甲基硫代膦酰二氯 | 676-99-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 中文名称: 甲基硫代膦酰二氯
• 英文名称: methylphosphonyl difluoride
• 英文别名: Methylphosphonic difluoride；difluorophosphorylmethane
• CAS: 676-99-3
• 化学式: CH₃F₂OP
• 分子量: 100.005
• InChiKey: PQIOSYKVBBWRRI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  5
• 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：
  17.1
• 氢给体数：
  0
• 氢受体数：
  3

ADMET

毒理性

• 毒性数据

LCLo（大鼠）= 1,842 毫克/立方米/30分钟

LCLo (rat) = 1,842 mg/m3/30min

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

毒理性

• 解毒与急救

/SRP:/ 立即急救：确保已经进行了充分的中毒物清除。如果患者停止呼吸，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。根据需要执行心肺复苏。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卧位（如果可能的话，头部向下）以保持呼吸道畅通，防止吸入性肺炎。保持患者安静，维持正常体温。寻求医疗救助。 /神经毒剂/

/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. /Nerve Agents/

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……。/神经毒剂/

/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 ... . /Nerve Agents/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 高级治疗：对于无意识、严重肺水肿或严重呼吸困难的病人，考虑进行口咽或鼻咽气管插管以控制气道。使用气囊面罩的正压通气技术可能有益。初始通气可能困难。由于分泌物和支气管收缩，气道阻力可能较高（50至70 cm H2O）。可能需要频繁抽吸。监测心率和必要时治疗心律失常...开始静脉输注D5W /SRP: "保持开放"，最小流量/。如果出现低血容量的迹象，使用0.9%生理盐水（NS）或乳酸林格液（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时低血压，考虑使用血管加压药。注意液体过载的迹象...给予阿托品。在给药前纠正低氧血症...对于严重中毒的病人，给予氯磷定（2-PAM）。...用适量的阿托品化、纠正低氧血症和必要时使用地西泮（安定）或劳拉西泮治疗癫痫...在大规模伤亡事件中建议使用自动注射器阿托品和2-PAM。这些自动注射器被称为Mark I ket。也有自动注射器地西泮可用...。给予缩瞳剂和眼痛的homatropine滴眼液...。使用丙美卡因氢氯化物协助眼部冲洗...。/神经毒剂/

/SRP:/ Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Positive-pressure ventilation techniques with a bag-valve-mask device may be beneficial. Initial ventilation may be difficult. Airway resistance may be high (50 to 70 cm H2O) because of secretions and bronchoconstriction. Frequent suctioning may be necessary. 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 ... . Administer atropine. Correct hypoxia before administration ... . In severely poisoned patients, administer pralidoxime chloride (2-PAM). ... Treat seizures with adequate atropinization, correction of hypoxia, and diazepam (Valium) or lorazepam as necessary ... . In mass casualty events the use of auto-injector atropine and 2-PAM is advised. These auto-injectors are know as the Mark I ket. An auto-injector diazepam is also available ... . Administer homatropine drops for miosis and eye pain ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Nerve Agents/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 非人类毒性摘录

实验室动物：急性暴露/本文报告了通过二进制化学药剂前体化学品DF（甲基磷酰二氟）和QL（2-[双（1-甲基乙基）氨基]乙基乙基甲基磷酰）的水解产生的中和剂的毒性和环境影响。在回顾了中和剂混合物和成分的文献之后，进行了基本毒性测试以填补数据空白，包括急性口服和皮肤中位致死剂量测试……对于DF中和剂的主要成分甲基磷酰酸（MPA），Sprague-Dawley大鼠的急性口服LD(50)测量值为1888 mg/kg……

/LABORATORY ANIMALS: Acute Exposure/ This paper reports the toxicity and environmental impact of neutralents produced from the hydrolysis of binary chemical agent precursor chemicals DF (methylphosphonic difluoride) and QL (2-[bis(1-methylethyl)amino]ethyl ethyl methylphosphonite). Following a literature review of the neutralent mixtures and constituents, basic toxicity tests were conducted to fill data gaps, including acute oral and dermal median lethal dose assays ... . For methylphosphonic acid (MPA), a major constituent of DF neutralent, the acute oral LD(50) in the Sprague-Dawley rat was measured at 1888 mg/kg ...

