSA-N

物化性质

• 熔点：
  −123 °C(lit.)
• 沸点：
  6 °C(lit.)
• 密度：
  0.8665
• 蒸气密度：
  1.66 (vs air)
• 闪点：
  <71℃
• 溶解度：
  溶于酒精、乙醚(Weast,1986)和石脑油(Hawley,1981)
• 暴露限值：
  TLV-TWA 0.5 ppm (～1.0 mg/m3 ) (ACGIH and MSHA); ceiling 10 ppm (OSHA); IDLH 400 ppm (NIOSH); the revised IDLH is 150 ppm in analogy to H2S.
• LogP：
  0.72
• 物理描述：
  Colorless gas with a disagreeable odor like garlic or rotten cabbage. [Note: A liquid below 43°F. Shipped as a liquefied compressed gas.]
• 颜色/状态：
  Water-white liquid when below boiling point, or colorless gas
• 气味：
  Odor of rotten cabbage
• 味道：
  Unpleasant cabbage taste
• 蒸汽密度：
  1.66 (EPA, 1998) (Relative to Air)
• 蒸汽压力：
  1,510 mm Hg at 25 °C
• 大气OH速率常数：
  3.29e-11 cm3/molecule*sec
• 分解：
  Upon decomposition, emits highly toxic fumes of /sulfur oxides/.
• 燃烧热：
  -11,054 Btu/lb = -6,141 cal/g = -257.0x10+5 J/kg
• 汽化热：
  510.21 kJ/kg
• 表面张力：
  31 dynes/cm = 0.031 N/m at 5 °C
• 电离电位：
  9.44 eV
• 气味阈值：
  0.0021 ppm (purity not specified)
• 折光率：
  1.430-1.436 (gas); 0.894 (liquid)
• 解离常数：
  pKa = 10.33 at 25 °C
• 保留指数：
  400;444;414;414;460;461;414;414;414;430;460
• 稳定性/保质期：

  1. 稳定性：稳定。

  2. 禁配物：强氧化剂、卤素、酸类。

  3. 避免接触的条件：潮湿空气。

  4. 聚合危害：不聚合。

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  2
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  1

ADMET

代谢

甲硫醇在大鼠体内的代谢进行了研究。通过吸入空气或注射到上结肠的非致昏迷剂量的甲硫醇，导致血清中甲硫醇混合二硫键（蛋白质-S-S-CH3和X-S-S- ，X尚未知）的浓度升高，以及尿液中（X-S-S- ）的浓度升高。甲硫醇混合二硫键的浓度被证明是接触甲硫醇的相对衡量指标。在通过结肠接触非致昏迷剂量的甲硫醇的大鼠呼出的空气中，挥发性硫化物甲硫醇、二甲基硫化物和二甲基二硫化物的水平也有所升高。由肝脏缺血引起的急性肝性脑病的大鼠在通过结肠或吸入空气接触甲硫醇的挑战下，也显示出甲硫醇混合二硫键水平的升高，但升高程度显著小于相应的假手术大鼠。这表明肝脏至少部分负责甲硫醇混合二硫键的形成。与正常大鼠相比，在甲硫醇暴露下，缺血肝脏的大鼠没有观察到额外的毒性效应，这表明肝脏在甲硫醇解毒过程中并不发挥重要作用。例如，血液将甲硫醇代谢为硫酸盐可能更为重要。在由肝脏缺血引起的急性肝性脑病的大鼠和患有慢性肝病导致的肝性脑病的狗中，测量到了大量的氨水平显著升高。然而，肝性脑病大鼠和狗的甲硫醇混合二硫键的平均水平与这些动物的正常平均水平没有差异...

