二对甲苯膦 | 1017-60-3

• 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 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 二对甲苯膦
• 中文别名: 二-P-二甲苯氯化磷；P-二甲苯氯化磷；二对甲苯基磷
• 英文名称: di-p-tolylphosphine
• 英文别名: bis(4-methylphenyl)phosphine；di-p-tolylphosphane；bis(p-tolyl)-phosphine；Di-p-tolyl-phosphin；di-p-methylphenylphosphine；bis(4-methylphenyl)phosphane
• CAS: 1017-60-3
• 化学式: C₁₄H₁₅P
• mdl: MFCD01630843
• 分子量: 214.247
• InChiKey: RRSCGNXXNRAXJC-UHFFFAOYSA-N

物化性质

• 沸点：
  122-124 °C(Press: 2 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.142
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 危险类别码：
  R17,R34
• 危险品运输编号：
  UN 2845
• 海关编码：
  2902909090
• 安全说明：
  S16,S26,S27,S36/37/39
• 储存条件：
  存放条件：室温且干燥环境中

SDS

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Section 1: Product Identification
Chemical Name: Di-p-tolylphosphine, 99%
CAS Registry Number: 1017-60-3
Formula: (CH3C6H4)2PH
EINECS Number: none
Chemical Family: organophosphine ligand
Synonym: none

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title Compound 1017-60-3 100% no data no data

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Section 3: Hazards Identification
Harmful by inhalation, in contact with skin and if swallowed. May ignite spontaneously on contact with air.
Emergency Overview:
Contact with skin may result in severe chemical burns.
Primary Routes of Exposure: Skin and inhalation
Eye Contact: May cause mild to severe irritation of the eyes.
Skin Contact: Harmful in contact with skin. May cause mild irritation of the skin, or thermal burns if ignited.
Inhalation: Harmful by inhalation. Inhalation may lead to dizziness and headaches.
Harmful if swallowed. Ingestion is an unlikely mode of entry as the material is pyrophoric and has a noxious
Ingestion:
odor.
Acute Health Affects: Harmful by inhalation, in contact with skin and if swallowed.
Chronic Health Affects: No information available on long term exposure to this material.
NTP: No
IARC: No
OSHA: No

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SECTION 4: First Aid Measures
Immediately flush the eyes with copious amounts of water for at least 15 minutes. A victim will need
Eye Exposure:
assistance in keeping their eye lids open. Get immediate medical attention.
Wash the affected area immediately with water. Remove contaminated clothing if necessary. Seek medical
Skin Exposure:
assistance if irritation persists.
Remove victim to fresh air immediately. Keep the victim lying down and warm. Give oxygen as soon as
Inhalation:
possible. If shock occurs, respond with appropriate first aid. Transport the victim to a hospital.
Seek medical attention immediately. Keep the victim calm. Give water to dilute the toxin (only if conscious).
Ingestion:
Induce vomiting only if directed by medical personnel.

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SECTION 5: Fire Fighting Measures
Flash Point: no data
Autoignition Temperature: Pyrophoric
Explosion Limits: Pyrophoric
Extinguishing Medium: carbon dioxide, dry powder or foam
The pyrophoric liquid may reignite. Fire fighters should be equipped with an approved positive pressure
Special Fire Fighting Procedures:
self-contained breathing apparatus and full protective clothing.
Hazardous Combustion and If involved in a fire this material may emit toxic organic fumes and vapors of phosphorus pentoxide.
Decomposion Products:
Unusual Fire or Explosion Hazards: Spontaneously flammable in air, especially in contact with organic matter such as paper or cloth.

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SECTION 6: Accidental Release Measures
'The material may ignite spontaneously in air. Avoid static discharge. Burning material may release
toxic fumes. In case of poor ventilation, leave the area unless fitted with a self-contained breathing apparatus.
Spill and Leak Procedures:
Small spills can be mixed with ground limestone, sodium bicarbonate, or other suitable absorbents, swept up,
and held in a closed metal can.

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SECTION 7: Handling and Storage
Store in a tightly sealed container under an inert atmosphere of nitrogen or argon. Keep away from heat.
Handling and Storage: Material should be transferred under an inert atmosphere of nitrogen or argon in a efficient fume hood. Fire
may occur in emptied container and transfer lines.

