双[2-(二异丙基膦基)乙基]胺 | 131890-26-1

• 物质功能分类: 有机原料 - 氨基化合物
• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 中文名称: 双[2-(二异丙基膦基)乙基]胺
• 中文别名: 双[2-(二异丙基膦基)乙基]胺, 1% W/W THF 溶液
• 英文名称: bis[(2-diisopropylphosphino)ethyl]amine
• 英文别名: bis(2-(diisopropylphosphaneyl)ethyl)amine；bis(diiso-propylphosphinoethyl)amine；Bis[(2-di-i-propylphosphino]ethyl)amine；2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanylethyl]ethanamine
• CAS: 131890-26-1
• 化学式: C₁₆H₃₇NP₂
• 分子量: 305.424
• InChiKey: FTVIGQGOGIHMBS-UHFFFAOYSA-N

物化性质

• 沸点：
  375.9±27.0 °C(Predicted)
• 密度：
  0.884 g/mL at 25 °C
• 闪点：
  -17 °C
• 暴露限值：
  ACGIH: TWA 50 ppm; STEL 100 ppm (Skin)OSHA: TWA 200 ppm(590 mg/m3)NIOSH: IDLH 2000 ppm; TWA 200 ppm(590 mg/m3); STEL 250 ppm(735 mg/m3)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

安全信息

• 危险等级：
  3
• 储存条件：
  | 室温 |

SDS

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Section 1: Product Identification
Chemical Name: Bis[(2-di-i-propylphosphino)ethyl]amine, min. 97% (10 wt% in tetrahydrofuran)
CAS Registry Number: 131890-26-1
Formula: C16H37NP2
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 131890-26-1 10% no data no data
THF 109-99-9 90% 50ppm 590mg/m3

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Section 3: Hazards Identification
Irritating to skin, eyes and respiratory tract. May be harmful if swallowed. Vapor can cause drowsiness and
Emergency Overview:
unconsciousness. Possible risk of harm to the unborn child and irreversible effects.
Primary Routes of Exposure: Ingestion, inhalation, skin, eyes
Eye Contact: Causes severe irritation to the eyes.
Skin Contact: Causes moderate to severe irritation of the skin.
Inhalation of vapors may cause coughing, chest pains, nausea, dizziness, headache, drowsiness and
Inhalation:
unconsciousness.
Ingestion: Harmful if swallowed. THF can cause liver and kidney damage. Harmful if swallowed.
Inhalation of vapors induces drowsiness and may cause coughing, chest pains, difficulty in breathing, nausea,
Acute Health Affects: dizziness, headache and unconsciousness. Skin and eye contact results in irritation. Possible risk of harm to
the unborn child.
Tetrahydrofuran is an eye and mucous membrane irritant and can cause liver and kidney damage. Possible
Chronic Health Affects:
risk of irreversible 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: 1°F (THF)
Autoignition Temperature: 610°F (THF)
Explosion Limits: 1.8%-11.8% (THF)
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 toxic and corrosive fumes.
Decomposion Products:
Unusual Fire or Explosion Hazards: Flammable liquid. Evolves flammable hydrogen gas with water. Hydrogen can ignite explosively.

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SECTION 6: Accidental Release Measures
Eliminate all potential ignition sources. Small spills can be absorbed into vermiculite or other chemical
Spill and Leak Procedures:
adsorbent suitable for flammable materials. Sweep up the mixture and dispose of properly.

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SECTION 7: Handling and Storage
Handling and Storage: Handle and store this material under an inert atmosphere of nitrogen or argon. Keep away from heat.

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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.
Wear protective clothing and gloves. Consult with a glove manufacturer to determine the proper type of glove.
Skin Protection:
Ventilation: It is imperative that this material is handled 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: It is imperative that this material is handled in an efficient fume hood.
Additional Protection: No additional protection required.

