甲基二氯膦 | 676-83-5

• 物质功能分类: 有机原料 - 有机膦化合物
• 分子结构分类: 有机化合物 - 有机磷化合物 - 烷基卤代膦
• 中文名称: 甲基二氯膦
• 中文别名: 二氯甲基磷(禁运)；甲基二氯化膦；二氯甲基磷；二氯甲基膦
• 英文名称: methyldichlorophosphane
• 英文别名: dichloromethylphosphine；methylphosphine dichloride；methylphosphorus dichloride；methyldichlorophosphine；methylphosphonyl dichloride；dichloro(methyl)phosphane
• CAS: 676-83-5
• 化学式: CH₃Cl₂P
• 分子量: 116.915
• InChiKey: CDPKWOKGVUHZFR-UHFFFAOYSA-N

物化性质

• 熔点：
  81.5 °C
• 沸点：
  81-82 °C
• 密度：
  1.3
• 闪点：
  48 °C
• 物理描述：
  Methyl phosphonous dichloride appears as a colorless liquid with a pungent odor. Very toxic by inhalation. Denser than water.
• 稳定性/保质期：

  不稳定，对水和空气都较为敏感。

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

毒理性

• 副作用

Dermatotoxin - 皮肤烧伤。

Dermatotoxin - Skin burns.

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

安全信息

• TSCA：
  Yes
• 危险等级：
  6.1
• 危险品标志：
  F,T-F,T
• 安全说明：
  S16,S23,S26,S33,S36/37/39,S43,S45,S8
• 危险类别码：
  R17,R14,R10,R29,R23/24/25,R34
• WGK Germany：
  3
• 海关编码：
  29310099
• 危险类别：
  6.1
• 危险品运输编号：
  UN 2845
• 储存条件：
  密封贮藏，存放在阴凉、干燥的地方，远离火源、易燃易爆区域和水源。通常采用氮气进行保护。

SDS

Name:	Dichloromethylphosphine tech. 90% Material Safety Data Sheet
Synonym:	Methyldichlorophosphine; Methylphosphonous dichlorid
CAS:	676-83-5

Section 1 - Chemical Product MSDS Name:Dichloromethylphosphine tech. 90% Material Safety Data Sheet
Synonym:Methyldichlorophosphine; Methylphosphonous dichlorid

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
676-83-5	Dichloromethylphosphine	90	211-631-8

Hazard Symbols: T
Risk Phrases: 14 17 23/24/25 34

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Reacts violently with water. Spontaneously flammable in air. Toxic by inhalation, in contact with skin and if swallowed. Causes burns.The toxicological properties of this material have not been fully investigated.Air sensitive.Lachrymator (substance which increases the flow of tears).Corrosive.
Potential Health Effects
Eye:
Lachrymator (substance which increases the flow of tears). Causes eye irritation and burns.
Skin:
Harmful if absorbed through the skin. Causes skin irritation and burns.
Ingestion:
Harmful if swallowed. May cause severe and permanent damage to the digestive tract. Causes gastrointestinal tract burns.
Inhalation:
Harmful if inhaled. Causes chemical burns to the respiratory tract.
Inhalation of decomposition products may cause severe injury or death.
Chronic:
Symptoms of exposure may include burning sensation, coughing, wheezing, laryngitis, shortness of breath, headache, nausea and vomiting. Chronic inhalation may cause spasm, inflammation and edema of the larynx and bronchi, chemical pneumonitis, and pulmonary edema.

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Section 4 - FIRST AID MEASURES
Eyes: Get medical aid immediately. Do NOT allow victim to rub eyes or keep eyes closed. Extensive irrigation with water is required (at least 30 minutes).
Skin:
Get medical aid immediately. Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse. Destroy contaminated shoes.
Ingestion:
Do not induce vomiting. If victim is conscious and alert, give 2-4 cupfuls of milk or water. Never give anything by mouth to an unconscious person. Get medical aid immediately. Wash mouth out with water.
Inhalation:
Get medical aid immediately. Remove from exposure and move to fresh air immediately. If breathing is difficult, give oxygen. Do NOT use mouth-to-mouth resuscitation. If breathing has ceased apply artificial respiration using oxygen and a suitable mechanical device such as a bag and a mask.
Notes to Physician:

