二氟甲烷 | 75-10-5

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 中文名称: 二氟甲烷
• 中文别名: HFC-32；R32；F32
• 英文名称: Difluoromethane
• CAS: 75-10-5
• 化学式: CH₂F₂
• 分子量: 52.0237
• InChiKey: RWRIWBAIICGTTQ-UHFFFAOYSA-N

物化性质

• 熔点：
  -136 °C
• 沸点：
  -51.6 °C
• 密度：
  0.5265 g/cm3
• 物理描述：
  Difluoromethane appears as a colorless odorless gas. Insoluble in water and has a high thermal stability. Its vapors are heavier than air. Under prolonged exposure to fire or intense heat the containers may rupture violently and rocket. Contact with the unconfined liquid can cause frostbite. Used as a refrigerant.
• 颜色/状态：
  Colorless gas
• 溶解度：
  In water, 1.285X10+4 mg/L at 25 °C (est)
• 蒸汽压力：
  1.26X10+4 mm Hg at 25 °C
• 大气OH速率常数：
  1.09e-14 cm3/molecule*sec
• 分解：
  When heated to decomposition it emits toxic vapors of /flouride/
• 保留指数：
  230
• 稳定性/保质期：
  在常温常压下，该物质是稳定的。

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  3
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  2

ADMET

代谢

二氟甲烷（HFC32）正在开发中，以替代某些制冷应用中的氯氟烃（CFCs）。它已经通过毒性、发育毒性和遗传毒性的标准研究进行了评估。此外，还研究了HFC32的代谢和处置，并建立了基于生理学的药代动力学（PB-PK）模型/使用大鼠和兔子/。... [(14)C]二氟甲烷（10,000至50,000 ppm/6小时）的药代动力学显示，吸入的HFC32约2.1%被吸收，稳态血药浓度在2小时内达到，并与剂量成正比。在所有暴露水平下，二氧化碳是HFC32的主要代谢物。未检测到一氧化碳。利用活体数据验证了描述HFC32的摄取和代谢的PB-PK模型。吸收和分布可以使用大鼠血液：空气和组织：空气分配系数充分描述。代谢在剂量范围内呈线性，由一级速率常数（Kf = 8.98 hr-1）描述。在所有剂量下，约63%的吸收HFC32被代谢；然而，当代谢以吸入剂量的百分比表示时，它要低得多，大约是进入气道的HFC32的1.4%。... /大鼠，兔子/

Difluoromethane (HFC32) is under development as a replacement for chlorofluorocarbons (CFCs) in some refrigeration applications. It has been evaluated by standard studies of toxicity, developmental toxicity, and genotoxicity. In addition, the metabolism and disposition of HFC32 was investigated and a physiologically based pharmacokinetic (PB-PK) model constructed /using rats and rabbits/. ... The pharmacokinetics of [(14)C]difluoromethane (10,000 to 50,000 ppm/6 hr) revealed that about 2.1% of the inhaled HFC32 was absorbed and that steady state blood levels were achieved within 2 hr and were proportional to dose. Carbon dioxide was the major metabolite of HFC32 at all exposure levels. Carbon monoxide was not detected. The in vivo data were used to validate a PB-PK model to describe the uptake and metabolism of HFC32. Absorption and distribution are adequately described using rat blood:air and tissue:air partition coefficients. Metabolism, which was linear across the dose range, was described by a first order rate constant (Kf = 8.98 hr-1). Of the absorbed HFC32, about 63% was metabolized at all doses; however, when metabolism was expressed as a percentage of the inhaled dose it was much lower, being about 1.4% of the HFC32 entering the airways. ... /rat, rabbit/

来源:Hazardous Substances Data Bank (HSDB)

代谢

二氟甲烷（HFC32）正在开发中，以替代某些制冷应用中的氯氟烃（CFCs）。通过让雄性瑞士小鼠在10,000 ppm的二氟甲烷（[(14)C]-HFC32）气氛中单次吸入暴露6小时，确定了[(14)C]-二氟甲烷的代谢和处置。吸入剂量的约1-2%在呼出的空气、尿液、粪便和尸体中回收，这表明这种氢氟烃从肺泡空气空间吸收到血液的系统性吸收较差。停止暴露后，大部分系统性吸收的HFC32在1小时内通过呼气排出。二氧化碳是HFC32的主要代谢物。暴露后测量的二氧化碳约占总吸入剂量的0.3%。非挥发性代谢物通过尿液和粪便排出的约占总吸入剂量的0.34%和0.07%。一氧化碳无法检测到。总代谢量，即尿液、粪便中回收的放射性、作为二氧化碳的一部分以及保留在尸体中的总和，约占总吸入剂量的0.8%，相当于回收的总放射性的64%。在暴露后4天对一系列组织进行分析，显示出放射性的相对均匀分布，肺、肝脏和肾脏的浓度最高。没有证据表明任何器官或组织有特定的滞留。

