（R）-2-[（（二苯基膦基）甲基]吡咯烷 | 428514-91-4

• 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: （R）-2-[（（二苯基膦基）甲基]吡咯烷
• 中文别名: (R)-(+)-2-(二苯基膦基甲基)吡咯烷, 97+%
• 英文名称: (R)-2-[(diphenylphosphino)methyl]pyrrolidine
• 英文别名: (R)-2-((diphenylphosphanyl)methyl)pyrrolidine；diphenyl-[[(2R)-pyrrolidin-2-yl]methyl]phosphane
• CAS: 428514-91-4
• 化学式: C₁₇H₂₀NP
• 分子量: 269.326
• InChiKey: IWRBGJKCDORZHK-OAHLLOKOSA-N

物化性质

• 沸点：
  387.1±15.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

SDS

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Section 1: Product Identification
Chemical Name: (R)-2-[(Diphenylphosphino)methyl]pyrrolidine, min. 97% (10 wt% in hexanes)
CAS Registry Number: 428514-91-4
Formula: C17H20NP
EINECS Number: none
Chemical Family: organophosphine ligand
Synonym: (R)-2-[(Diphenylphosphano)methyl]pyrrolidine

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 428514-91-4 10% no data no data
Hexane 73513-42-5 90% 50ppm 1800mg/m3

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Section 3: Hazards Identification
Extremely flammable liquid. Vapors irritating to skin, eyes and respiratory tract. Inhalation of vapors may
Emergency Overview:
depress central nervous system causing dizziness, headache and nausea.
Primary Routes of Exposure: Ingestion, inhalation, skin, eyes
Eye Contact: Contact will cause irritation, redness and a burning sensation.
Skin Contact: Contact with skin can result in local irritation. May be absorbed throuh skin.
Inhalation of vapors may depress the central nervous system causing dizziness, difficulty in walking and
Inhalation:
irritation to the lungs.
Ingestion may cause gastrointestinal irritation, nausea, vomiting and headache. May cause lung damage if
Ingestion:
swallowed.
Irritating to skin, eyes and respiratory tract. Harmful by inhalation. Ingestion may cause gastrointestinal
Acute Health Affects:
irritation, nausea, vomiting and headache. Possible risk of harm to the unborn child.
Chronic Health Affects: No information on long-term chronic effects. Possible risk of impaired fertility.
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: -14.8°F (hexane)
Autoignition Temperature: no data
Explosion Limits: LEL (1.7%) UEL (7.7%)
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 irritating fumes.
Decomposion Products:
Unusual Fire or Explosion Hazards: Extremely flammable

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SECTION 6: Accidental Release Measures
If spilled, all personnel must be immediately evacuated and the area sealed off. The material may self-ignite
Spill and Leak Procedures: releasing toxic and corrosive fumes of phosphorus pentoxide. Ventilation should be available. If entry into the
area is requires, personnel should be fitted with a self-contained breathing apparatus.

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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 an efficient fume hood.

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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: 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: colorless liquid
Molecular Weight: 269.32
Melting Point: no data
Boiling Point: 68°C (hexane)
Vapor Pressure: no data
Specific Gravity: no data
Odor: pungent and noxious
Solubility in Water: Insoluble

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SECTION 10: Stability and Reactivity
Stability: air sensitive
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: contact with oxidizing agents, ignition sources and prolonged exposure to air
Incompatibility: strong oxidizing agents and halogens
Decomposition Products: carbon monoxide, carbon dioxide, phosphorous pentoxide and organic fumes

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SECTION 11: Toxicological Information
No information available on title compound. For hexane -- Standard Draize Test (rabbit); 10mg (mild).
Inhalation (human); TCLo: 190ppm/8W. Oral (rat); LD50: 28710mg/kg. Inhalation (rat); LC50: 48000ppm/4H.
Intraperitoneal (rat); LDLo: 9100mg/kg. Intravenous (mouse); LDLo: 831mg/kg. Inhalation (rat); TCLo:
RTECS Data:
2000ppm/12H/24W-I. Acts a general anesthetic, respiratory depression, altered sleep time, effects on nerves,
decreased weight gain, muscle weakness, and changes to the liver and blood. Toxic effects observed in the
embryo and fetus of test animals.
Carcinogenic Effects: No data
Mutagenic Effects: For hexane: Possible mutagen
Tetratogenic Effects: For hexane: Possible reproductive effector

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SECTION 12: Ecological Information
Ecological Information: Toxic to aquatic organisms. May cause long-term adverse effects in the aquatic environment.

