1,2-二乙烷 | 3563-36-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 中文名称: 1,2-二乙烷
• 中文别名: 2-氯乙硫基乙烷
• 英文名称: 1,2-bis(2-chloroethylthio)ethane
• 英文别名: 1,8-dichloro-3,6-dithiaoctane；Sesquimustard；1,2-bis(2-chloroethylsulfanyl)ethane
• CAS: 3563-36-8
• 化学式: C₆H₁₂Cl₂S₂
• 分子量: 219.199
• InChiKey: AMGNHZVUZWILSB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  10
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

ADMET

代谢

混合气体和氧化芥子气对军事力量和平民构成了重大威胁，因为它们是有效的起泡剂。我们开发了一种同位素稀释高效液相色谱-大气压化学电离-串联质谱法，利用负离子多反应监测分析混合芥子气代谢物双（2-羟基乙硫基）烷烃（n = 1-5）和氧化芥子气代谢物双（2-羟基乙硫基乙基）醚在人类尿液中的含量。相对标准偏差小于10%，报告的检测限为0.5毫升尿液中1纳克/毫升。我们将这种方法应用于从没有已知接触混合气体或氧化芥子气的个体收集的100个样本，没有任何尿液显示出可检测到任何分析物的水平，这表明这些代谢物可能用于监测对混合气体和氧化芥子气的暴露。

Sesqui- and oxy-mustards pose a significant threat to military forces and civilians because they are potent vesicants. We have developed an isotope-dilution high-performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry method utilizing negative ion multiple reaction monitoring for the analysis of sesqui-mustard metabolites bis(2-hydroxyethylthio)alkanes (n = 1-5) and oxy-mustard metabolite bis(2-hydroxyethylthioethyl)ether in human urine. Relative standard deviations were < 10% and the reportable limits of detection were 1 ng/mL in 0.5 mL of urine. We applied this method to 100 samples collected from individuals with no known exposure to sesqui- or oxy-mustards, and no urines showed detectable levels of any of the analytes, suggesting that these metabolites may be used for monitoring exposure to sesqui- and oxy-mustards.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

识别和使用： sesquimustard（Q）是一种比纯芥子气（HD）更强的发疱剂/糜烂剂。 与HD结合形成代理HQ。 在HD的吨容器储存过程中，也可能以少量形成。 人体研究：发疱剂，也被称为“糜烂剂”，是一战期间最常见的化学战剂。 最可能的接触途径是吸入、皮肤接触和眼睛接触。 发疱剂是高度反应性的化学品，与蛋白质、DNA和其他细胞成分结合，在接触后立即导致细胞变化。 临床效果可能在2到24小时后延迟出现。 接触后，最常见的临床效果包括皮肤（皮肤红斑和水疱）、呼吸系统（咽炎、咳嗽、呼吸困难）、眼睛（结膜炎和烧伤）和消化系统（恶心和呕吐）。 接触发疱剂的量和途径、发疱剂的类型以及接触者的病前状况将影响发病时间和疾病的严重程度。 例如，摄入发疱剂会导致比吸入接触同一剂量和类型的发疱剂更为突出的胃肠道症状。 动物研究：用sesquimustard对小鼠、大鼠、豚鼠、仓鼠、鸽子和狗进行了急性吸入毒性研究。 接触后，动物表现出体重减轻、咳嗽、呼吸困难、共济失调和腹泻，然后死亡。 在14天的观察期内死亡，主要在第三到第六天达到高峰。 大多数动物的器官损伤仅限于上呼吸道和消化道。

IDENTIFICATION AND USE: Sesquimustard (Q) is a vesicant/blister agent more potent than distilled mustard (HD). It is combined with HD to form agent HQ. It could also be formed in small amounts during storage of HD in ton containers. HUMAN STUDIES: Vesicants, also referred to as "blister agents," were the most commonly used chemical warfare agents during World War I. The most likely routes of exposure are inhalation, dermal contact, and ocular contact. Vesicants are highly reactive chemicals that combine with proteins, DNA, and other cellular components to result in cellular changes immediately after exposure. Clinical effects may be delayed for 2 to 24 hours. Following exposure, the most commonly encountered clinical effects include dermal (skin erythema and blistering), respiratory (pharyngitis, cough, dyspnea), ocular (conjunctivitis and burns), and gastrointestinal (nausea and vomiting). The amount and route of exposure to the vesicant, the type of vesicant, and the premorbid condition of the person exposed will contribute to the time of onset and the severity of illness. For example, ingestion of a vesicant leads to gastrointestinal symptoms more prominent than those that would result from inhalation exposure to the same dose and type of vesicant. ANIMAL STUDIES: Acute inhalation toxicity studies with sesquimustard have been made in mice, rats, guinea pigs, hamsters, pigeons, and dogs. Following exposure, animals show loss of body weight, coughing, dyspnea, ataxia, and diarrhea prior to death. Deaths occurred over a 14-day observation period with a primary peak between the third and sixth day. Tissue damage in most animals was limited to the upper respiratory tract and digestive tract.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 立即急救：确保已经进行了充分的中和。如果患者停止呼吸，请开始人工呼吸，最好使用需求阀复苏器、袋阀面罩装置或口袋面罩，按训练操作。如有必要，执行心肺复苏。立即用缓慢流动的水冲洗受污染的眼睛。不要催吐。如果发生呕吐，让患者前倾或将其置于左侧（如果可能的话，头部向下）以保持呼吸道畅通，防止吸入。保持患者安静，维持正常体温。寻求医疗帮助。 /糜烂性毒剂（发疱剂）/