The metabolism of methanethiol was studied in rats. Administration of a noncomatogenic dose of methanethiol through inspired air or injection into the upper colon resulted in an elevation of the concentrations of methanethiol mixed disulfides in serum (protein--S--S--CH3 and X--S--S--CH3, X yet unknown) and in urine (X--S--S--CH3). The concentrations of methanethiol mixed disulfides proved to be a relative measure of exposure to methanethiol. The levels of volatile sulfur compounds methanethiol, dimethylsulfide and dimethyldisulfide in the air expired by rats exposed to a noncomatogenic dose of methanethiol through the colon were also elevated. Rats with acute hepatic encephalopathy caused by liver ischemia also showed elevation of methanethiol mixed disulfide levels on challenge of methanethiol through the colon or inspired air, but to a significantly smaller extent than did the corresponding sham-operated rats. This suggests that the liver is at least partly responsible for formation of methanethiol mixed disulfides. No additional toxic effects were observed in the rats with ischemic livers on methanethiol exposition when compared with normal rats, suggesting that the liver does not play an essential role in methanethiol detoxification. Metabolism of methanethiol by blood to sulfate, for example, might be more important. In rats with acute hepatic encephalopathy caused by liver ischemia and in dogs suffering from hepatic encephalopathy resulting from chronic liver disease, large and significant increases in ammonia levels were measured. However, the mean levels of methanethiol mixed disulfides in rats and dogs with hepatic encephalopathy were not different from the mean normal levels in these animals. ...

来源:Hazardous Substances Data Bank (HSDB)

代谢

甲硫醇通过氧化代谢成二硫化物，如二甲基硫醚，或硫酸盐；通过甲基化代谢成二甲基硫醚；通过乙酰化代谢成硫醇酯；以及通过葡萄糖苷酸化代谢成硫葡萄糖苷酸酯。

/Methanethiol/ is metabolized by oxidation to disulfides such as dimethyl disulfide or to sulfate, methylation to dimethyl sulfide, acetylation to thiolesters, and glucuronylation to thioglucuronides.

来源:Hazardous Substances Data Bank (HSDB)

代谢

硫醇可能会发生甲基化反应，形成甲基烷基硫化物，这些硫化物会被氧化成相应的磺酰化合物。然而，这些含硫化合物最终大多数会被代谢成硫酸盐。

Mercaptans ... may undergo methylation to form methyl alkyl sulfides, which are oxidized to the corresponding sulfones. However, most of these sulfur compounds are eventually metabolized into sulfate. /Mercaptans/

来源:Hazardous Substances Data Bank (HSDB)

代谢

甲硫醇被大鼠代谢成二氧化碳和硫酸盐。硫酸盐通过尿液排出，21小时内从体内清除了94%的甲硫醇硫。氨对甲硫醇的代谢没有影响。由于辛酸酯或肝脏坏死而昏迷的大鼠在尿液中排出的硫酸盐很少。

Methyl mercaptan was metabolized to carbon dioxide and sulfate by rats. The sulfate was excreted in the urine and 94% of the sulfur of methanethiol was removed from the body within 21 hr. Ammonia had no effect on methanethiol metabolism. Rats in a coma from octanoate or due to heptic necrosis excreted little sulfate in the urine.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 暴露途径

这种物质可以通过吸入被身体吸收。

The substance can be absorbed into the body by inhalation.

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

毒理性

• 暴露途径

吸入，皮肤和/或眼睛接触（液体）

inhalation, skin and/or eye contact (liquid)

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；麻醉；发绀；抽搐；液体：冻伤

irritation eyes, skin, respiratory system; narcosis; cyanosis; convulsions; liquid: frostbite

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

毒理性

• 吸入症状

咳嗽。喉咙痛。眩晕。头痛。恶心。呕吐。昏迷。

Cough. Sore throat. Dizziness. Headache. Nausea. Vomiting. Unconsciousness.

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

毒理性

• 皮肤症状

接触液体时：冻伤。

ON CONTACT WITH LIQUID: FROSTBITE.

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

吸收、分配和排泄

甲基硫醇在食用芦笋后一小时内出现在尿液中。

Methyl mercaptan appears in urine within an hour after eating asparagus.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

硫化氢或任何其他挥发性硫代谢物在给予小鼠腹膜内注射硫化钠的呼出气体中均未被发现，剂量高达LD50。检测系统对给定剂量中不到0.1%的硫敏感。腹膜内给药二甲基二硫化物导致小鼠呼出气体中出现该物质，以及更小量的甲硫醇和二甲基硫化物。腹膜内给药甲硫醇导致其通过肺部排出，以及二甲基硫化物的排出。...先用乙酸铵预处理小鼠，然后注射二甲基二硫化物，通过肺部排出上述同样的三种化合物，但它们的出现比例和时间顺序发生了复杂的变化。三种化合物的绝对量都有所增加，每种化合物的排出峰值都有所延迟。特别是作为二甲基硫化物排出的量显著增加。