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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: Not listed in the TSCA inventory
SARA (Title 313): Not reportable under SARA 313
Second Ingredient: Listed on the TSCA inventory. 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：

  (+)-氯甲酸薄荷醇酯 、 （R）-2-[（（二苯基膦基）甲基]吡咯烷 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以70.6 mg的产率得到(1S,2R,5S)-2-isopropyl-5-methylcyclohexyl (R)-2-((diphenylphosphanyl) methyl)pyrrolidine-1-carboxylate
  参考文献：
  名称：

  使用膦/钯的自动串联协同催化：Morita–Baylis–Hillman碳酸盐与烯丙醇的反应

  摘要：

  自动串联催化（ATC）（其中一种催化剂以级联模式促进两个或多个机械上不同的反应）提供了一种从简单的起始原料制备复杂产品的有效策略。此处报道的是使用简单的Pd（PPh 3）4从靛红和烯丙基碳酸酯中对森田-贝利斯-希尔曼碳酸盐进行的史无前例的自动串联协同催化（ATCC ）4前体。离解的磷化氢生成磷酰化物，Pd生成π-烯丙基钯络合物，并且它们进行γ-区域选择性烯丙基-烯丙基烷基化反应。重要的是，进行分子级联的Heck型偶联最终可以提供具有4－亚甲基－2－环戊烯基序的螺硫醇。实验结果表明，Pd和膦都在催化Heck反应中起着至关重要的作用。另外，探索了具有手性膦或手性助剂的不对称形式，并获得了适度的结果。

  DOI：

  10.1002/anie.201814403
• 作为产物：
  描述：

  Boc-D-脯氨醇 在 正丁基锂 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 22.5h， 生成 （R）-2-[（（二苯基膦基）甲基]吡咯烷
  参考文献：
  名称：

  使用膦/钯的自动串联协同催化：Morita–Baylis–Hillman碳酸盐与烯丙醇的反应

  摘要：

  自动串联催化（ATC）（其中一种催化剂以级联模式促进两个或多个机械上不同的反应）提供了一种从简单的起始原料制备复杂产品的有效策略。此处报道的是使用简单的Pd（PPh 3）4从靛红和烯丙基碳酸酯中对森田-贝利斯-希尔曼碳酸盐进行的史无前例的自动串联协同催化（ATCC ）4前体。离解的磷化氢生成磷酰化物，Pd生成π-烯丙基钯络合物，并且它们进行γ-区域选择性烯丙基-烯丙基烷基化反应。重要的是，进行分子级联的Heck型偶联最终可以提供具有4－亚甲基－2－环戊烯基序的螺硫醇。实验结果表明，Pd和膦都在催化Heck反应中起着至关重要的作用。另外，探索了具有手性膦或手性助剂的不对称形式，并获得了适度的结果。

  DOI：

  10.1002/anie.201814403

文献信息

• Asymmetric [3+2] Cycloaddition of Olefins with Morita–Baylis–Hillman Carbonates Catalyzed by BINOL-Based Bifunctional Phosphine
  作者：Hai-Lei Cui、Xue Tang、Meng-Fan Li、Xing-Jie Xu、Yin Shi

  DOI：10.1055/s-0037-1611752

  日期：2019.4

  series of novel BINOL-based phosphines. These bifunctional organocatalysts can be used in the [3+2] cycloaddition of electron-deficient olefins and Morita–Baylis–Hillman (MBH) carbonates. Moderate to excellent yields (up to >99%) and good to excellent enantioselectivities (up to 95% ee) can be obtained in the cycloaddition reaction of maleimides and MBH carbonates. The application of these novel phosphines