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SECTION 8: Exposure Controls and Personal Protection
Always wear approved safety glasses. When handling this substance wear a face shield as added protection.
Eye Protection:
Skin Protection: Wear protective clothing and gloves. Consult with glove manufacturer to determine the proper type of glove.
Ventilation: Material has a pungent odor. Always handle material in an efficient fume hood.
If ventilation is not available a respirator should be worn. The use of respirators requires a Respirator
Respirator:
Protection Program to be in compliance 29 CFR 1910.134.
Ventilation: Material has a pungent odor. Always handle material in an efficient fume hood.
Additional Protection: Wear a full face shield, flame resistant lab apron and suitable gloves.

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SECTION 9: Physical and Chemical Properties
Color and Form: colorless liq.
Molecular Weight: 214.25
Melting Point: no data
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: pungent and noxious odor
Solubility in Water: insoluble

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SECTION 10: Stability and Reactivity
Stability: air-sensitive liquid - pyrophoric
Hazardous Polymerization: no hazardous polymerization
Contact with air. Material may spontaneously ignite, especially in the presence of organic matter such as
Conditions to Avoid:
paper or cloth.
Incompatibility: oxidizing agents, halogens, air (pyrophoric), halocarbons, sulfur.
Decomposition Products: carbon dioxide, carbon monoxide, organic vapors, and phosphorus pentoxide.

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SECTION 11: Toxicological Information
RTECS Data: No information available in the RTECS files.
Carcinogenic Effects: No information available.
Mutagenic Effects: No information available.
Tetratogenic Effects: No information available.

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SECTION 12: Ecological Information
Ecological Information: No information available.

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SECTION 13: Disposal Considerations
Disposal: Dispose of this material according to local, state and federal regulations.

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SECTION 14: Transportation
Shipping Name (CFR): Pyrophoric liquids, organic, N.O.S.
Hazard Class (CFR): 4.2
Additional Hazard Class (CFR): NA
Packaging Group (CFR): I
UN ID Number (CFR): UN# 2845
Shipping Name (IATA): Forbidden
Hazard Class (IATA): NA
Additional Hazard Class (IATA): NA
Packaging Group (IATA): NA
UN ID Number (IATA): NA

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SECTION 15: Regulatory Information
TSCA: not listed on the TSCA inventory
SARA (Title 313): not regulated by SARA 313
Second Ingredient: none

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  二对甲苯膦 在 1,1'-双(二苯基膦)二茂铁 、 tris-(dibenzylideneacetone)dipalladium(0) 、 caesium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 18.0h， 生成 三对苯甲基膦
  参考文献：
  名称：

  通过将 ArBr/ArOTf 与酰基膦偶联形成钯催化的 C-P(III) 键

  摘要：

  据报道，钯催化的 ArBr/ArOTf 的 C-P 键形成反应使用酰基膦作为差异膦化试剂。酰基膦显示出与作为膦化试剂的 ArBr 和 ArOTf 的实际反应性，尽管它们对空气和湿气呈惰性。该反应直接以良好的收率提供三价膦，具有广泛的底物范围和官能团耐受性。该反应揭示了酰基膦作为直接合成三价膦的新磷源的能力。

  DOI：

  10.1021/acs.joc.1c00937
• 作为产物：
  描述：

  对氯甲苯 在 二异丁基氢化铝 、 magnesium 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 7.0h， 生成 二对甲苯膦
  参考文献：
  名称：

  氯化锂卡宾选择性脱氢偶联膦

  摘要：

  介绍了一种通过膦脱氢偶联形成磷-磷键的简单、无过渡金属的方法的发展。该反应由电子稳定的氯化锂卡宾介导，并在温和的反应条件下提供各种不同的二膦。开发的协议简单高效，可以高产率地分离新型功能化二膦。

  DOI：

  10.1021/ja509381w
• 作为试剂：
  描述：

  (S)-1-(isoquinolin-1-yl)naphthalen-2-yl triflate 、 二苯基膦 在 4-二甲氨基吡啶 、 (R,SFc)-Josiphos SL-J₀₀₃-1 、 二对甲苯膦 作用下， 以 1,4-二氧六环 、 均三甲苯 为溶剂， 反应 14.0h， 生成 1-(2-二苯基庚基1萘酚)硫酸甲基酯
  参考文献：
  名称：

  Asymmetric Synthesis of QUINAP via Dynamic Kinetic Resolution

  摘要：

  A palladium-catalyzed, atroposelective C-P coupling process has been developed for the asymmetric synthesis of QUINAP and its derivatives in high enantiomeric excess. Bromide, triflate (OTf) and 4-methanesulfonylbenzenesulfonate (OSs) precursors were studied, leading in the case of the triflate to a novel dynamic kinetic resolution involving isomerization of an arylpalladium intermediate. The operationally simple methods described in this communication afford these important ligands in good to high yields and selectivity using low catalyst loading (<= 3 mol % Pd).

