1,3-双(二叔丁基膦甲基)苯 | 149968-36-5

• 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 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1,3-双(二叔丁基膦甲基)苯
• 中文别名: 1,3-双[(二叔丁基膦基)甲基]苯；PCP螯合剂
• 英文名称: 1,3-bis[(di-tert-butylphosphino)methyl]benzene
• 英文别名: 1,3-Bis((di-tert-butylphosphino)methyl)benzene；ditert-butyl-[[3-(ditert-butylphosphanylmethyl)phenyl]methyl]phosphane
• CAS: 149968-36-5
• 化学式: C₂₄H₄₄P₂
• 分子量: 394.561
• InChiKey: VNLHPVUKSKTUPA-UHFFFAOYSA-N

物化性质

• 熔点：
  68-75°C
• 沸点：
  459.3±38.0 °C(Predicted)
• 稳定性/保质期：
  遵照规定使用和储存，则不会发生分解。

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 危险类别码：
  R36/37/38,R
• WGK Germany：
  3
• 安全说明：
  S26
• 储存条件：
  存放于阴凉干燥处

SDS

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Section 1: Product Identification
Chemical Name: 1,3-Bis(di-t-butylphosphinomethyl)benzene, 99%
CAS Registry Number: 149968-36-5
Formula: C6H4[CH2P(C4H9)2]2
EINECS Number: none
Chemical Family: organophosphine ligand
Synonym: 1,3-Bis di-tert-butylphosphanylmethyl-benzene

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 149968-36-5 100% no data no data

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Section 3: Hazards Identification
Emergency Overview: Irritating to skin, eyes and respiratory tract.
Primary Routes of Exposure: Ingestion, inhalation, skin, eyes
Eye Contact: Causes irritation to eyes
Skin Contact: Causes irritation to skin
Inhalation: Irritating to the nose, mucous membranes and respiratory tract.
Ingestion: No information available on the physiological effects of ingestion. May be harmful if swallowed.
Acute Health Affects: Irritating to skin, eyes and respiratory tract.
Chronic Health Affects: No information on long-term chronic effects.
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 10-15 minutes. A victim may need
Eye Exposure:
assistance in keeping their eye lids open. Get immediate medical attention.
Wash the affected area with water. Remove contaminated clothes if necessary. Seek medical assistance if
Skin Exposure:
irritation persists.
Remove the victim to fresh air. Closely monitor the victim for signs of respiratory problems, such as difficulty
Inhalation:
in breathing, coughing, wheezing, or pain. In such cases seek immediate medical assistance.
Seek medical attention immediately. Keep the victim calm. Give the victim water (only if conscious). Induce
Ingestion:
vomiting only if directed by medical personnel.

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SECTION 5: Fire Fighting Measures
Flash Point: none
Autoignition Temperature: none
Explosion Limits: none
Extinguishing Medium: carbon dioxide, dry powder or foam
If this product is involved in a fire, fire fighters should be equipped with a NIOSH 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 irritating fumes.
Decomposion Products:
Unusual Fire or Explosion Hazards: No unususal fire or explosion hazards.

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SECTION 6: Accidental Release Measures
Spill and Leak Procedures: Small spills can be mixed with vermiculite or sodium carbonate and swept up.

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SECTION 7: Handling and Storage
Handling and Storage: Store in a tightly sealed container. Keep in a cool, dry, well ventilated place.

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SECTION 8: Exposure Controls and Personal Protection
Eye Protection: Always wear approved safety glasses when handling a chemical substance in the laboratory.
Skin Protection: Wear protective clothing and gloves.
Ventilation: Handle the 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 with 29 CFR 1910.134.
Ventilation: Handle the material in an efficient fume hood.
Additional Protection: No additional protection required.

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SECTION 9: Physical and Chemical Properties
Color and Form: white powder
Molecular Weight: 394.56
Melting Point: no data
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: not determined
Solubility in Water: insoluble

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SECTION 10: Stability and Reactivity
Stability: air sensitive
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: none
Incompatibility: oxidizing agents, halogens
Decomposition Products: carbon monoxide, carbon dioxide, phosphorus pentoxide, organic fumes

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

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SECTION 12: Ecological Information
Ecological Information: No information available

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

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SECTION 14: Transportation
Shipping Name (CFR): Non-hazardous
Hazard Class (CFR): NA
Additional Hazard Class (CFR): NA
Packaging Group (CFR): NA
UN ID Number (CFR): NA
Shipping Name (IATA): Non-hazardous
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 in the TSCA inventory
SARA (Title 313): Title compound not listed
Second Ingredient: none