/SRP:/ Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR as necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Blister Agents (Vesicants)/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 基本治疗：建立专利气道（如有需要，使用口咽或鼻咽气道）。如有必要，进行吸痰。可能需要积极控制气道。观察呼吸不足的迹象，如有必要，协助通气。通过非循环呼吸面罩以10至15升/分钟的速度给予氧气。监测肺水肿，如有必要，进行治疗……。监测休克，如有必要，进行治疗……。预期可能出现癫痫，如有必要，进行治疗……。对于眼睛污染，立即用水冲洗眼睛。在转运过程中，用0.9%的生理盐水（NS）连续冲洗每只眼睛……。/糜烂性毒剂（发疱剂）/

/SRP:/ Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Aggressive airway control may be needed. Watch for signs of respiratory insufficiency and assist ventilations it necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . /Blister Agents (Vesicants)/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 高级治疗：对于失去意识或严重呼吸困难的病人，考虑进行口咽或鼻咽插管以控制气道。在上呼吸道阻塞的第一个迹象出现时，可能需要早期插管。使用气囊面罩装置的正压通气技术可能有益。监测心率和必要时治疗心律失常...开始静脉输注5%葡萄糖（D5W）/SRP: "保持开放"，最低流速/。如果出现低血容量的迹象，使用0.9%盐水（NS）或乳酸钠林格氏液（LR）。对于伴有低血容量迹象的低血压，谨慎给予液体。如果病人在正常血容量下出现低血压，考虑使用血管加压药。注意液体过载的迹象...用地西泮（安定）或劳拉西泮（安定文）治疗癫痫...使用丙美卡因氢氯化物协助眼部冲洗.../糜烂性毒剂（发泡剂）/

/SRP:/ Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious or is in severe respiratory distress. Early intubation at the first sign of upper airway obstruction may be necessary. Positive-pressure ventilation techniques with a bag-valve-mask device may be beneficial. Monitor cardiac rhythm and treat arrhythmias as necessary ... . Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's (LR) if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Consider vasopressors if patient is hypotensive with a normal fluid volume. Watch for signs of fluid overload ... . Treat seizures with diazepam (Valium) or lorazepam (Ativan) ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Blister Agents (Vesicants)/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

/症状和体征/ 腐蚀剂，也被称为“疱剂”，是一战中使用最普遍的化学战剂。暴露的最可能途径是吸入、皮肤接触和眼睛接触。腐蚀剂是与蛋白质、DNA和其他细胞成分反应性极高的化学物质，在暴露后立即导致细胞变化。根据腐蚀剂的种类，临床效果可能立即出现（如光气亚砜或路易斯毒剂）或者可能在2到24小时后延迟出现（如芥子气）。暴露后，最常见的临床效果包括皮肤（皮肤红斑和水疱）、呼吸系统（咽炎、咳嗽、呼吸困难）、眼睛（结膜炎和烧伤）和消化系统（恶心和呕吐）。暴露于腐蚀剂的量和途径、腐蚀剂的类型以及暴露者的原先健康状况将影响病情发作的时间和严重程度。例如，摄入腐蚀剂会导致比吸入同一剂量和类型的腐蚀剂更突出的胃肠道症状。/腐蚀剂/