  DOI：

  10.1021/ja409383f

文献信息

• Eine einfache synthese von tripod-liganden H3CC(CH2PAr2)3: Anwendungsbreite und komplexchemie
  作者：A. Muth、O. Walter、G. Huttner、A. Asam、L. Zsolnai、Ch. Emmerich

  DOI：10.1016/0022-328x(94)80044-8

  日期：1994.4

  The reaction of 1,1,1-tris(chlormethyl)ethane H3CC(CH2Cl)3 with Ar2PH in DMSO as the solvent using KOH/H2O as the base gives good yields of tripod ligands H3CC(CH2PAr2)3, 2. Using Ph2PH as the phosphine component, it is shown that the chloride substituents of H3CC(CH2Cl)3 are exchanged in sequence by the formation of H3CC(CH2Cl)2(CH2PPh2), 1a, and H3CC(CH2Cl)(CH2PPh2)2, 1b, respectively. The product

  1,1,1-三（氯甲基）乙烷H 3 CC（CH 2 Cl）3与Ar 2 PH在DMSO中的溶剂以KOH / H 2 O为碱的反应产生了良好的三脚架配体H 3 CC收率（CH 2 PAR 2）3，2。使用Ph 2 PH作为膦组分，表明H 3 CC（CH 2 Cl）3的氯取代基通过形成H 3 CC（CH 2 Cl）2（CH 2 PPh 2）依次交换，图1A和H 3 CC（CH 2 Cl）的（CH 2 PPH 2）2，1B，分别。产品组成几乎完全由所应用的化学计量确定。获得三脚架配体2，其中Ar =苯基，2a，3-甲苯基，2b，4-甲苯基，2c，4-叔丁基苯基，2d，1-萘基，2f和Ar 2 P二苯并磷酰基，2e作为Ar 2个P组。它们在钼和铁的配合物的面部的协调能力是通过所述类型的化合物的表征证实三球的Mo（CO）3，3，和[三脚架-铁（NCCH 3）3 ]（BF 4）2，4。化合物1-4的
• Gold(<scp>I</scp>) complexes derived from secondary phosphines: [{Au(µ-PR₂)}_n],[(AuBr)₂(µ-PPh₂)]^–, [AuX(PHR₂)], and [{Au(PHR₂)_n}]⁺. Crystal structure of [AuBr(PHPh₂)]
  作者：David B. Dyson、R. V. Parish、Charles A. McAuliffe、Robin G. Pritchard、Roy Fields、Brian Beagley

  DOI：10.1039/dt9890000907

  日期：——

  The interaction of secondary phosphines with a variety of gold(I) compounds has been studied. In the presence of bases or polar solvents, polymeric gold(I) phosphides [Au(µ-PR2)}n] are formed. When these are obtained in the absence of additional ligands they are soluble, presumably with ring structures. More usually, insoluble forms are found, presumably with chain structures. The probable formation

  已经研究了次膦与各种金（I）化合物的相互作用。在碱或极性溶剂的存在下，形成聚合的金（I）磷化物[Au（µ-PR 2）} n ]。当在没有其他配体的情况下获得它们时，它们是可溶的，大概具有环结构。更通常地，发现不溶形式，大概具有链结构。讨论了由[AuX（PH R 2）]型配合物形成这些物质的可能性，并分离了后者的配合物（X = Cl或Br，R = Ph或对甲苯基）和新型单体磷酸酯桥联阴离子[（AuBr）2（µ-PPh 2）] –描述。在非极性溶剂中，会形成一系列仲膦配合物，[Au（PHPh 2）n ] +（n = 2-4），但是对于n = 3而言，似乎歧化不稳定。该化合物的特征在于31 P nmr和197 AuMössbauer光谱学，[AuBr（PH Ph 2）]情况下的X射线晶体学。
• Monophosphine and diphosphine ligands for diplatinum polyynediyl complexes: Efficient syntheses of new functionality-containing systems and model compounds
  作者：Laura de Quadras、Jürgen Stahl、Fedor Zhuravlev、John A. Gladysz