  我们开发了一系列新型的基于 BINOL 的膦。这些双功能有机催化剂可用于缺电子烯烃和 Morita-Baylis-Hillman (MBH) 碳酸酯的 [3+2] 环加成。在马来酰亚胺和 MBH 碳酸酯的环加成反应中可以获得中等至优异的产率（高达 >99%）和良好至优异的对映选择性（高达 95% ee）。这些新型膦的应用可以进一步扩展到手性螺环吲哚的不对称合成（高达 85% ee）。本研究的结果表明 BINOL 部分在立体控制中起着重要作用。
• C₃-symmetry Mo₃S₄ aminophosphino clusters combining three sources of stereogenicity: stereocontrol directed by hydrogen bond interactions and ligand configuration
  作者：Carmina Alfonso、Marta Feliz、Vicent S. Safont、Rosa Llusar

  DOI：10.1039/c6dt00755d

  日期：——

  dichroism, nuclear magnetic resonance and X-ray techniques confirm that the (P)-[Mo-(SN,RC)]Cl and (P)-[Mo-(SN,SC)]Cl cluster cations are diastereoisomers which combine three sources of stereogenicity provided by the cluster framework, one carbon atom of the aminophosphine ligand and the nitrogen stereogenic center. The higher stability of the (P)-[Mo-(SN,SC)]+ cation is due to stabilizing vicinal Cl⋯HN interactions

  非对映选择性合成脯氨酸的含氨基膦类古巴型Mo 3 S 4簇，（P）-[Mo 3 S 4 Cl 3（（1 S，2 R）-PPro）3 ] Cl（（P）-[Mo-（S N，R C）] Cl）和（P）-[Mo 3 S 4 Cl 3（（1 S，2 S）-PPro）3 ] Cl（（P）-[Mo-（S N，SC）]Cl），是通过使相应的对映体纯PPro（（R）-和（S）-2-[（（二苯基膦基）甲基]吡咯烷）配体与Mo 3 S 4 Cl 4（PPh）反应而高收率获得的3） 3（H 2 O） 2络合物。圆二色性，核磁共振和X射线技术证实了（ P）-[Mo-（ S N， R C）]Cl和（ P）-[Mo-（ S N， S C）]C1簇阳离子是非对映异构体，其结合了簇构架提供的三种立体异构来源，一个氨基膦配体的碳原子和一个氮立体异构中心。（P）-[Mo-（S N，S C）] +阳离子的较高稳定性是由于稳定邻位
• [EN] METHOD FOR PRODUCING AMIDINE DERIVATIVES<br/>[FR] PROCÉDÉ DE PRODUCTION DE DÉRIVÉS D'AMIDINE
  申请人：BIOCRYST PHARM INC

  公开号：WO2016029216A2

  公开（公告）日：2016-02-25

  The invention provides methods and intermediates useful in the synthesis of a compound of formula (I): or a pharmaceutically acceptable salt, solvate, ester or prodrug thereof; wherein the variables are as defined herein.

  本发明提供了用于合成式(I)化合物的方法和中间体，或其药学上可接受的盐、溶剂和前药酯；其中变量如本文所定义。
• Preparation of new chiral pyridine–phosphine ligands and their Pd-catalyzed asymmetric allylic alkylations
  作者：Jun'ichi Uenishi、Masahiro Hamada

  DOI：10.1016/s0957-4166(01)00535-3

  日期：2001.11

  Enantiomerically pure 2-(diphenylphosphino)methyl-N-[1-(2-pyridinyl)ethyl]pyrrolidines 1 and 2 have been prepared by the stereospecific substitution of enantiomerically pure 1-(2-pyridinyl)ethyl methanesulfonate 6 with enantiomerically pure 2-(diphenylphosphino)methylpyrrolidine. Asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate 11 with dimethyl malonate sodium salt using the (S,S)-ligand 1 affords the (R)-product 12 with up to 86% e.e. in good yield. (C) 2002 Elsevier Science Ltd. All rights reserved.
• METHOD FOR THE PREPARATION OF AMINOPHOSPHINE LIGANDS AND THEIR USE IN METAL CATALYSTS
  申请人：Kanata Chemical Technologies Inc.

  公开号：EP2167515A1

  公开（公告）日：2010-03-31