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  1,3-双(二叔丁基膦甲基)苯 以 四氢呋喃 、 乙二醇甲醚 为溶剂， 反应 0.67h， 生成 [(2,6-C6H3(CH2PtBu2)2)Pd(H2O)]PF6
  参考文献：
  名称：

  Catalytic amine-borane dehydrogenation by a PCP-pincer palladium complex: a combined experimental and DFT analysis of the reaction mechanism

  摘要：

  氨硼烷（NH3·BH3，AB）和二甲胺硼烷（NHMe2·BH3，DMAB）在PdII络合物[(tBuPCP)Pd(H2O)]PF6的催化下发生脱氢反应产生聚合物，并形成通用公式为cyclo-[BH2–NR2]n（n = 2,3；R = H, Me）的消耗产物，同时每当产生一个氨基硼烷时会释放出一个氢气分子。这个过程通过多核（31P，1H，11B）可变温NMR光谱进行监测；同时也对氢气产生速率和相对速率常数进行了动力学测量。在低温下可以检测到一个非氢化中间体，其化学性质通过DFT建模反应机制进行了探讨，计算水平为M06//6-31+G(d,p)。计算结果有助于提出该过程的可靠机理图像。

  DOI：

  10.1039/c2dt32273k
• 作为产物：
  描述：

  在 magnesium 作用下， 以 乙腈 为溶剂， 反应 4.0h， 以507 mg的产率得到1,3-双(二叔丁基膦甲基)苯
  参考文献：
  名称：

  One-Pot Synthesis of 1,3-Bis(phosphinomethyl)arene PCP/PNP Pincer Ligands and Their Nickel Complexes

  摘要：

  A one-pot synthesis of arene-based PCP/PNP ligands has been developed. The reaction of 1,3-bis(bromomethyl)benzene or 2,6-bis(bromomethyl)pyridine with various chlorophosphines in acetonitrile afforded bis-phosphonium salts. These salts can then be reduced by magnesium powder to yield PCP or PNP ligands. In comparison to traditional synthetic methods for making PCP/PNP ligands involving the use of secondary phosphines, this new alternative method allows for the use of chlorophosphines, which are cheaper, safer to handle, and have a broader range of commercially available derivatives. This is especially true for the chlorophosphines with less bulky alkyl groups. Moreover, the one-pot procedure can be extended to allow for the direct synthesis of PCP/PNP nickel complexes. By using nickel powder as the reductant, the resulting nickel halide was found to directly undergo metalation with the PCP or PNP ligand to generate nickel complexes in high yields.

  DOI：

  10.1021/acs.organomet.5b00671
• 作为试剂：
  描述：

  (E)-5-bromo-4,4,5,5-tetrafluoro-1-phenylpent-2-en-1-one 、 苯硼酸 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 1,3-双(二叔丁基膦甲基)苯 作用下， 以 水 、 甲苯 为溶剂， 反应 3.0h， 以40%的产率得到5-bromo-4,4,5,5-tetrafluoro-1,3-diphenylpentan-1-one
  参考文献：
  名称：

  具有四氟乙烯（–CF 2 CF 2 –）片段的不对称叔碳中心：新的构建方法及其在手性液晶分子中的应用

  摘要：

  通过各种芳基硼酸与β-（溴四氟乙基）-α，β-不饱和酮的高度对映选择性共轭加成反应，可以有效地构建具有四氟乙烯片段的不对称碳中心。该系统可以成功地应用于对映体富集的四氟乙烯化液晶分子。

  DOI：

  10.1016/j.jfluchem.2017.12.013

文献信息

• [EN] SYSTEM PROVIDING CONTROLLED DELIVERY OF GASEOUS CO FOR CARBONYLATION REACTIONS<br/>[FR] SYSTÈME PERMETTANT LA LIBÉRATION CONTRÔLÉE DE CO GAZEUX POUR RÉACTIONS DE CARBONYLATION
  申请人：UNIV AARHUS

  公开号：WO2012079583A1

  公开（公告）日：2012-06-21

  A carbonylation system comprising at least one carbon monoxide producing chamber and at least one carbon monoxide consuming chamber forming an interconnected multi-chamber system, said interconnection allowing carbon monoxide to pass from the at least one carbon monoxide producing chamber to the at least one carbon monoxide consuming chamber, said at least one carbon monoxide producing chamber containing a reaction mixture comprising a carbon monoxide precursor and a catalyst, said at least one carbon monoxide consuming chamber being suitable for carbonylation reactions, said interconnected multi- chamber system being sealable from the surrounding atmosphere during carbonylation.