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

实验大鼠通过吸入和非吸入途径暴露于碳-14标记的甲基膦酰二氟化物（difluoro）或其水解产物。暴露的大鼠被连续杀死和解剖，以便追踪放射性标记物在7天内的移动。非吸入给药后，水解产物迅速清除（半衰期小于24小时）。吸入的difluoro主要沉积在上颌窦和筛窦，清除主要通过粘液纤毛清除和吞咽。计算了与总沉积蒸气相关的difluoro与各种呼吸道组织剂量的常数。这些常数表明，鼻腔前部的上颌窦接收到的difluoro剂量比筛窦多四倍以上，而气管和肺的剂量则远低于鼻腔组织。导出的常数可能适用于计算其他不饱和粘液（例如，不可逆地与水反应）的吸入蒸气对呼吸道组织的剂量。

Rats were exposed by both inhalation and noninhalation routes to carbon-14-labeled methylphosphonic difluoride (difluoro) or its hydrolysis products. Exposed rats were serially killed and dissected so that the movement of the radiolabel could be traced over 7 days. Hydrolysis products cleared rapidly after noninhalation administration (t 1/2 <24 hr). The deposition of inhaled difluoro was mainly in the maxillo- and ethmoturbinates, and clearance was mainly by mucociliary clearance and swallowing. Constants were calculated for relating doses of difluoro to various respiratory tract tissues as a function of total deposited vapor. These constants indicate that the maxilloturbinates in the anterior of the nose receive more than four times the dose of difluoro than do the ethmoturbinates, whereas the trachea and lung receive much lower doses than do the nasal tissues. The derived constants may be applicable for calculating doses to respiratory tract tissues for other inhaled vapors that do not saturate the mucus (e.g, irreversibly react with water).

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 储存条件：
  库房应保持低温、通风和干燥，并将食品原料与其他物品分开存放。

反应信息

• 作为反应物：
  描述：

  甲基硫代膦酰二氯 在 甲基膦酸 作用下， 生成 甲基膦酰氟
  参考文献：
  名称：

  Bender,R. et al., Phosphorus and the Related Group V Elements, 1974, vol. 4, p. 183 - 186

  摘要：

  DOI：
• 作为产物：
  描述：

  甲醚 在 三氯化铝 、 氟化磷(III) 作用下， 生成 甲基硫代膦酰二氯
  参考文献：
  名称：

  Production of organic phosphonyl halide

  摘要：

  公开号：

  US02882315A1

文献信息

• A New Microscale Method for the Conversion of Phosphorus Oxyacids to Their Fluorinated Analogues, Using Cyanuric Fluoride in Solution and on Solid Support
  作者：Rikard Wärme、Lars Juhlin

  DOI：10.1080/10426501003671445

  日期：2010.11.23

  Cyanuric fluoride, in solution or loaded onto a Wang resin, is successfully used as a fluorinating agent for phosphorus oxy acids. The reaction is very efficient with high yields and easy workup procedures, thereby in general generating products in quantitative yields. The cyanuric fluoride is proven suitable for micromolar scale synthesis of analytical standards, particularly in its resin-bound form

  溶液中或负载在 Wang 树脂上的氰尿酰氟已成功用作含氧磷酸的氟化剂。该反应非常有效，产率高，后处理程序简单，因此通常以定量产率产生产物。氰尿酰氟已被证明适用于分析标准品的微摩尔级合成，特别是其树脂结合形式。
• α-Haloenamines as Reagents for the Conversion of Phosphorus Oxyacids to Their Halogenated Analogues
  作者：Rikard Norlin、Lars Juhlin、Per Lind、Lars Trogen

  DOI：10.1055/s-2005-865363

  日期：——

  Phosphorus oxyacids are converted to their halogenated analogues under mild conditions. α-Haloenamines are shown to be effective halogen transfer reagents affording good to high yields of the desir ...