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SECTION 9: Physical and Chemical Properties
Color and Form: colorless to pale yellow liquid
Molecular Weight: 305.42
Melting Point: no data
Boiling Point: 66°C (THF)
Vapor Pressure: 0.173 Atm at 20°C (THF)
Specific Gravity: no data
Odor: ethereal
Solubility in Water: Insoluble

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SECTION 10: Stability and Reactivity
Stability: air sensitive
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: heat, ignition sources, air exposure
Incompatibility: water, oxidizing agents, halogens, air and mineral acids
Decomposition Products: carbon monoxide, carbon dioxide, nitrogen oxides, phosphorous oxides and organic fumes

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SECTION 11: Toxicological Information
Title compound: No information available in the RTECS files. THF: Inhalation(human); TCLo: 25000ppm.
Oral(rat); LD50: 1650mg/kg. Inhalation(rat); LC50: 21000ppm/3H. Intraperitoneal(rat); LD50: 2900mg/kg.
RTECS Data:
Inhalation(mouse); LCLo: 24000mg/m3/2H. Inhalation(rabbit); LC: >1200ppm/4H. Oral(guinea pig); LDLo:
500mg/kg. Inhalation(rat); TCLo: 1800ppm/6H/2Y-I.
Carcinogenic Effects: THF: Insufficient data
Mutagenic Effects: THF: Possible mutagen
Tetratogenic Effects: THF: Possible reproductive effector

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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): Flammable liquids, N.O.S.
Hazard Class (CFR): 3
Additional Hazard Class (CFR): NA
Packaging Group (CFR): I
UN ID Number (CFR): UN# 1993
Shipping Name (IATA): Flammable liquid, N.O.S.
Hazard Class (IATA): 3
Additional Hazard Class (IATA): NA
Packaging Group (IATA): I
UN ID Number (IATA): UN# 1993

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SECTION 15: Regulatory Information
TSCA: Title compound: Not listed in the TSCA inventory.
SARA (Title 313): Not reportable under SARA 313.
Second Ingredient: THF: Listed in the TSCA inventory. Not reportable under SARA 313.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  双[2-(二异丙基膦基)乙基]胺 在 KO-t-Bu 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成 2-di(propan-2-yl)phosphanyl-N-[2-di(propan-2-yl)phosphanylethyl]-N-methylethanamine;palladium(2+);trifluoromethanesulfonate;chloride
  参考文献：
  名称：

  Palladium N(CH₂CH₂PⁱPr₂)₂-Dialkylamides: Synthesis, Structural Characterization, and Reactivity

  摘要：

  Palladium(II) aminodiphosphine PNP pincer complexes [PdR(PNPH]PF6 (1(R); R = Cl Me, Ph; PNPH = HN((CH2CH2PPr2)-Pr-i)(2)) were prepared. Deprotonation with (KOBu)-Bu-t affords dialkylamides [PdR(PNP)] (2(R); R = Cl Me, Ph; PNP = ((NCH2CH2PPr2)-Pr-i)(2)) in high yield which are stable toward beta-H elimination. While AgPF6 oxidizes the amides, cationic amido complexes [PdL(PNP)]PF6 (3(L); L = (CNBu)-Bu-t, PMe3) were obtained upon chloride abstraction from 1(Cl) with TIPF6. The reaction of amide 2(Cl) with MeOTf results in N-methylation yielding [PdCl(PNPMe)]OTf (5) quantitatively. N-H acidities of the amino complexes 1(Me) (pK(a) = 24.2(1)) and 1(Ph) (pK(a) = 23.2(1)) were determined in dmso. Complexes 1(Cl), 1(Me), 2(Cl) 2(Me), 3(CNf8u), and 5 were structurally characterized by single crystal X-ray diffraction. The amido complexes feature pyramidal nitrogen atoms in the solid state. The molecular structures, high N-basicity, and reactivity of the amido complexes can be explained with Pd-N-amido bonding that is characterized by strong N -> Pd sigma-donation and repulsive d(pi)-p(pi) pi-interactions. This interpretation was confirmed by density functional theory (DFT) calculations of 2(Cl).