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Section 5 - FIRE FIGHTING MEASURES
General Information:
Evacuate area and fight fire from a safe distance. As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. Water runoff can cause environmental damage. Dike and collect water used to fight fire. Vapors can travel to a source of ignition and flash back. Material can spontaneously ignite (pyrophoric) when exposed to air at normal or slightly elevated temperatures. May burn with invisible flame. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Water Reactive. Material will react with water and may release a flammable and/or toxic gas. Spontaneously ignitable in air. Vapors may be heavier than air. They can spread along the ground and collect in low or confined areas. May ignite or explode on contact with steam or moist air. May re-ignite after fire is extinguished. May burn rapidly with flare-burning effect.
Extinguishing Media:
Do NOT get water inside containers. Contact professional fire-fighters immediately. Cool containers with flooding quantities of water until well after fire is out. Use dry sand, dry chemical, soda ash or lime. DO NOT USE WATER, CO2, OR FOAM DIRECTLY ON FIRE ITSELF. For large fires, use dry sand, dry chemical, soda ash or lime or withdraw from area and let fire burn.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Avoid runoff into storm sewers and ditches which lead to waterways.
Clean up spills immediately, observing precautions in the Protective Equipment section. Remove all sources of ignition. Use a spark-proof tool. Isolate area and deny entry. Provide ventilation. Place under an inert atmosphere. Do not use combustible materials such as paper towels to clean up spill. Do not get water on spilled substances or inside containers. Cover with dry earth, dry sand, or other non-combustible material followed with plastic sheet to minimize spreading and contact with water.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Do not allow water to get into the container because of violent reaction. Use spark-proof tools and explosion proof equipment. Do not breathe dust, vapor, mist, or gas. Do not get in eyes, on skin, or on clothing. Keep container tightly closed.
Do not ingest or inhale. Handle under an inert atmosphere. Use only in a chemical fume hood. Store and handle protected from air. Discard contaminated shoes. Keep from contact with moist air and steam.
Storage:
Keep away from heat, sparks, and flame. Keep away from sources of ignition. Keep container closed when not in use. Store in a tightly closed container. Keep away from water. Flammables-area. Do not expose to air. Store under an inert atmosphere.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Use explosion-proof ventilation equipment. Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use only under a chemical fume hood.
Exposure Limits CAS# 676-83-5: Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
A respiratory protection program that meets OSHA's 29 CFR 1910.134 and ANSI Z88.2 requirements or European Standard EN 149 must be followed whenever workplace conditions warrant respirator use.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Liquid
Color: colorless to pale yellow
Odor: pungent odor
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: 81 - 82 deg C @ 760.00mm Hg
Freezing/Melting Point: Not available.
Autoignition Temperature: Not applicable.
Flash Point: 48 deg C ( 118.40 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: Reacts.
Specific Gravity/Density: 1.3040g/cm3
Molecular Formula: CH3Cl2P
Molecular Weight: 116.92

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Powder or liquid is pyrophoric. Combines vigorously or explosively with water. Air sensitive.
Conditions to Avoid:
Incompatible materials, ignition sources, exposure to air, excess heat, strong oxidants, exposure to moist air or water.
Incompatibilities with Other Materials:
Water, strong oxidizing agents, strong bases, air.
Hazardous Decomposition Products:
Hydrogen chloride, phosphine, carbon monoxide, oxides of phosphorus, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 676-83-5 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Dichloromethylphosphine - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION

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Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

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Section 14 - TRANSPORT INFORMATION

IATA
Shipping Name: PYROPHORIC LIQUID, ORGANIC, N.O.S.*
Hazard Class: 4.2
UN Number: 2845
Packing Group:
IMO
Shipping Name: PYROPHORIC LIQUID, ORGANIC, N.O.S.
Hazard Class: 4.2
UN Number: 2845
Packing Group: I
RID/ADR
Shipping Name: PYROPHORIC LIQUID, ORGANIC, N.O.S.
Hazard Class: 4.2
UN Number: 2845
Packing group: I

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: T
Risk Phrases:
R 14 Reacts violently with water.
R 17 Spontaneously flammable in air.
R 23/24/25 Toxic by inhalation, in contact with skin
and if swallowed.
R 34 Causes burns.
Safety Phrases:
S 16 Keep away from sources of ignition - No
smoking.
S 23 Do not inhale gas/fumes/vapour/spray.
S 26 In case of contact with eyes, rinse immediately
with plenty of water and seek medical advice.
S 36/37/39 Wear suitable protective clothing, gloves
and eye/face protection.
WGK (Water Danger/Protection)
CAS# 676-83-5: No information available.
Canada
CAS# 676-83-5 is listed on Canada's NDSL List.
CAS# 676-83-5 is listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 676-83-5 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