  磷含氧酸在温和条件下转化为它们的卤代类似物。α-卤代烯胺被证明是有效的卤素转移试剂，可提供良好至高产率的所需...
• Verification of the Chemical Weapons Convention: Mass Spectrometry of Alkyl Methylphosphonofluoridates
  作者：VT Borrett、RJ Mathews、ER Mattsson

  DOI：10.1071/ch9942065

  日期：——

  Under the provisions of the United Nations Chemical Weapons Convention (CWC), certain parts of chemical industry will be monitored to verify compliance with the Convention. This will include analysis of samples from industrial sites to check for the presence or absence of chemical warfare related compounds. One of the problems in screening the chemicals to be monitored under the CWC is that certain classes of chemical warfare agents are represented as families of chemicals, with many of the individual chemicals having no analytical data available. One example is the alkyl methylphosphonofluoridate family with an alkyl ester substituent from CH3 to C10H21. In this work, the mass spectra of 60 alkyl methylphosphonofluoridate family members have been studied to enable the development of rapid on-site screening methods for this family of chemicals.

  根据《联合国化学武器公约》（CWC）的规定，将对化学工业的某些部分进行监测，以核查遵守公约的情况。这包括分析工业场所的样本，检查是否存在与化学战有关的化合物。根据《化学武器公约》筛选要监测的化学品时遇到的一个问题是，某些类别的化学战剂是以化学品家族的形式出现的，其中许多单个化学品没有分析数据。其中一个例子是烷基甲基膦酰氟家族，其烷基酯取代基为 CH3 至 C10H21。在这项工作中，对 60 种烷基甲基膦酰氟家族成员的质谱进行了研究，以便为这一化学品家族开发快速的现场筛选方法。
• FT-IR Analysis of the Laser-Induced Dissociation of Methylphosphonic Difluoride
  作者：Ann E. Stanley

  DOI：10.1366/0003702953964219

  日期：1995.4

  The output of a continuous-wave carbon dioxide laser was used successfully for the dissociation of methylphosphonic difluoride. End product analysis using Fourier transform infrared spectroscopy revealed that the phosphorus-to-carbon bond was cleaved, yielding the products methane, ethene, ethyne, hydrophosphoryl difluoride, and a mixture of phosphorus compounds. These results are presented and discussed

  连续波二氧化碳激光的输出成功地用于分解甲基膦酰二氟化物。使用傅里叶变换红外光谱对最终产物进行分析表明，磷-碳键被裂解，产生产物甲烷、乙烯、乙炔、氢磷酰二氟化物和磷化合物的混合物。提出并讨论了这些结果。解离得到优化。提出了解离的反应机制。
• Nucleoside 3'-methylphosphonofluoridates and nucleoside 3'-methylfluorido-phosphonothioates. New convenient intermediates in large scale synthesis of dinucleoside-(3',5')-methylphosphonates
  作者：Wojciech Dabkowski、Izabela Tworowska、Roustem Saiakhov

  DOI：10.1016/0040-4039(95)01946-f

  日期：1995.12

  Nucleoside 3'-methylphosphonofluoridates 3 and nucleoside 3'-methylfluoridophosphonothioates 5 for the first time are used directly in the synthesis of dinucleosidemethylphosphonates and methylphosphonothioates. The fluoridophosphonothioates 5 were separated into pure diastereomers.

  首次将核苷3'-甲基氟代膦酸酯3和核苷3'-甲基氟代硫代磷酸酯5直接用于合成二核苷甲基代膦酸酯和甲基硫代膦酸酯。氟代硫代磷酸膦酸酯5被分离成纯的非对映异构体。

表征谱图