  一个包括至少一个一氧化碳产生室和至少一个一氧化碳消耗室的羰基化系统，形成一个相互连接的多室系统，所述的连接允许一氧化碳从至少一个一氧化碳产生室传递到至少一个一氧化碳消耗室，所述的至少一个一氧化碳产生室包含一个反应混合物，其中包括一氧化碳前体和催化剂，所述的至少一个一氧化碳消耗室适用于羰基化反应，所述的相互连接的多室系统在羰基化过程中可以密封免受周围大气的影响。
• Synthesis, Characterization, and Catalytic Properties of Iridium Pincer Complexes Containing NH Linkers
  作者：Reuben B. Leveson-Gower、Paul B. Webb、David B. Cordes、Alexandra M. Z. Slawin、David M. Smith、Robert P. Tooze、Jianke Liu

  DOI：10.1021/acs.organomet.7b00713

  日期：2018.1.8

  hydridochloro complexes (tBu4PXCYP)IrHCl (2e, X = Y = NH; 2f, X = NH; Y = O) were prepared with moderate yields and high purity and were fully characterized by 1H and 31P NMR spectroscopy. Unsymmetrical hybrid pincer ligands R2PNCOPtBu2 (1g, R = isopropyl; 1h, R = cyclohexyl) were prepared conveniently in high yield via a one-pot procedure by judiciously choosing reaction conditions and base; the corresponding

  基于1,3-二氨基苯和3-氨基酚骨架的一系列叔丁基取代的钳位配体，tBu4 PXCYP（1e，X = Y = NH; 1f，X = NH; Y = O）和相应的铱氢化氯络合物（tBu4 PXCYP）IrHCl（2e，X = Y = NH; 2f，X = NH; Y = O）的制备具有中等收率和高纯度，并通过1 H和31 P NMR光谱进行了全面表征。不对称杂种钳配体R2 PNCOP tBu2（1g，R =异丙基; 1h通过明智地选择反应条件和碱，通过一锅法方便地以高收率制备R，（R ＝环己基）。通过[IrCl（COE）2 ] 2与配体的反应合成了相应的铱氢化氯络合物iPr2 PNCOP tBu2 IrHCl（2g）和Cy2 PNCOP tBu2 IrHCl（2h）。X射线晶体学表明，这些铱钳形配合物采用相似的正方形-金字塔形几何形状，并且在固态下，相邻的铱配合物的NH连接子和氯离子之间显示出很强的分子间氢键。叔丁基的1
• [EN] SYSTEM PROVIDING CONTROLLED DELIVERY OF GASEOUS 11CO FOR CARBONYLATION REACTIONS IN THE PREPARATION OF RADIOPHARMACEUTICALS FOR PET IMAGING<br/>[FR] SYSTÈME D'ALIMENTATION CONTRÔLÉE EN 11CO GAZEUX POUR RÉACTIONS DE CARBONYLATION DANS LA PRÉPARATION DE PRODUITS RADIOPHARMACEUTIQUES POUR IMAGERIE TEP
  申请人：UNIV AARHUS

  公开号：WO2013041106A1

  公开（公告）日：2013-03-28

  A carbonylation system comprising an enclosure sealed from the surrounding atmosphere. The enclosure comprises at least one solid support arranged for 11CO being sorped thereto, and at least one carbon monoxide consuming chamber comprising carbonylation reagents. The at least one carbon monoxide consuming chamber is arranged for performing carbonylation reactions in a gas-diffusion process between 11CO from the solid support and said carbonylation reagents to form a reaction product.

  一个羰基化系统，包括一个密封于周围大气的封闭空间。该封闭空间包括至少一个固体支撑物，用于吸附11CO，并且至少一个消耗一氧化碳的室，包括羰基化试剂。至少一个消耗一氧化碳的室被设计用于在固体支撑物的11CO和羰基化试剂之间进行气体扩散过程中进行羰基化反应，形成反应产物。
• Ti and Zr bidentate bis-phosphinimide complexes
  作者：Emily Hollink、Jeffrey C. Stewart、Pingrong Wei、Douglas W. Stephan