Neither hydrogen sulfide nor any other volatile sulfur metabolites were found in the expired breath of mice given sodium sulfide intraperitoneally in doses up to the LD50. The detection system was sensitive to less than 0.1% of the sulfur in the given dose. The intraperitoneal administration of dimethyl disulfide resulted in its appearance in the expired breath of mice as well as much smaller amounts of both methanethiol and dimethyl sulfide. The intraperitoneal administration of methanethiol resulted in its pulmonary excretion as well as that of dimethyl sulfide. ... Mice pretreated with ammonium acetate and then injected with dimethyl disulfide excreted the same three compounds via the lungs as above, but there were complex changes in the proportions and in the time sequence of their appearance. The absolute amounts of all three were increased, and the peak excretion for each was delayed. The amount excreted as dimethyl sulfide was particularly increased.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在向小鼠腹腔注射甲硫醇后，未改变的母体和其代谢物二甲基硫醚出现在呼出的气体中。在大鼠腹腔注射放射性甲硫醇6小时后，23%的放射性物质与血浆蛋白相关，较少的量在肝脏（18%）、肠道（17%）、肺（12%）、肾脏（11%）、脾脏（10%）和睾丸（9%）中找到。注射的甲硫醇在红细胞中没有发现放射性，这一发现与其在红细胞内快速氧化形成甲酸盐和硫酸盐一致，这些物质最终出现在尿液中。在大鼠尿液中排出的量中，94%以硫酸盐形式存在。

Following intraperitoneal injection of methyl mercaptan in mice, the unchanged parent and its metabolite, dimethyl sulfide, appeared in exhaled air. By 6 hours after parenteral injection of radioactive methyl mercaptan in rats, 23% of the radioactivity was associated with plasma protein, with lesser amounts found in liver (18%), intestine (17%), lungs (12%), kidney (11%), spleen (10%), and testes (9%). No radioactivity from the injected methyl mercaptan was found in erythrocytes,a finding consistent with its rapid intraerythrocytic oxidation to formate and sulfate, which ultimately appeared in the urine. Of the amount eliminated in rat urine, 94% was present as the sulfate. ...

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

它主要通过吸入方式被引入哺乳动物系统。皮肤和眼睛吸收较少。气体通过呼吸系统迅速吸收并直接转移到血管系统。甲硫醇与蛋白质和红细胞结合，对稳定红细胞膜以防止低渗性溶血非常有效。该化合物直接与胶原蛋白反应。甲硫醇可以通过作为甲基、硫或甲基硫供体来代谢，用于合成氨基酸和蛋白质。该化合物容易被氧化成二氧化碳和无机硫酸盐。给雄性大鼠注射放射性标记物质后，大约有40%的剂量在给药后6小时内以二氧化碳的形式通过呼出气排出，首小时内以未变化的硫醇形式排出的占6%。在8小时内的尿液排出约占总给药量的30%。在血浆蛋白、肝脏、肾脏、肺、脾脏和睾丸中的组织水平值得注意。

It is introduced exogenously into the mammalian system primarily by inhalation. Skin and eye absorption are minimal. The gas is absorbed rapidly through the respiratory system and directly translocated to the vascular system. Methyl mercaptan binds to protein and erythrocytes and is extremely effective in stabilizing erythrocyte membranes against hypotonic hemolysis. The compound reacts directly with collagen. Methyl mercaptan can be metabolized by serving as a methyl, sulfur, or methylthio donor for the synthesizing amino acids and proteins. The compound is readily oxidized to carbon dioxide and inorganic sulfates. Ip admin of radiolabeled materials to male rats resulted in approx 40% excretion as carbon dioxide in expired air within 6 hr of admin, and 6% in expired air as unchanged mercaptan in the first hr. Urinary excretion over an 8-hr period accounted for approx 30% of the admin dose. Tissue levels were notable in plasma protein, liver, kidney, lung, spleen, and testis.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