Difluoromethane (HFC32) is under development as a replacement for chlorofluorocarbons (CFCs) in some refrigeration applications. The metabolism and disposition of [(14)C]-difluoromethane ([(14)C]-HFC32) was determined in male Swiss mice as a consequence of a single 6 hr inhalation exposure to atmospheres of 10 000 ppm. Of the inhaled dose, about 1-2% was recovered in expired air, urine, feces and carcass suggesting that systemic absorption of this hydrofluorocarbon from the alveolar air space of the lung into blood is poor. Upon cessation of exposure the majority of the systemically absorbed HFC32 was exhaled within 1 hr. Carbon dioxide was a major metabolite of HFC32. Carbon dioxide measured post-exposure accounted for about 0.3% of the inhaled dose. Urinary and fecal excretion of non-volatile metabolites accounted for about 0.34% and 0.07% of the inhaled dose, respectively. Carbon monoxide could not be detected. Total metabolism, measured as the sum of the radioactivity recovered in urine, feces, as carbon dioxide and that retained in the carcass, amounted to about 0.8% of the inhaled dose, equivalent to 64% of the total radioactivity recovered. Analysis of a range of tissues at 4 days post-exposure showed a relatively uniform distribution of radioactivity with the highest concentration in the lung, liver and kidney. There was no evidence of a specific retention in any organ or tissue.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

识别和使用：二氟甲烷（HFC32）是一种无色气体。它用于制冷、有机合成，并在气相色谱和光声光谱中作为示踪气体。人类暴露和毒性：没有可用数据。动物研究：吸入HFC32（高达50,000 ppm）未引起器官特异性效应。HFC32未使心脏对肾上腺素敏感。在大鼠中，HFC32在50,000 ppm的浓度下对母体和发育有轻微毒性，但在兔中则没有。在大鼠或兔中没有发现致畸性的证据。

IDENTIFICATION AND USE: Difluoromethane (HFC32) is a colorless gas. It is used in refrigeration, organic synthesis, and as a tracer gas in gas chromatography and photoacoustic spectroscopy. HUMAN EXPOSURE AND TOXICITY: There are no data available. ANIMAL STUDIES: Inhalation of HFC32 (up to 50,000 ppm) caused no organ-specific effects. HFC32 did not sensitize the heart to adrenaline. HFC32 is slightly maternally and developmentally toxic at 50,000 ppm in rats, but not in rabbits. No evidence of teratogenicity was noted in rats or rabbits.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 副作用

神经毒素 - 急性溶剂综合征

Neurotoxin - Acute solvent syndrome

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

毒理性

• 毒性数据

大鼠LC50 = 1,890,000毫克/立方米/4小时

LC50 (rat) = 1,890,000 mg/m3/4h

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

毒理性

• 解毒与急救

急救响应：将受害者移至新鲜空气处；呼叫紧急医疗救助。如果受害者停止呼吸，进行人工呼吸。如果呼吸困难，给予吸氧。在冻伤的情况下，用水融化冻僵的部位。保持受害者静卧，并维持正常体温。

First aid responses: Move victim to fresh air; call emergency medical care. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. In case of frostbite, thaw frozen parts with water. Keep victim quiet and maintain normal body temperatures.