制备方法

由三氯化磷与一氯甲烷和三氯化铝混合反应得到粗品，随后蒸馏去除多余的氯甲烷，获得半固体状物质。再经铝-氯化钾处理并蒸馏后，即可得到成品。

用途简介

它是合成除草剂草铵膦和含膦阻燃剂的重要中间体。此外，该物质还可作为双官能团磷酰胺偶联试剂，用于制备含磷维悌希试剂，并可用于与其他烯烃类单体制备含磷共聚物。

反应信息

• 作为反应物：
  描述：

  甲基二氯膦 在 水 作用下， 反应 0.33h， 生成 甲基-次磷酸
  参考文献：
  名称：

  一锅法制备甲基次膦酸铝盐

  摘要：

  本发明公开了一锅法制备甲基次膦酸铝盐的方法，属于化工合成技术领域。本发明提供了一种一锅法制备甲基次膦酸铝盐，包括：以二氯甲基膦为原料，与水反应，制得甲基次磷酸水溶液；调节甲基次磷酸水溶液pH至3≦pH＜7，加入硫酸铝，反应制得甲基次膦酸铝盐。本发明以二氯甲基膦为起始原料一锅法制备甲基次膦酸铝盐，无需分离甲基次膦酸；通过对水用量控制，可避免二氯甲基膦的副反应发生，提高甲基次膦酸产率；对成盐pH进行优化，提高甲基次膦酸铝盐收率；本发明方法原料廉价易得，操作简单，后处理方便，有利于实现甲基次膦酸铝盐的工业化生产。

  公开号：

  CN109293694B
• 作为产物：
  描述：

  氯甲烷 在 aluminum (III) chloride 、 三氯化磷 作用下， 85.0 ℃ 、1.5 MPa 条件下， 反应 8.0h， 以85%的产率得到甲基二氯膦
  参考文献：
  名称：

  一种草铵膦中间体甲基二氯化磷的合成方法

  摘要：

  本发明公开一种草铵膦中间体甲基二氯化磷的合成方法，属于草铵膦中间体合成技术领域。该合成方法是以氯甲烷、三氯化铝和三氯化磷为原料，在0.5‑3.0MPa压力下反应6.5‑10h得到三元络合物，再加入铝粉和氯化钠，在一定温度下反应得到甲基二氯化磷。本发明方法中，三氯化磷同时作为反应物和溶剂，并提高反应压强，使氯甲烷气体与固、液两相充分反应，不需要另外加入溶剂，提高了产品纯度，避免了溶剂分离、回收等问题，减少了三氯化磷回收难度，大大降低了生产成本。

  公开号：

  CN106046052A
• 作为试剂：
  描述：

  1,4-二氯苯 在 正丁基锂 、 甲基二氯膦 、 magnesium 作用下， 以 正己烷 为溶剂， 反应 2.5h， 生成 (4-Chlorphenyl)-2-(dimethylamino)ethyl-methylchlorsilan
  参考文献：
  名称：

  Aslanidis, Paraskevas; Grobe, Joseph, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1983, vol. 38, # 3, p. 289 - 298

  摘要：

  DOI：

文献信息

• Rh(I)-Catalyzed Arylation of Heterocycles via C−H Bond Activation:  Expanded Scope through Mechanistic Insight
  作者：Jared C. Lewis、Ashley M. Berman、Robert G. Bergman、Jonathan A. Ellman

  DOI：10.1021/ja0748985

  日期：2008.2.1

  A practical, functional group tolerant method for the Rh-catalyzed direct arylation of a variety of pharmaceutically important azoles with aryl bromides is described. Many of the successful azole and aryl bromide coupling partners are not compatible with methods for the direct arylation of heterocycles using Pd(0) or Cu(I) catalysts. The readily prepared, low molecular weight ligand, Z-1-tert-butyl-2

  描述了一种实用的、官能团耐受的方法，用于各种药学上重要的唑类与芳基溴化物的 Rh 催化直接芳基化。许多成功的唑和芳基溴偶联伙伴与使用 Pd(0) 或 Cu(I) 催化剂直接芳基化杂环的方法不兼容。容易制备的低分子量配体 Z-1-叔丁基-2,3,6,7-四氢膦以双齿 P-烯烃方式与 Rh 配位，提供高活性但热稳定的芳基化催化剂，是这种方法的成功至关重要。通过使用相应鏻的四氟硼酸盐，反应可以在手套箱外组装，无需纯化试剂或溶剂。反应也在四氢呋喃或二恶烷中进行，与大多数其他使用高沸点酰胺溶剂直接芳基化唑类的方法相比，这大大简化了产品的分离。反应在微波反应器中加热进行，在 2 小时内获得优异的产品收率。
• Zur Synthese und Pyrolyse von Organoelement-benzasolderivaten des Phosphors, Arsens, Siliciums und Zinns
  作者：Joachim Heinicke

  DOI：10.1016/0022-328x(89)87152-9

  日期：1989.4

  3-Organo-1,3-benzazaphospholes and -benzazarsoles as well as 3,3-disubstituted 1,3-benzazasiloles and -benzazastannoles are prepared from o-LiC6H6NC(Li)But and the relevant organoelement dichlorides. The heterocycles obtained are converted by flash vacuum pyrolysis into the aromatic 1H-1,3-benzazaphospholes and benzazarsoles, respectively.