/SIGNS AND SYMPTOMS/ Vesicants, also referred to as "blister agents," were the most commonly used chemical warfare agents during World War I. The most likely routes of exposure are inhalation, dermal contact, and ocular contact. Vesicants are highly reactive chemicals that combine with proteins, DNA, and other cellular components to result in cellular changes immediately after exposure. Depending on the vesicant, clinical effects may occur immediately (as with phosgene oxime or lewisite) or may be delayed for 2 to 24 hours (as with mustards). Following exposure, the most commonly encountered clinical effects include dermal (skin erythema and blistering), respiratory (pharyngitis, cough, dyspnea), ocular (conjunctivitis and burns), and gastrointestinal (nausea and vomiting). The amount and route of exposure to the vesicant, the type of vesicant, and the premorbid condition of the person exposed will contribute to the time of onset and the severity of illness. For example, ingestion of a vesicant leads to gastrointestinal symptoms more prominent than those that would result from inhalation exposure to the same dose and type of vesicant. /Vesicants/

来源:Hazardous Substances Data Bank (HSDB)

反应信息

• 作为反应物：
  描述：

  1,2-二乙烷 在 disodium telluride 作用下， 以 四氢呋喃 、 氨 为溶剂， 生成 1,4-Dithia-7-telluracyclononane
  参考文献：
  名称：

  Synthesis and properties of the first series of mixed thioether/telluroether macrocycles

  摘要：

  本文介绍了通过 "变相稀释 "方法制备硫醚/四氢醚混合大环的第一个实例：[9]aneS2Te（1,4-二硫杂-7-碲基十四烷）、[11]aneS2Te（1,4-二硫杂-8-碲基十四烷）、[12]aneS2Te（1,5-二硫杂-9-碲基十四烷）和[14]aneS3Te（1、和[14]aneS3Te（1,4,7-三硫杂-11-碲基十四烷）的晶体结构，同时还描述了[Ag([11]aneS2Te)]BF4 的晶体结构。

  DOI：

  10.1039/b008370o
• 作为产物：
  描述：

  3,6-二硫杂-1,8-辛二醇 在 氯化亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以91%的产率得到1,2-二乙烷
  参考文献：
  名称：

  长链硫芥末降解过程中导致硫代二甘醇的意外反应途径

  摘要：

  用各种商业净化剂降解长链硫芥末，通过未报告的反应途径意外地形成了硫二甘醇（TDG）。化学战剂（CWA）降解产物必须与其参考化合物明确相关，才能实现国际验证协议。因此，使用水基去污剂形成TDG会导致该化学物质来源的不确定性，该不确定性已系统地用于明确证明环境和生物医学样品中存在钇铁矿。因此，这些新颖而空前的降解途径将导致出于法医目的对国际验证协议的修改，或者将TDG排除为堇青石的唯一标记。

  DOI：

  10.1021/acs.joc.8b01670

文献信息

• Mass Spectral Studies on Vinylic Degradation Products of Sulfur Mustards under Gas Chromatography/Mass Spectrometry Conditions
  作者：L. Sai Sachin、R. Karthikraj、K. Kalyan Kumar、T. Sony、N. Prasada Raju、S. Prabhakar

  DOI：10.1255/ejms.1398

  日期：2015.12

  Sulfur mustards are a class of vesicant chemical warfare agents that rapidly degrade in environmental samples. The most feasible degradation products of sulfur mustards are chloroethyl vinylic compounds and divinylic compounds, which are formed by the elimination of one and two HCl molecules from sulfur mustards, respectively. The detection and characterization of these degradation products in environmental samples are an important proof for the verification of sulfur mustard usage. In this study, we synthesized a set of sulfur mustard degradation products, i.e., divinylic compounds (1–7) and chloroethyl vinylic compounds (8–14), and characterized using gas chromatography/mass spectrometry (GC/MS) under electron ionization (EI) and chemical ionization (CI) (methane) conditions. The EI mass spectra of the studied compounds mainly included the fragment ions that resulted from homolytic cleavages with or without hydrogen migrations. The divinylic compounds (1–7) showed [M – SH]⁺ ions, whereas the chloroethylvinyl compounds (8–14) showed [M – Cl]⁺ and [M – CH₂CH₂Cl]⁺ ions. Methane/CI mass spectra showed [M + H]⁺ ions and provided molecular weight information. The GC retention index (RI) values were also calculated for the studied compounds. The EI and CI mass spectral data together with RI values are extremely useful for off-site analysis for the verification of the chemical weapons convention and also to participate in official Organization for the Prohibition of Chemical Weapons proficiency tests.