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，让患者前倾或置于左侧（如果可能，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。寻求医疗关注。 /氯氟烃（CFCs）及相关化合物/

/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. /Chlorinated fluorocarbons (CFCs) and related compounds/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

二氟甲烷（HFC32）正在开发中，以替代某些制冷应用中的氯氟烃（CFCs）。它已经通过毒性、发育毒性和遗传毒性的标准研究进行了评估。此外，还研究了HFC32的代谢和处置，并建立了基于生理学的药代动力学（PB-PK）模型/使用大鼠和兔子/。... [(14)C]二氟甲烷（10,000至50,000 ppm/6小时）的药代动力学显示，吸入的HFC32约2.1%被吸收，稳态血药浓度在2小时内达到，并且与剂量成正比。在所有暴露水平下，二氧化碳是HFC32的主要代谢物。没有检测到一氧化碳。利用实验数据验证了一个PB-PK模型，以描述HFC32的摄取和代谢。吸收和分布可以通过大鼠血液：空气和组织：空气分配系数来充分描述。代谢是线性的，在整个剂量范围内，由一级速率常数（Kf = 8.98小时-1）描述。在所有剂量下，约63%的吸收HFC32被代谢；然而，当代谢以吸入剂量的百分比表示时，它要低得多，大约是进入气道的HFC32的1.4%。...

Difluoromethane (HFC32) is under development as a replacement for chlorofluorocarbons (CFCs) in some refrigeration applications. It has been evaluated by standard studies of toxicity, developmental toxicity, and genotoxicity. In addition, the metabolism and disposition of HFC32 was investigated and a physiologically based pharmacokinetic (PB-PK) model constructed /using rats and rabbits/. ... The pharmacokinetics of [(14)C]difluoromethane (10,000 to 50,000 ppm/6 hr) revealed that about 2.1% of the inhaled HFC32 was absorbed and that steady state blood levels were achieved within 2 hr and were proportional to dose. Carbon dioxide was the major metabolite of HFC32 at all exposure levels. Carbon monoxide was not detected. The in vivo data were used to validate a PB-PK model to describe the uptake and metabolism of HFC32. Absorption and distribution are adequately described using rat blood:air and tissue:air partition coefficients. Metabolism, which was linear across the dose range, was described by a first order rate constant (Kf = 8.98 hr-1). Of the absorbed HFC32, about 63% was metabolized at all doses; however, when metabolism was expressed as a percentage of the inhaled dose it was much lower, being about 1.4% of the HFC32 entering the airways. ...

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

二氟甲烷（HFC32）正在开发中，以替代某些制冷应用中的氯氟烃（CFCs）。通过让雄性瑞士小鼠在10,000 ppm的二氟甲烷（[(14)C]-HFC32）气氛中单次吸入暴露6小时，确定了[(14)C]-二氟甲烷的代谢和处置。吸入剂量的约1-2%在呼出的空气、尿液、粪便和尸体中回收，这表明这种氢氟烃从肺泡空气空间进入血液的系统吸收较差。停止暴露后，大部分系统吸收的HFC32在1小时内呼出。二氧化碳是HFC32的主要代谢物。测量呼出后的二氧化碳约占吸入剂量的0.3%。尿液和粪便中非挥发性代谢物的排泄分别约占吸入剂量的0.34%和0.07%。一氧化碳无法检测到。总代谢量，即尿液、粪便中回收的放射性、作为二氧化碳的量和保留在尸体中的量的总和，约占吸入剂量的0.8%，相当于回收的总放射性的64%。在暴露后4天对一系列组织进行分析，显示出放射性的相对均匀分布，肺、肝脏和肾脏的浓度最高。没有证据表明任何器官或组织有特定的滞留。

Difluoromethane (HFC32) is under development as a replacement for chlorofluorocarbons (CFCs) in some refrigeration applications. The metabolism and disposition of [(14)C]-difluoromethane ([(14)C]-HFC32) was determined in male Swiss mice as a consequence of a single 6 hr inhalation exposure to atmospheres of 10,000 ppm. Of the inhaled dose, about 1-2% was recovered in expired air, urine, feces and carcass suggesting that systemic absorption of this hydrofluorocarbon from the alveolar air space of the lung into blood is poor. Upon cessation of exposure the majority of the systemically absorbed HFC32 was exhaled within 1 hr. Carbon dioxide was a major metabolite of HFC32. Carbon dioxide measured post-exposure accounted for about 0.3% of the inhaled dose. Urinary and fecal excretion of non-volatile metabolites accounted for about 0.34% and 0.07% of the inhaled dose, respectively. Carbon monoxide could not be detected. Total metabolism, measured as the sum of the radioactivity recovered in urine, feces, as carbon dioxide and that retained in the carcass, amounted to about 0.8% of the inhaled dose, equivalent to 64% of the total radioactivity recovered. Analysis of a range of tissues at 4 days post-exposure showed a relatively uniform distribution of radioactivity with the highest concentration in the lung, liver and kidney. There was no evidence of a specific retention in any organ or tissue.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 危险品标志：
  F
• 安全说明：
  S16,S33,S9
• 危险类别码：
  R11
• WGK Germany：
  1
• 危险品运输编号：
  UN 3252 2.1
• RTECS号：
  PA8537500
• 海关编码：
  2903399090
• 危险类别：
  2.1
• 储存条件：
  应存放在通风干燥处，并密封保存。

