亚硝酸甲酯 | 624-91-9

• 物质功能分类: 有机原料 - 无机酸酯
• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 亚硝酸甲酯
• 英文名称: methyl nitrite
• CAS: 624-91-9
• 化学式: CH₃NO₂
• mdl: MFCD01711662
• 分子量: 61.0403
• InChiKey: BLLFVUPNHCTMSV-UHFFFAOYSA-N

物化性质

• 熔点：
  -16.99°C
• 沸点：
  -12°C
• 密度：
  0.9910
• 物理描述：
  Methyl nitrite appears as a liquid or gas Boils at 10.4°F. Moderately toxic by inhalation. Narcotic in high concentrations. Used as a rocket propellant. Differs from nitromethane (H3CNO2).
• 颜色/状态：
  Gas
• 溶解度：
  In water, 2.4X10-4 mg/L @ 25 °C /Estimated/
• 蒸汽压力：
  1,650 mm Hg @ 25 °C /Estimated/
• 大气OH速率常数：
  2.20e-13 cm3/molecule*sec
• 保留指数：
  268
• 稳定性/保质期：
  1. 稳定性^[12]：稳定。
  2. 禁配物^[13]：易燃或可燃物、强氧化剂、氰化物。
  3. 避免接触的条件^[14]：受热、光照。
  4. 聚合危害^[15]：不聚合。
  5. 分解产物^[16]：氮氧化物。

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  4
• 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：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

ADMET

毒理性

• 副作用

高铁血红蛋白血症 - 血液中高铁血红蛋白含量增加；该化合物被归类为主要毒性效应。

Methemoglobinemia - The presence of increased methemoglobin in the blood; the compound is classified as primary toxic effect.

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

毒理性

• 毒性数据

大鼠LC50 = 176 ppm/4小时

LC50 (rat) = 176 ppm/4h

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

毒理性

• 解毒与急救

保持呼吸道通畅，必要时协助通风。给予补充氧气。通过仰卧位、静脉晶体液和必要时低剂量升压药治疗低血压。监测生命体征和心电图4至6小时。有症状的methemoglobinemia可以用亚甲蓝治疗。血液透析和血液灌流无效。对亚甲蓝治疗无反应的婴儿严重methemoglobinemia可能需要交换输血。

Maintain an open air way and assist ventilations if necessary. Administer supplemental oxygen. Treat hypotension with supine positioning, intravenous crystalloid fluids. and low-dose pressors if needed.Monitor vital signs and ECG for 4 to 6 hours. Symptomatic methemoglobinemia may be treated with methylene blue. Hemodialysis and hemoperfusion are not effective. Sever methemoglobinemia in infants not responsive to methylene blue therapy may require exchange transfusion.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

基本治疗：建立专利气道。如有必要，进行吸痰。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。监测休克并视需要进行治疗……预见并治疗癫痫发作……。对于眼睛污染，立即用水冲洗眼睛。在运输过程中，用生理盐水连续冲洗每只眼睛……。不要使用催吐剂。对于摄入，如果患者能吞咽、有强烈的干呕反射并不流口水，则用水冲洗口腔，并给予5毫升/千克，最多200毫升的水进行稀释。给予活性炭……。/硝酸盐、亚硝酸盐及相关化合物/

Basic treatment: Establish a patent airway. Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for shock and treat if necessary ... . Anticipate seizures and treat as necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with normal saline during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 ml/kg up to 200 d of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . /Nitrates, nitrites, and related compounds/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

高级治疗：对于无意识或呼吸暂停的患者，考虑进行口咽或鼻咽气管插管以控制气道。监测心率和必要时治疗心律失常。用D5W/SRP（5%葡萄糖盐水/生理盐水）开始静脉输液："保持开放"，最低流速。如果出现低血容量的迹象，使用乳酸钠林格氏液。对于伴有低血容量迹象的低血压，谨慎给予液体。如果对这些措施无反应，血管加压药可能有所帮助。注意液体过载的迹象……。用安定（Valium）治疗癫痫……。如果患者出现严重低氧血症、发绀和心脏功能不全，且对吸氧无反应，给予1%亚甲蓝溶液……。使用丙美卡因氢氯化物以协助眼部冲洗……。/硝酸盐、亚硝酸盐及相关化合物/

Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious or in respiratory arrest. Monitor cardiac rhythm and treat arrhythmias if necessary. Start an IV with D5W /SRP: "To keep open", minimal flow rate/. Use lactated Ringer's if signs of hypovolemia are present For hypotension with signs of hypovolemia, administer fluid cautiously. If unresponsive to these measures, vasopressors may be helpful. Watch for signs of fluid overload ... . Treat seizures with diazepam (Valium) ... . Administer 1% solution methylene blue if patient is symptomatic with severe hypoxia, cyanosis, and cardiac compromise not responding to oxygen. ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Nitrates, nitrites, and related compounds/

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 危险等级：
  2.2
• 危险类别：
  2.2
• 危险品运输编号：
  UN 2455
• 储存条件：
  储存注意事项：应将物品储存在阴凉、通风的专用库房中，并确保库温不超过30℃。远离火源和热源，避免阳光直射。与易燃物、氧化剂、氰化物等分开存放，切忌混合储存。使用防爆型照明和通风设备，禁止使用能产生火花的机械设备和工具。储区应配备泄漏应急处理设备。

SDS

第一部分：化学品名称

制备方法与用途

类别：有害气体

• 毒性分级：中毒
• 急性毒性：吸入-大鼠 LC50: 176 PPM/4小时
• 爆炸物危险特性：与空气混合易爆
• 可燃性危险特性：易燃；遇水分解生成有毒的亚硝酸；遇热分解产生有毒的氧化氮气体；防止烫伤
• 储运特性：库房应保持通风、低温和干燥，需与氧化剂、可燃物及铵盐分开存放
• 灭火剂：雾状水、泡沫、二氧化碳

反应信息

• 作为反应物：
  描述：

  亚硝酸甲酯 在 HCl 作用下， 生成 亚硝酰氯
  参考文献：
  名称：

  THE GAS PHASE EQUILIBRIUM BETWEEN METHYL NITRITE, HYDROGEN CHLORIDE, METHYL ALCOHOL, AND NITROSYL CHLORIDE. THE ABSORPTION SPECTRUM OF NITROSYL CHLORIDE

  摘要：

  DOI：

  10.1021/ja01344a015
• 作为产物：
  描述：

  硝酸甲酯 以0.6%的产率得到亚硝酸甲酯
  参考文献：
  名称：

  硝酸甲酯在分子束中的光解离

  摘要：

  The photodissociation of methyl nitrate, CH3ONO2, has been investigated by photofragment translational spectroscopy. At the photolysis wavelength of 193 nm the predominant primary decay (approximately 70%) involves the fission of the weak CH3O-NO2 bond (D0I approximately 41 kcal/mol) to yield CH3O + NO2 fragment pairs which show a bimodal translational energy distribution. The component consisting of the fast fragment pairs has an average translational energy [E(T)] = 41 kcal/mol and a recoil anistropy beta = 0.9, while the slow component is characterized by [E(T)] = 19 kcal/mol and beta = 0. A significant portion of the NO2 fragments of the slow component is subject to a unimolecular decay to NO + O(3P). An additional primary decay route leads to the formation of methyl nitrite, CH3ONO, and atomic oxygen O(1D) with [E(T)] = 6 kcal/mol and beta = 1.2. This competing reaction requires fission of the strong N-O bond (D0II approximately 118 kcal/mol) and its occurrence indicates an initial localization of the photoexcitation on the NO2 moiety in the parent molecule. At higher laser fluence secondary photodissociation of the primary fragments CH3ONO was observed. Photolysis at 248 nm is shown to produce CH3O + NO2 fragment pairs exclusively, with [E(T)] = 17 kcal/mol.