大约40%的甲基巯醇（MM）以二氧化碳的形式排出，而30%的MM以硫酸盐的形式通过尿液排出。

About 40% /methyl mercaptan (MM)/ is excreted as /carbon dioxide/ and 30% MM in the urine as sulfates.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 职业暴露限值：
  Ceiling: 0.5 ppm (1 mg/m3) [15-minute]
• 危险等级：
  2.3
• 立即威胁生命和健康浓度：
  150 ppm
• 危险品标志：
  T,F+,N
• 安全说明：
  S16,S25,S60,S61
• 危险类别码：
  R12
• WGK Germany：
  3
• 危险品运输编号：
  UN 2037 2.3
• 海关编码：
  2931909090
• 危险类别：
  2.3
• RTECS号：
  PB4375000
• 包装等级：
  O52
• 危险标志：
  GHS02,GHS06,GHS09
• 危险性描述：
  H220,H280,H331,H410
• 危险性防范说明：
  P210,P261,P273,P311,P410 + P403,P501
• 储存条件：
  储存注意事项： - 储存于阴凉、通风的专用库房中。 - 远离火种、热源，库温不宜超过30℃。 - 保持容器密封。 - 应与氧化剂、酸类、卤素分开存放，切忌混储。 - 使用防爆型照明和通风设施，禁止使用易产生火花的机械设备和工具。 - 储区应备有泄漏应急处理设备。

SDS

第一部分：化学品名称

制备方法与用途

甲硫醇是一种重要的有机化合物，具有广泛的应用领域。以下是关于甲硫醇的一些关键信息：

物理化学性质

• 外观与形态：常温下为无色易燃气体（低温下为无色液体）。
• 溶解性：微溶于水；易溶于醇、醚、石油醚等有机溶剂中。

用途

1. 农药生产：

   • 杀虫剂的中间体，如灭多威、涕灭威、氯硫磷、久效威、杀线威、倍硫磷、硫双灭多威等。
   • 除草剂西草净、扑草净、莠灭净、敌草净、特丁净等。

2. 医药制品：

   • 生产蛋氨酸等重要药物成分。

3. 有机合成：

   • 合成染料、农药、医药产品，如苄菊酯、丙虫磷、扑草净等。
   • 作为甲烷磺酰氯和甲硫基丙醇的中间体。

制备方法

1. 气相合成法：以活性氧化铝为主催化剂，由甲醇与硫化氢在280～450℃，0.74～0.25MPa条件下进行气相反应。
2. 卤代烃与硫氢化物反应：
   • 使用氯甲烷和硫氢化钠反应得到甲硫醇。

安全信息

• 毒性分级：高毒
• 急性毒性：吸入LC50（大鼠）675 PPM；小鼠 6.53 毫克/立方米/2小时。
• 火灾与爆炸危险性：
  • 遇明火、高温、氧化剂易燃，燃烧产生有毒硫氧化物烟雾；
  • 遇水、酸生成有毒、易燃气体（硫化氢）。

储存运输

• 应库房通风低温干燥；
• 与氧化剂和酸类分开存放。

以上信息总结了甲硫醇的基本性质及其在工业中的应用。由于其高毒性和可燃性，处理时应特别小心并遵循安全操作规程。

反应信息

• 作为反应物：
  描述：

  甲硫醇 在 吡啶 、 盐酸 、 potassium fluoride 、 水 作用下， 以 乙腈 为溶剂， 反应 15.0h， 以51%的产率得到甲基磺酰氟
  参考文献：
  名称：

  硫醇和氟化钾电化学氧化偶联合成磺酰氟

  摘要：

  磺酰氟是具有多种应用价值的合成基序，其中基于硫 (VI) 氟化物交换的“点击化学”是目前最突出的。因此，开发新的和有效的合成方法来访问这些官能团是非常有趣的。在此，我们报告了一种温和且环境友好的电化学方法，使用硫醇或二硫化物作为广泛可用的起始材料，结合 KF 作为廉价、丰富和安全的氟化物来源来制备磺酰氟。不需要额外的氧化剂或额外的催化剂，由于反应条件温和，反应显示出广泛的底物范围，包括各种烷基、苄基、芳基和杂芳基硫醇或二硫化物。