  DOI：

  10.1021/ic802286u
• 作为产物：
  描述：

  在 水 作用下， 以 四氢呋喃 、 六氯乙烷 为溶剂， 反应 5.0h， 生成 双[2-(二异丙基膦基)乙基]胺
  参考文献：
  名称：

  IRIDIUM CATALYSTS FOR CATALYTIC HYDROGENATION

  摘要：

  本公开涉及一种用于还原含有一个或多个碳-氧（C═O）双键的化合物以提供相应醇的过程，包括将该化合物与氢气在大于3大气压力下接触，并且使用包含铱氨基二膦配合物的催化剂。

  公开号：

  US20080300430A1
• 作为试剂：
  描述：

  碘环己烷 、 (4-chlorobenzylidene)hydrazine 在 双[2-(二异丙基膦基)乙基]胺 、 potassium tert-butylate 、 cobalt(II) chloride 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 24.0h， 以56%的产率得到1-chloro-4-(cyclohexylmethyl)benzene
  参考文献：
  名称：

  温和条件下钴催化的 Umpolung 羰基化合物与卤代烷的交叉偶联

  摘要：

  虽然经典的交叉偶联以钯和镍催化剂为主，但钴基催化剂在这种交叉偶联反应中表现出独特的优势，即更高的催化活性和更低的毒性。在此，我们描述了一种新型钴催化的腙与卤代烷在温和反应条件下的烷基-烷基交叉偶联反应，其中使用 PNP 型钳形配体对催化至关重要。醛和酮腙都与该反应相容，以中等至良好的产率产生一系列 C(sp 3 )–C(sp 3 ) 偶联产物。

  DOI：

  10.1039/d2cc04302e

文献信息

• Dynamic Kinetic Resolution of Alcohols by Enantioselective Silylation Enabled by Two Orthogonal Transition‐Metal Catalysts
  作者：Jan Seliger、Martin Oestreich

  DOI：10.1002/anie.202010484

  日期：2021.1.4

  A nonenzymatic dynamic kinetic resolution of acyclic and cyclic benzylic alcohols is reported. The approach merges rapid transition‐metal‐catalyzed alcohol racemization and enantioselective Cu‐H‐catalyzed dehydrogenative Si‐O coupling of alcohols and hydrosilanes. The catalytic processes are orthogonal, and the racemization catalyst does not promote any background reactions such as the racemization

  报道了无环和环状苯甲醇的非酶动态动力学拆分。该方法融合了快速过渡金属催化的醇外消旋化和对映选择性 Cu-H 催化的醇和氢硅烷的脱氢 Si-O 偶联。催化过程是正交的，并且外消旋催化剂不会促进任何背景反应，例如甲硅烷基醚的外消旋及其非选择性形成。常用的钌半夹心配合物并不合适，但双功能钌钳形配合物完美地实现了这一目的。由此，可以高产率和良好的对映选择水平实现外消旋醇混合物的对映选择性硅烷化。
• Additive‐Free Isomerization of Allylic Alcohols to Ketones with a Cobalt PNP Pincer Catalyst
  作者：Brian Spiegelberg、Andrea Dell'Acqua、Tian Xia、Anke Spannenberg、Sergey Tin、Sandra Hinze、Johannes G. de Vries

  DOI：10.1002/chem.201901148

  日期：2019.6.12

  Catalytic isomerization of allylic alcohols in ethanol as a green solvent was achieved by using air and moisture stable cobalt (II) complexes in the absence of any additives. Under mild conditions, the cobalt PNP pincer complex substituted with phenyl groups on the phosphorus atoms appeared to be the most active. High rates were obtained at 120 °C, even though the addition of one equivalent of base