  DOI：10.1016/j.jorganchem.2006.12.023

  日期：2007.4

  similarly yield R2P(CH2)mPR2 (m/R = 8/a, 95%; 14/a, 96%; 14/p-C6H4-t-Bu, 98%). Reactions of KPPh2 with Br(CH2)m′CHCH2and Br(CH2)7CH3 give the corresponding monophosphines Ph2P(CH2)m′CHCH2 (m′ = 7, 82%; 10, 84%) and Ph2P(CH2)7CH3 (85%). When the former is combined with [Pt(μ-Cl)(C6F5)(tht)]2 (tht = tetrahydrothiophene), trans-(C6F5)(Ph2P(CH2)m′CHCH2)2PtCl (77–70%) is isolated. When the latter (excess)

  Br（CH 2）4 Br和NaO（CH 2）2 CHCH 2在合适的条件下反应，生成Br（CH 2）4 O（CH 2）2 CHCH 2（55％），将其用KPPh 2处理后得到含醚的膦Ph 2 P（CH 2）4 O（CH 2）2 CHCH 2（83％）。CH 3 CH 2 OC（O）CHC（CH 3）2与BrMg（CH 2）3的反应在CuCl（cat。）和ClSiMe 3存在下的CHCH 2生成CH 3 CH 2 OC（O）CH 2 C（CH 3）2（CH 2）3 CHCH 2（67％），将其还原为醇将其溴化，与Grubbs的催化剂反应，氢化，并用KPPh 2处理，得到双（双甲基化）二膦Ph 2 P（CH 2）2 C（CH 3）2（CH 2）8 C（CH 3）2（通道2）2 PPh 2（整体47％）。I（CF 2）8 I和H 2 CCHCH 2 SnBu 3的光化学反应产生H 2 CCHCH
• Rapid Metal-Free Formation of Free Phosphines from Phosphine Oxides
  作者：Cei B. Provis-Evans、Emma A. C. Emanuelsson、Ruth L. Webster

  DOI：10.1002/adsc.201800723

  日期：2018.10.18

  A rapid method for the reduction of secondary phosphine oxides under mild conditions has been developed, allowing simple isolation of the corresponding free phosphines. The methodology involves the use of pinacol borane (HBpin) to effect the reduction while circumventing the formation of a phosphine borane adduct, as is usually the case with various other commonly used borane reducing agents such as

  已经开发出一种在温和条件下还原仲膦氧化物的快速方法，可以简单地分离相应的游离膦。该方法涉及使用频哪醇硼烷（HBpin）的，以实现同时避免膦硼烷加合物的形成的减少，如通常与各种其它常用的甲硼烷还原剂的情况下，如硼烷四氢呋喃复合物（BH 3 ⋅THF）和硼烷二甲硫醚复合物（BH 3 ⋅SMe 2）。此外，这种方法只需要少量过量的还原剂，因此不仅可以与不需要金属助催化剂的其他硼烷还原剂进行比较，而且可以与硅烷和铝基试剂进行比较。
• A Superior Method for the Reduction of Secondary Phosphine Oxides
  作者：Carl A. Busacca、Jon C. Lorenz、Nelu Grinberg、Nizar Haddad、Matt Hrapchak、Bachir Latli、Heewon Lee、Paul Sabila、Anjan Saha、Max Sarvestani、Sherry Shen、Richard Varsolona、Xudong Wei、Chris H. Senanayake

  DOI：10.1021/ol0517832

  日期：2005.9.1

  to be outstanding reductants for secondary phosphine oxides (SPOs). All classes of SPOs can be readily reduced, including diaryl, arylalkyl, and dialkyl members. Many SPOs can now be reduced at cryogenic temperatures, and conditions for preservation of reducible functional groups have been found. Even the most electron-rich and sterically hindered phosphine oxides can be reduced in a few hours at 50-70

  [反应：见正文]已发现氢化二异丁基铝（DIBAL-H）和三异丁基铝是仲氧化膦（SPO）的杰出还原剂。所有类别的SPO都可以轻松还原，包括二芳基，芳基烷基和二烷基成员。现在可以在低温下还原许多SPO，并发现了保存可还原官能团的条件。即使是最富电子和位阻的膦氧化物，也可以在50-70摄氏度的温度下在几小时内还原。这种新的还原方法与现有技术相比具有明显的优势。