  DOI：

  10.1021/jacs.9b06126
• 作为产物：
  描述：

  氯甲烷 在 mercapto radical 作用下， 以 gas 为溶剂， 生成 甲硫醇
  参考文献：
  名称：

  卤代烷的气相SN2和E2反应

  摘要：

  已测量甲基、乙基、正丙基、异丙基、叔丁基和新戊基氯化物和溴化物与以下亲核试剂的气相反应的速率系数，按碱度递减的顺序列出：HO - 、CH 3 O - 、F - 、HO - (H 2 O)、CF 3 CH 2 O - 、H 2 NS - 、C 2 F 5 CH 2 O - 、HS - 和Cl - 。对于氯甲烷，反应效率首先显着低于 1，以 HO - (H 2 O) 作为亲核试剂，而对于甲基溴，以 HS - 作为亲核试剂；在这两种情况下，总反应放热度约为 30 kcal mol -1 。这些卤化物与强碱反应缓慢的早期结论被证明是错误的。在速率较慢的区域，氧阴离子通过消除与烷基氯化物和溴化物反应，而相同碱度的硫阴离子通过取代反应。这种差异是由于硫碱的消除速度减慢；与相同碱度的氧阴离子相比，硫阴离子没有增加亲核性

  DOI：

  10.1021/ja00180a003
• 作为试剂：
  描述：

  秋水仙碱 在 甲硫醇 、 对甲苯磺酸 作用下， 以80%的产率得到硫代秋水仙碱
  参考文献：
  名称：

  Photochemical Isomerization of Colchicine and Thiocolchicine

  摘要：

  The photochemical reactivity of colchicine and thiocolchicine is described. Although the irradiation of colchicine gave a well-known transposition reaction to beta- and gamma-lumicolchicines, thiocolchicine did not react. Femtosecond transient spectroscopy of colchicine showed a strong band with maximum at 510 nm appearing at tau = 0. It disappeared within few hundred femtoseconds, leaving a broad structureless band with a maximum around 470 urn. A second band is observed around 410 nm. The analysis in time showed that the 510-nm component appeared instantaneously and decayed following a biexponential low with time constants of 300 +/- 100 fs and 40 ps. The kinetics at 420 nm has a measurable rise lime of 300 +/- 150 fs. Quantum mechanical calculations on colchicine showed that this absorption is due to a S-1 --> S-11 transition. In thiocolchicine, the instantaneous formation of a structure with maxima out of the investigated spectral region was observed. A strong absorption around 650 nm indicated the presence of a band with a maximum at longer wavelengths (> 700 nm) and a peak around 380 nm, which partially coincides with the ground-state absorption and therefore strongly affected absorption around 650 nm and its rapid (similar to500 fs) decay by its bleaching. The instantaneous formation of an absorption was observed. At shorter wavelengths (400 nm), the t decay was fitted with a biexponential curve with the first time constant of about 80 ps. The second part of,the decay had a very long tail up to 500 ps. Transient spectroscopy and configuration interaction calculations are in agreement with a mechanism involving a disrotatory cyclization of colchicine in its first excited singlet state. The lack of reactivity observed in thiocolchicine was explained by considering the presence of efficient ISC to the triplet state.

  DOI：

  10.1021/jp035507l

文献信息

• [EN] NOVEL COMPOUNDS AND PHARMACEUTICAL COMPOSITIONS THEREOF FOR THE TREATMENT OF INFLAMMATORY DISORDERS<br/>[FR] NOUVEAUX COMPOSÉS ET COMPOSITIONS PHARMACEUTIQUES LES COMPRENANT POUR LE TRAITEMENT DE TROUBLES INFLAMMATOIRES
  申请人：GALAPAGOS NV

  公开号：WO2017012647A1

  公开（公告）日：2017-01-26

  The present invention discloses compounds according to Formula (I), wherein R1, R3, R4, R5, L1, and Cy are as defined herein. The present invention also provides compounds, methods for the production of said compounds of the invention, pharmaceutical compositions comprising the same and their use in allergic or inflammatory conditions, autoimmune diseases, proliferative diseases, transplantation rejection, diseases involving impairment of cartilage turnover, congenital cartilage malformations, and/or diseases associated with hypersecretion of IL6 and/or interferons. The present invention also methods for the prevention and/or treatment of the aforementioned diseases by administering a compound of the invention.

  本发明公开了根据式（I）的化合物，其中R1、R3、R4、R5、L1和Cy如本文所定义。本发明还提供了该发明的化合物、制备该化合物的方法、包括相同化合物的药物组合物以及它们在过敏或炎症症状、自身免疫疾病、增殖性疾病、移植排斥、涉及软骨周转障碍的疾病、先天软骨畸形和/或与IL6和/或干扰素过度分泌相关的疾病中的使用。本发明还提供了通过给予该发明的化合物来预防和/或治疗上述疾病的方法。
• SYNTHESIS OF THIOHYDROXIMATES THE ADDITION OF THIOLS TO NITRILE OXIDES
  作者：M. H. Benn

  DOI：10.1139/v64-352

  日期：1964.11.1

  The addition of thiols to nitrile oxides is shown to constitute a general synthesis of thiohydroximates.