制备方法与用途

制备方法

1. 天然气氟化：[ \text{CH}_4 + 2\text{F}_2 \rightarrow \text{CH}_2\text{F}_2 + 2\text{HF} ]
2. 氟甲烷氟化：[ \text{CH}_3\text{F} + \text{F}_2 \rightarrow \text{CH}_2\text{F}_2 + \text{HF} ]

合成制备方法

1. 天然气氟化：[ \text{CH}_4 + 2\text{F}_2 \rightarrow \text{CH}_2\text{F}_2 + 2\text{HF} ]
2. 氟甲烷氟化：[ \text{CH}_3\text{F} + \text{F}_2 \rightarrow \text{CH}_2\text{F}_2 + \text{HF} ]

用途简介

作为制冷剂和干刻剂。

用途

作为制冷剂和干刻剂。

反应信息

• 作为反应物：
  描述：

  二氟甲烷 以 neat (no solvent) 为溶剂， 生成 difluoromethylium
  参考文献：
  名称：

  Lifshitz; Long, Journal of Physical Chemistry, 1965, vol. 69, p. 3731

  摘要：

  DOI：
• 作为产物：
  描述：

  二氯甲烷 在 氯 氢氟酸 作用下， 250.0 ℃ 、1.2 MPa 条件下， 反应 1050.0h， 生成 二氟甲烷
  参考文献：
  名称：

  Process for the manufacture of defluoromethane

  摘要：

  该发明的主题是在气相中，在氯的存在下，利用氯化亚甲烷（F30）和氟化氢制备二氟甲烷（F32）的连续工艺。根据该发明，从反应器排出的气流经过蒸馏，以便在顶部分离出一个含几乎所有HCl和至少90%由反应产生的F32的流动，在底部分离出一个含至少90%未转化的反应物（F31、F30和HF）的流动，后者直接回收到反应器中，无需任何纯化操作。

  公开号：

  US06635790B1
• 作为试剂：
  描述：

  D-对甲砜基苯丝氨酸乙酯 在 钾硼氢 、 六氟丙烯 、 二氟甲烷 、 3H-四氟丙酸 、 溶剂黄146 、 二乙胺 、 甘油 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 18.0h， 生成
  参考文献：
  名称：

  氟苯尼考的制备方法

  摘要：

  本发明涉及一种氟苯尼考的制备方法，属于药物合成的技术领域。本发明的氟苯尼考的制备方法，以D‑对甲砜基苯丝氨酸乙酯为原料，经过还原反应、环合反应、氟化反应和水解反应制备得到。所述氟化反应以二氯甲烷溶剂，以环合产物、氟化试剂为反应原料，其中所述环合产物与氟化试剂的质量比为1.25～1.30∶1。本发明的制备方法具有工艺操作简单、成本低的优点，通过反应条件的控制和添加剂的使用减少了氟化反应的副产物，使得本发明的方法仅经过一步脱色和精制步骤就可得到纯度高、杂质少的氟苯尼考产品，有利于控制产品成本，提高生产效率。

  公开号：

  CN106278964B

文献信息

• Selective reduction of a C Cl bond in halomethanes with Et3GeH at nanoscopic Lewis acidic Aluminium fluoride
  作者：Gisa Meißner、Michael Feist、Thomas Braun、Erhard Kemnitz

  DOI：10.1016/j.jorganchem.2017.04.030

  日期：2017.10

  activation of CCl bonds of hydrochlorofluoromethanes and chloromethanes at moderate reaction conditions using ACF in a combination with Et3GeH is presented. The reactions of the chloromethanes (CH3Cl, CH2Cl2, CHCl3 and CCl4) in the presence of Et3GeH and ACF as catalyst led to the activation of only one CCl bond resulting in the hydrodechlorination. Friedel-Crafts reactions with benzene as solvent are suppressed