  硫芥子是一类气泡剂化学战剂，它们在环境样品中迅速降解。硫芥子最可行的降解产物是氯乙基乙烯化合物和二乙烯化合物，它们分别通过从硫芥子中消除一个和两个HCl分子形成。在环境样品中检测和表征这些降解产物对于验证硫芥子的使用是重要的证据。在这项研究中，我们合成了一组硫芥子降解产物，即二乙烯化合物（1-7）和氯乙基乙烯化合物（8-14），并使用气相色谱/质谱联用（GC/MS）在电子电离（EI）和化学电离（CI）（甲烷）条件下进行表征。研究化合物的EI质谱主要包括由于有或无氢迁移而导致的自由裂解的碎片离子。二乙烯化合物（1-7）显示[M - SH]⁺离子，而氯乙基乙烯化合物（8-14）显示[M - Cl]⁺和[M - CH₂CH₂Cl]⁺离子。甲烷/CI质谱显示[M + H]⁺离子并提供分子量信息。还计算了研究化合物的GC保留指数（RI）值。EI和CI质谱数据以及RI值对于离线分析以验证化学武器公约以及参加官方禁化武组织的熟练测试非常有用。
• [EN] VITAMIN D RECEPTOR MODULATORS<br/>[FR] MODULATEURS DE RECEPTEUR DE VITAMINE D
  申请人：LILLY CO ELI

  公开号：WO2004048309A1

  公开（公告）日：2004-06-10

  The present invention relates to novel, non-secosteroidal, diaryl compounds with vitamin D receptor (VDR) modulating activity that are less hypercalcemic than 1a,25 dihydroxy vitamin D3. These compounds are useful for treating bone disease and psoriasis.

  本发明涉及一种新颖的、非类固醇的、二芳基化合物，具有维生素D受体（VDR）调节活性，比1a,25二羟基维生素D3更少引起高钙血症。这些化合物可用于治疗骨疾病和牛皮癣。
• THERMAL DEGRADATION OF BIS (2-CHLOROETHYL) SULFIDE (MUSTARD GAS)
  作者：George W. Wagner、Brian K. Maciver、Dennis K. Rohrbaugh、Yu-Chu Yang

  DOI：10.1080/10426509908031618

  日期：1999.9.1

  Abstract The thermal degradation of mustard gas (ClCH2CH2SCH2CH2Cl, “HD”), with and without 5% added water, is examined. GC/MS, LC/MS and NMR were employed to comprehensively analyze the products. After 75 days at 90°C, 91% HD remains (80% with 5% water). After 40 days at 140°C, 30% HD remains (24% with 5% water) and black “tar” precipitates form. The apparent Ea is 22.4 kcal/mol. Major products include

  摘要 研究了芥子气（ClCH2CH2SCH2CH2Cl，“HD”）在添加和不添加 5% 水的情况下的热降解。采用GC/MS、LC/MS和NMR对产物进行综合分析。在 90°C 下 75 天后，仍有 91% 的 HD（80% 与 5% 的水）。在 140°C 下 40 天后，仍有 30% 的 HD（24% 与 5% 水）并形成黑色“焦油”沉淀物。表观 Ea 为 22.4 kcal/mol。主要产品包括Q（ClCH2CH2SCH2CH2SCH2Cl）、1,2-二氯乙烷、多硫化物和1,4-二噻烷。使用 5% 的水，会产生 1,4-噻烷和 2-氯乙醇等含氧化合物以及许多锍离子，包括 S-(2-氯乙基)-1,4-二噻鎓，这是“芥末脚跟”的主要成分。由于在这些温度下反应的平衡性质，分解不会完全。
• Vesicant treatment with phenyl-phenyl type vitamin d receptor modulators
  申请人：Nagpal Sunil

  公开号：US20060094778A1

  公开（公告）日：2006-05-04

  The present invention relates to a method of treating or preventing damage to human skin cells by chemical vesicants by administering a non-secosteroidal, diphenyl compound with vitamin D receptor (VDR) modulating activity.

  本发明涉及一种通过给予一种具有维生素D受体（VDR）调节活性的非类固醇二苯基化合物来治疗或预防化学性水疱剂对人体皮肤细胞的损伤的方法。
• [EN] VITAMIN D RECEPTOR MODULATORS<br/>[FR] MODULATEURS DE RECEPTEUR DE LA VITAMINE D
  申请人：LILLY CO ELI

  公开号：WO2005051938A1

  公开（公告）日：2005-06-09

  The present invention relates to novel, non-secosteroidal, phenyl-benzofuran compounds with vitamin D receptor (VDR) modulating activity that are less hypercalcemic than 1α,25 dihydroxy vitamin D3. These compounds are useful for treating bone disease and psoriasis.

  本发明涉及一种新颖的非类固醇、苯基-苯并呋喃化合物，具有维生素D受体（VDR）调节活性，比1α,25二羟基维生素D3更少引起高钙血症。这些化合物可用于治疗骨疾病和牛皮癣。

表征谱图