  DOI：

  10.1021/j100144a002
• 作为试剂：
  描述：

  1-(氰基乙酰基)吡咯烷 在 亚硝酸甲酯 、 三乙胺 作用下， 以 丙醇 、 水 为溶剂， 生成
  参考文献：
  名称：

  N-吡咯烷-氰肟及其Ni(II)配合物显着的结构多样性

  摘要：

  合成了一种新型氰肟，2-肟基-2-氰基-N-吡咯烷-乙酰胺（又称为HPyrCO），并通过光谱方法、热分析和X射线晶体学对其进行了表征。该结构揭示了八个独立的分子，在不对称单元中具有复杂的分子间氢键，并采用了氰肟的反式构型。此后，从水溶液中获得了一系列Ni(II)配位化合物、结晶水合物，以及这种新型氰肟，在过滤主产物并随后从母液中结晶出新产物后，从同一系统中分离出四种配合物。这些是红色，主要产物[Ni(PyrCO) 2 (H 2 O) 2 ](H 2 O)，以及两种不同颜色的多晶型物绿色 [Ni(PyrCO) 2 (H 2 O) 2 ] 和紫色 [Ni(PyrCO) 2 (H 2 O) 2 ]，仅含有少量的 fac-Na[Ni(PyrCO) 3 ] 三氰肟酯。另外两个配合物，二聚体 [Ni 2 (PyrCO) 4 (H 2 O) 2 ]·2C 3 OH和三氰肟酯[Ni{HPyrCO}(PyrCO)

  DOI：

  10.1021/acs.cgd.4c00496

文献信息

• Processes for Producing an Oxalate by Coupling of CO
  申请人：LIU Juntao

  公开号：US20100160671A1

  公开（公告）日：2010-06-24

  Provided are processes for producing an oxalate by coupling of CO in the presence of a nitrite, wherein two or more reaction zones in series are used, and at least a portion of the oxalate as reaction product is separated between the reaction zones, and/or the nitrite is fed stagewise. The processes described herein can effectively enhance the selectivity to the oxalate and the single-pass conversion of the feedstock.

  提供了在存在亚硝酸盐的情况下通过CO偶联制备草酸盐的方法，其中使用了两个或更多个串联的反应区，并且至少将部分草酸盐作为反应产物在反应区之间分离，和/或亚硝酸盐分阶段供给。本文描述的方法可以有效地提高对草酸盐的选择性和原料的单程转化率。
• Gas-Phase Reaction of Methyl Isothiocyanate and Methyl Isocyanate with Hydroxyl Radicals under Static Relative Rate Conditions
  作者：Zhou Lu、Vincent R. Hebert、Glenn C. Miller

  DOI：10.1021/jf404526t

  日期：2014.2.26

  Gaseous methyl isothiocyanate (MITC), the principal breakdown product of the soil fumigant metam sodium (sodium N-methyldithiocarbamate), is an inhalation exposure concern to persons living near treated areas. Inhalation exposure also involves gaseous methyl isocyanate (MIC), a highly reactive and toxic transformation product of MITC. In this work, gas-phase hydroxyl (OH) radical reaction rate constants

  气态异硫氰酸甲酯（MITC）是土壤熏蒸剂间位钠（N-甲基二硫代氨基甲酸钠）的主要分解产物，它对居住在受治疗区域附近的人而言是吸入接触的问题。吸入暴露还涉及气态异氰酸甲酯（MIC），这是MITC的高反应性和高毒性转化产物。在这项工作中，已经使用静态相对速率技术在受控实验室条件下确定了MITC和MIC的气相羟基（OH）自由基反应速率常数。MITC获得的速率常数为15.36×10 –12 cm 3分子–1 s –1，分子常数为3.62×10 –12 cm 3分子–1 sMIC为–1。MITC和MIC在大气中的平均半衰期估计分别为15.7和66.5 h。对于OH自由基反应，MITC向MIC的摩尔转化率为67％±8％，这表明MIC是气相中MITC-OH反应的主要产物。
• Atmospheric chemistry of t-CF₃CHCHCl: products and mechanisms of the gas-phase reactions with chlorine atoms and hydroxyl radicals
  作者：M. P. Sulbaek Andersen、O. J. Nielsen、M. D. Hurley、T. J. Wallington