  通过在不存在任何添加剂的情况下使用空气和湿气稳定的钴（II）配合物，可以实现烯丙醇在乙醇中的催化异构化（绿色溶剂）。在温和的条件下，被磷原子上的苯基取代的钴PNP钳形络合物似乎是活性最高的。即使加入一当量的碱可大大提高反应速度，但在120°C时仍可获得较高的反应速率。尽管获得了支持脱氢-加氢机理的一些证据，但已证明这不是主要机理。取而代之的是，乙醇脱氢形成的氢化钴配合物能够通过烯烃插入-消除反应实现双键异构化。
• Selective Construction of C−C and C=C Bonds by Manganese Catalyzed Coupling of Alcohols with Phosphorus Ylides
  作者：Xin Liu、Thomas Werner

  DOI：10.1002/adsc.202001209

  日期：2021.2.16

  manganese catalyzed coupling of alcohols with phosphorus ylides. The selectivity in the coupling of primary alcohols with phosphorus ylides to form carbon‐carbon single (C−C) and carbon‐carbon double (C=C) bonds can be controlled by the ligands. In the conversion of more challenging secondary alcohols with phosphorus ylides the selectivity towards the formation of C−C vs. C=C bonds can be controlled by the

  在本文中，我们报道了锰与磷酰化物的锰催化偶联。伯醇与磷酰化物偶联形成碳碳单键（CC）和碳碳双键（C = C）的选择性可以通过配体控制。在更具挑战性的仲醇与磷酰化物的转化中，通过反应条件，即碱的量，可以控制形成CC与C = C键的选择性。偶联反应的范围和局限性通过21种醇和15种烷基化物的转化得到了彻底评估。值得注意的是，与基于贵金属络合物作为催化剂的现有方法相比，本催化体系基于富含稀土的锰催化剂。该反应也可以在顺序的一锅法反应中进行，该反应在锰催化的C-C和C = C键形成后就地生成磷叶立德。机理研究表明，CC键是通过借位氢途径生成的，而C = C键的形成遵循无受体的脱氢偶联途径。
• Osmium and Ruthenium Catalysts for Dehydrogenation of Alcohols
  作者：Marcello Bertoli、Aldjia Choualeb、Alan J. Lough、Brandon Moore、Denis Spasyuk、Dmitry G. Gusev

  DOI：10.1021/om200437n

  日期：2011.7.11

  of pincer-type complexes of Os and Ru have been synthesized and investigated in catalytic alcohol dehydrogenation. The hydrides OsHCl(CO)[HN(C2H4PiPr2)2] and OsH2(CO)[HN(C2H4PiPr2)2] possess good air, moisture, and thermal stability and are outstanding versatile dehydrogenation catalysts for primary alcohols for reactions of transfer hydrogenation, dehydrogenative coupling, and amine alkylation.

  合成了一系列Os和Ru的钳型配合物，并在催化醇脱氢中进行了研究。氢化物OsHCl（CO）[HN（C 2 H 4 P i Pr 2）2 ]和OsH 2（CO）[HN（C 2 H 4 P i Pr 2）2 ]具有良好的空气，湿气和热稳定性，并且是用于伯醇的杰出通用型脱氢催化剂，用于转移氢化，脱氢偶联和胺烷基化反应。
• Iron-Catalyzed Alkylation of Nitriles with Alcohols
  作者：Wei Ma、Suya Cui、Huamin Sun、Weijun Tang、Dong Xue、Chaoqun Li、Juan Fan、Jianliang Xiao、Chao Wang

  DOI：10.1002/chem.201803762

  日期：2018.9.6

  A general, efficient iron‐catalyzed α‐alkylation of nitriles with primary alcohols through a hydrogen‐borrowing pathway has been developed, allowing a wide variety of alkylated nitriles to be readily accessible. Detailed mechanistic studies suggest that the reaction proceeds via an olefin intermediate with the turnover rate limited by the hydrogenation of the olefin with an iron hydride. Apart from

  已经开发了一种普遍的，通过氢借入途径与伯醇进行的高效铁催化的腈与伯醇的α-烷基化反应，使各种烷基化的腈均易于获得。详细的机理研究表明，反应是通过烯烃中间体进行的，其转化率受烯烃与氢化铁的氢化作用所限制。除了参与烷基化以外，还发现腈在促进活性催化物质的形成和稳定中起着重要作用。