  向腈氧化物添加硫醇被证明构成了硫代羟基肟酸盐的一般合成。
• Geometrical isomerism in the S-alkyl thiohydroximate series: a new oxime fragmentation
  作者：J. H. Davies、R. H. Davis、P. Kirby

  DOI：10.1039/j39680000431

  日期：——

  S-alkyl thiohydroximates from the results of Beckmann rearrangements on both geometrical isomers. The anti-(alkylthio)-isomers undergo fragmentation under Beckmann conditions. The syn-(alkylthio)-isomers may be converted to the anti-isomers by irradiation with u.v. light. Other evidence concerning the geometry of this series of compounds is discussed.

  根据两个几何异构体上贝克曼重排的结果，已将顺式（烷硫基）-构型分配给了S-烷基硫代氢氧肟酸酯的热力学稳定形式。的抗- （烷硫基） -异构体贝克曼条件下经受碎裂。的顺式- （烷硫基） -异构体可以被转换到反通过用UV光照射-异构体。讨论了有关这一系列化合物的几何形状的其他证据。
• New Antifungal 1,2,4-Triazoles with Difluoro(substituted sulfonyl)methyl Moiety.
  作者：Hiromichi ETO、Yasushi KANEKO、Sunao TAKEDA、Minoru TOKIZAWA、Susumu SATO、Kouiti YOSHIDA、Setsuo NAMIKI、Masaki OGAWA、Kazuki MAEBASHI、Kazuya ISHIDA、Masaru MATSUMOTO、Takemitsu ASAOKA

  DOI：10.1248/cpb.49.173

  日期：——

  New 1, 2, 4-triazoles (2) having a difluoro(substituted sulfonyl)methyl moiety were designed and synthesized via α, α-difluoro-α-(substituted thio)acetophenones (3). Compounds (2) showed potent antifungal activities against C. albicans, C. krusei, A. flavus and A. fumigatus in vitro and against C. albicans in vivo for oral and i.v. administrations. Especially, (−)-2a, (−)-2b and (−)-2d showed potent antifungal activities.

  新型的1, 2, 4-三氮唑衍生物（2），其结构中含有一个二氟（取代磺酰基）甲基，通过α, α-二氟-α-（取代硫基）苯乙酮（3）的设计与合成得以实现。化合物（2）在体外展现出对白色念珠菌、克鲁斯念珠菌、黄曲霉和烟曲霉的强效抗真菌活性，并且在体内对于口服和静脉注射途径的白色念珠菌也表现出显著的抗真菌作用。特别是（−）-2a、（−）-2b和（−）-2d显示出强大的抗真菌活性。
• Synthesis and reactions of xanthate and thioxanthate carbonyl complexes of molybdenum and tungsten
  作者：Walter K. Dean、Barbara L. Heyl

  DOI：10.1016/s0022-328x(00)82316-5

  日期：1978.10

  A series of complexes CpM(CO)nS2CX (M = Mo, W; n = 2, 3; X = OR, SR; R = Me, Et) has been prepared by the reaction of xanthates and thioxanthates with CpM(CO)3Cl. The dicarbonyl compounds are the exclusive products after sufficiently long reaction times and are produced at least partially through the tricarbonyl species as intermediates. The conversion of CpM(CO)2S2CX to CpM(CO)2S3CX is not a simple

  通过黄药和硫代黄药与CPM（）的反应制备了一系列配合物CPM（CO）n S 2 CX（M = Mo，W; n = 2，3; X = OR，SR; R = Me，Et） CO）3 Cl。二羰基化合物是经过足够长的反应时间后的排他产物，并且至少部分地通过三羰基物质作为中间体生产。CPM（CO）的转化率2小号2 CX至CPM（CO）2小号3 CX不是一个简单的一阶过程，但由氯催化-和/或S 2 CX -。三羰基物质可在未配位的硫原子上烷基化，得到离子型二硫代或三硫代碳酸盐络合物。

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