  DOI：10.1039/c1cp22925g

  日期：——

  chamber techniques were used to study the products and mechanisms of the Cl atom and OH radical initiated oxidation of trans-3,3,3-trifluoro-1-chloro-propene, t-CF3CHCHCl, in 700 Torr of air or N2/O2 diluent at 296 ± 2 K. The reactions of Cl atoms and OH radicals with t-CF3CHCHCl occur via addition to the CC double bond; chlorine atoms add 15 ± 5% at the terminal carbon and 85 ± 5% at the central carbon,

  FTIR烟室技术用于研究产品的机理和机理。 氯 原子和 哦自由基引发的反式3,3,3-三氟-1-氯-的氧化丙烯，t- CF 3 CH CHCl，在296±2 K的700 Torr空气或N 2 / O 2稀释剂中。氯 原子和 哦t- CF 3 CH CHCl的自由基是通过在C C双键上加成而形成的；氯 原子在末端增加15±5％ 碳 中央为85±5％ 碳， 哦 自由基在末端增加约40％ 碳 中央的60％ 碳。主要产品氯原子引发的t- CF 3 CH CHCl氧化CF 3氯仿 和 CF 3 C（O）CHCl 2，次要产品是 CF 3 CHO， 碳酸氢盐 和 CF 3氯化钴。的产量CF 3 C（O）CHCl 2， CF 3 CHClCOCl 和 CF 3氯化钴 以牺牲为代价而增加 CF 3 CHO， 碳酸氢盐 和 CF 3氯仿当O 2分压在10–700 Torr范围内增加时。化学活化在人类的命运中起着重要作用CF
• S-Alkylation of Thiacalixarenes: A Long-Neglected Possibility in the Calixarene Family
  作者：Ondrej Kundrat、Vaclav Eigner、Hana Dvorakova、Pavel Lhotak

  DOI：10.1021/ol201546y

  日期：2011.8.5

  of sulfur atoms, thiacalixarenes have been alkylated only on oxygen atoms thus far. Using strong alkylating agents (triflates, trialkyloxonium salts), the substitution of the sulfur bridges has been successfully accomplished. The corresponding sulfonium salts of thiacalix[4]arene are formed regio- and stereoselectively as a completely new type of substitution pattern in thiacalixarene chemistry. These

  尽管硫原子具有很高的亲核性，但到目前为止，硫杂杯芳烃仅在氧原子上被烷基化。使用强烷基化剂（三氟甲磺酸盐，三烷基氧鎓盐），硫桥的取代已成功完成。噻吩并[4]芳烃的相应sulf盐是区域选择性和立体选择性形成的，是噻邻苯并芳烃化学中的一种新型取代基。这些化合物具有令人感兴趣的构象行为，并且可以以不常见的选择性用作不寻常的烷基化剂。
• An ultra-low Pd loading nanocatalyst with high activity and stability for CO oxidative coupling to dimethyl oxalate
  作者：Si-Yan Peng、Zhong-Ning Xu、Qing-Song Chen、Yu-Min Chen、Jing Sun、Zhi-Qiao Wang、Ming-Sheng Wang、Guo-Cong Guo

  DOI：10.1039/c3cc00219e

  日期：——

  A Pd/α-Al2O3 nanocatalyst with ultra-low Pd loading exhibits high activity and stability for CO oxidative coupling to dimethyl oxalate, which was prepared by a Cu2+-assisted in situ reduction method at room temperature. The small size and high dispersion of Pd nanoparticles facilitated by Cu2+ ions are responsible for the excellent catalytic activity.

  一种Pd/α-Al2O3纳米催化剂，其Pd负载量极低，但在室温下通过Cu2+辅助的原位还原法制备，具备出色的活性和稳定性，适用于将CO氧化偶联成草酸二甲酯。铜离子辅助下Pd纳米颗粒的小尺寸和高分散性是催化活性优异的原因。

表征谱图