  3-有机-1,3- benzazaphospholes和-benzazarsoles以及3,3-二取代的1,3- benzazasiloles和-benzazastannoles从制备ø -LiC 6 ħ 6 NC（Li）的卜吨和有关有机元素基氯化物。通过闪蒸真空热解法将获得的杂环分别转化为芳族1 H -1,3-苯并zaphooles和苯扎那唑。
• [EN] NOVEL CHIRAL PHOSPHORUS LIGANDS<br/>[FR] NOUVEAUX LIGANDS DE PHOSPHORE CHIRAUX
  申请人：BOEHRINGER INGELHEIM INT

  公开号：WO2011056737A1

  公开（公告）日：2011-05-12

  The invention relates to a series of novel chiral phosphorus ligands of formulae (Ia) and (Ib): wherein R, 1 - rR> 4 and X are as defined herein. The invention also relates to chiral metal complexes prepared with these chiral phosphorus ligands. The chiral metal complexes are useful as catalysts for carrying out asymmetric hydro genation.

  本发明涉及一系列新颖的具有公式（Ia）和（Ib）的手性磷配体：其中R，1 - rR> 4和X如本文所定义。本发明还涉及用这些手性磷配体制备的手性金属配合物。手性金属配合物可用作实施不对称氢化的催化剂。
• Mononuclear Five- and Six-Coordinate Iron Hydrazido and Hydrazine Species
  作者：Caroline T. Saouma、Connie C. Lu、Jonas C. Peters

  DOI：10.1021/ic301704f

  日期：2012.9.17

  [PhBPmter3]Fe(η2-N2H3) (1), in which the hydrazido serves as an L2X-type ligand. Upon coordination of an L-type ligand, the hydrazido shifts to an LX-type ligand, generating [PhBPmter3]Fe(L)(η2-N2H3) (L = N2H4 (2) or NH3 (3)). In contrast, treatment of [PhBPPh3]FeMe with hydrazine forms the adduct [PhBPPh3]Fe(Me)(η2-N2H4) (5). Complex 5 is thermally unstable to methane loss, generating intermediate [PhBPPh3]Fe(η2-N2H3)

  本文介绍了几种协调肼 (N 2 H 4 )、肼基 (N 2 H 3 – ) 和氨的低自旋铁 (II) 配合物的合成和表征。引入空间位阻的三（二-间三联苯膦基）硼酸盐配体 [PhBP m ter 3 ] -以提供无法用 [PhBP Ph 3 ] -配体（[PhBP R 3 ] - = PhB(CH 2 PR 2 ) 3 – )。[PhBP的治疗m ter 3 ]FeMe 与肼生成不寻常的 5 配位酰肼络合物 [PhBP m ter 3 ]Fe(η 2 -N 2 H 3 ) ( 1 )，其中酰肼作为 L 2 X 型配体。在与 L 型配体配位后，酰肼转变为 LX 型配体，生成 [PhBP m ter 3 ]Fe(L)(η 2 -N 2 H 3 ) (L = N 2 H 4 ( 2 ) 或NH 3 ( 3 ))。相比之下，[PhBP Ph 3]FeMe 与肼形成加合物 [PhBP Ph 3 ]Fe(Me)(η
• Some novel phosphoranides containing pentafluorophenyl groups
  作者：Rusmidah Ali、Keith B. Dillon

  DOI：10.1039/dt9900002593

  日期：——

  elemental analysis and (in some cases) i.r. spectroscopy. These ions apart from [P(C6F5)2(CN)Y]–} represent the first simple phosphoranides with an organo-group attached to phosphorus and no cyano-groups present. The species with two pentafluorophenyl groups are the first phosphoranides with two organo-groups directly bound to phosphorus. No acceptor properties towards halide ions were shown by P(CCl3)Cl2

  [P（C 6 F 5）X 2 Y] –（X = Cl，Y = Cl，Br或I； X = Br，Y = Br或I； X = NCS， Y = Cl，Br，I或NCS）或[P（C 6 F 5）2 X（Y）] –（X = Cl，Y = Cl，Br或I； X = Br，Y = Br或I ； X = CN，Y = Cl，Br，I或NCS）已通过31 P nmr光谱法在溶液中鉴定。大多数物种已分离为与四烷基铵离子的盐，并通过元素分析和（在某些情况下）红外光谱进一步表征。这些离子除[P（C 6 F 5）2（CN）Y] – }代表第一个简单的磷酰胺，其有机基团与磷相连，并且不存在氰基。具有两个五氟苯基的物质是具有两个直接键合于磷的有机基团的第一磷酰胺。P（CCl 3）Cl 2或P（C 6 F 5）2（NCS）没有显示出对卤离子的受体性质。

表征谱图