  DOI：10.1039/b308114a

  日期：——

  The diphosphines m-C6H4(CH2Pt-Bu2)21 and m-C6H4(CH2PCy2)22 were prepared and oxidized with Me3SiN3 to m-C6H4(CH2(t-Bu2)PNSiMe3)23 and m-C6H4(CH2(Cy2)PNSiMe3)24, and subsequently converted to m-C6H4(CH2(t-Bu)2PNH)25 and m-C6H4(CH2(Cy)2PNH)26. Reaction of 5 and 6 with Ti(NMe2)4 afforded the yellow compounds m-C6H4(CH2(t-Bu)2PN)2Ti(NMe2)27 and m-C6H4(CH2(Cy)2PN)2Ti(NMe2)28, and the low abundance by-product m-C6H4(CH2(t-Bu)2PN)2TiBr(NMe2) 9. In a similar manner, the species m-C6H4(CH2(t-Bu)2PN)2Zr(NEt2)210 was prepared from Zr(NEt2)4. Compounds 8, 9 and 10 were converted to C6H4(CH2(t-Bu)2PN)2TiBr211, m-C6H4(CH2(Cy)2PN)2TiCl213 and C6H4(CH2(t-Bu)2PN)2ZrCl214via reaction with Me3SiX (X = Br, Cl). Alternatively, m-C6H4(CH2(t-Bu)2PN)2TiCl212 and 13 were prepared in low yield from reaction of 3 or 4 with TiCl4. Alkylation of 11 with MeMgBr and PhCH2MgBr proceeded to give m-C6H4(CH2(t-Bu)2PN)2TiMe215 and m-C6H4(CH2(t-Bu)2PN)2Ti(CH2Ph)216, respectively. The species (m-C6H4(CH2(t-Bu)2PN)2)2Zr 17 was prepared from Zr(CH2Ph)4. These synthetic routes are described and the implications for applications in olefin polymerization catalysis are considered. X-Ray structural data for compounds 1, 3, 4, 5, 8, 9 and 16 are reported.

  合二膦化合物 m-C6H4(CH2Pt-Bu2)21 和 m-C6H4(CH2PCy2)22 被合成并用 Me3SiN3 氧化成 m-C6H4(CH2(t-Bu2)PNSiMe3)23 和 m-C6H4(CH2(Cy2)PNSiMe3)24，随后转化为 m-C6H4(CH2(t-Bu)2PNH)25 和 m-C6H4(CH2(Cy)2PNH)26。化合物 5 和 6 与 Ti(NMe2)4 反应生成黄色化合物 m-C6H4(CH2(t-Bu)2PN)2Ti(NMe2)27 和 m-C6H4(CH2(Cy)2PN)2Ti(NMe2)28，以及少量副产物 m-C6H4(CH2(t-Bu)2PN)2TiBr(NMe2)9。以类似方法，从 Zr(NEt2)4 制备出物种 m-C6H4(CH2(t-Bu)2PN)2Zr(NEt2)210。化合物 8、9 和 10 通过与 Me3SiX (X = Br, Cl) 反应转化为 C6H4(CH2(t-Bu)2PN)2TiBr211、m-C6H4(CH2(Cy)2PN)2TiCl213 和 C6H4(CH2(t-Bu)2PN)2ZrCl214。或者，m-C6H4(CH2(t-Bu)2PN)2TiCl212 和 13 是通过化合物 3 或 4 与 TiCl4 的反应获得的低产率化合物。化合物 11 与 MeMgBr 和 PhCH2MgBr 的烷基化反应分别生成 m-C6H4(CH2(t-Bu)2PN)2TiMe215 和 m-C6H4(CH2(t-Bu)2PN)2Ti(CH2Ph)216。物种 (m-C6H4(CH2(t-Bu)2PN)2)2Zr 17 是从 Zr(CH2Ph)4 制备的。这些合成路线被描述，并考虑了在烯烃聚合催化应用中的意义。报告了化合物 1、3、4、5、8、9 和 16 的 X 射线结构数据。
• Practical Gas Cylinder-Free Preparations of Important Transition Metal-Based Precatalysts Requiring Gaseous Reagents
  作者：Hongwei Sun、Alexander Ahrens、Steffan K. Kristensen、Laurynas Gausas、Bjarke S. Donslund、Troels Skrydstrup

  DOI：10.1021/acs.oprd.1c00205

  日期：2021.10.15

  corresponding precatalysts are of high relevance in the active research fields of C–H bond activation, dehydrogenation, hydrogenation, and coupling reactions. The selection of complexes shown is meant to serve as examples for the usefulness and broadness of the presented methods, allowing precatalysts requiring gaseous reagents to become available for the research community.

  报道了一种用于合成一系列重要的过渡金属基预催化剂的简单而安全的设置，所有这些都需要低分子量气态试剂来制备。氢气、一氧化碳、乙烯和乙炔均以受控方式从封闭的两室反应器中的相应易于处理的前体中释放出来。因此可以避免使用与处理文献中报道的有毒和/或易燃气体相关的气瓶和复杂的设置/技术。相应的预催化剂在 C-H 键活化、脱氢、加氢和偶联反应等活跃的研究领域具有重要意义。所示复合物的选择旨在作为所提出方法的有用性和广泛性的示例，