  提出了在中等反应条件下，使用ACF与Et 3 GeH的组合，选择性活化氢氯氟甲烷和氯甲烷的C Cl键。在作为催化剂的Et 3 GeH和ACF的存在下，氯甲烷（CH 3 Cl，CH 2 Cl 2，CHCl 3和CCl 4）的反应导致仅一个C Cl键的活化而导致加氢脱氯。Et 3 GeH抑制了以苯为溶剂的Friedel-Crafts反应。实现了氢氯氟甲烷的选择性加氢脱氯，因为C F键转变为C没有发生由ACF和Et 3 GeH结合的H键。支撑脉冲TA ®实验中示出的固体催化剂和Et之间的相互作用3 GeH的，溶剂苯或CH 2氯2。
• [EN] A PROCESS FOR THE PRODUCTION OF DIFLUOROMETHANE<br/>[FR] PROCEDE DE PRODUCTION DE DIFLUOROMETHANE
  申请人：SRF LTD

  公开号：WO2004007410A1

  公开（公告）日：2004-01-22

  A process for vapor phase fluorination of methylene chloride with anhydrous hydrogen fluoride (AHF) in the presence of a coprecipitated chromia-alumina impregnated with zinc salt as catalyst, removing (HCl) and heavier components by distillation, subjecting (HFC-32) rich cut to a further step of fluorination catalyst.

  一种利用共沉淀的铬铝氧化物浸渍锌盐作为催化剂，在无水氢氟酸（AHF）存在下对氯甲烷进行蒸汽相氟化的方法，通过蒸馏去除（HCl）和较重组分，将富含（HFC-32）的馏分经过进一步的氟化催化剂处理。
• Process for the production of difluoromethane
  申请人：——

  公开号：US20040010168A1

  公开（公告）日：2004-01-15

  A process for vapor phase fluorination of methylene chloride with anhydrous hydrogen fluoride (AHF) in the presence of a coprecipitated chromia-alumina impregnated with zinc salt as catalyst, removing HCl and heavier components by distillation, subjecting HFC-32 rich cut to a further step of fluorination in the presence of a fluorination catalyst.

  一种用无水氢氟酸（AHF）在共沉淀的铬铝氧化物浸渍锌盐作为催化剂的情况下对氯甲烷进行蒸汽相氟化的方法，通过蒸馏去除HCl和较重组分，将富含HFC-32的馏分在氟化催化剂存在下进一步氟化的过程。
• Method of making hydrofluorocarbons
  申请人：Honeywell International Inc.

  公开号：US20040236160A1

  公开（公告）日：2004-11-25

  A manufacturing process for making hydrofluorocarbons (HFCs), by reacting a hydrochlorocarbon and HF in a liquid phase catalytic reactor using a large mole ratio of HF to hydrochlorocarbon to minimize formation of high boiling by-products and improve HF consumption and hydrofluorocarbon yields.

  一种制造氢氟碳化合物（HFCs）的制造工艺，通过在液相催化反应器中反应氢氯碳烃和氢氟酸，使用大量的氢氟酸与氢氯碳烃的摩尔比，以最小化高沸点副产物的生成，提高氢氟酸的消耗和氢氟碳化合物的产量。
• [EN] METHOD OF PRODUCING HYDROFLUOROCARBONS<br/>[FR] PROCEDE DE PRODUCTION D'HYDROFLUOROCARBONES
  申请人：HONEYWELL INT INC

  公开号：WO2005037740A1

  公开（公告）日：2005-04-28

  A process for producing fluorinated C1 HFCs comprising fluorinating a reactive organic compound, such as dichloromethane, to produce a reaction product comprising at least the desired C1 HFC, such as difluoromethane (HFC-32), unreacted reactive organic compound and a byproduct, such as chloromethane (HCC-40), having a boiling point between the boiling point of said desired hydrofluorocarbon compound and said reactive organic compound; and removing from the reaction product at least a substantial portion of the byproduct to produce a high purity product stream.

  生产氟化C1 HFCs的过程包括氟化反应性有机化合物，例如二氯甲烷，以产生至少包含所需的C1 HFC的反应产物，例如二氟甲烷（HFC-32），未反应的反应性有机化合物和副产物，例如氯甲烷（HCC-40），其沸点介于所述所需氢氟烃化合物和所述反应性有机化合物的沸点之间；并从反应产物中去除至少大部分副产物，以产生高纯度产品流。

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