(2R,3R)-(-)-2,3-Bis(diphenylphosphino)bicyclo[2.2.1]hept-5-ene | 71042-55-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3R)-(-)-2,3-Bis(diphenylphosphino)bicyclo[2.2.1]hept-5-ene
• 英文别名: (3-diphenylphosphanyl-2-bicyclo[2.2.1]hept-5-enyl)-diphenylphosphane
• CAS: 71042-55-2；71042-54-1
• 化学式: C₃₁H₂₈P₂
• 分子量: 462.511
• InChiKey: CDJHPMXMJUCLPA-UHFFFAOYSA-N

物化性质

• 熔点：
  120 °C
• 比旋光度：
  +47° (c 1, CHCl3)
• 沸点：
  577.0±50.0 °C(Predicted)
• 稳定性/保质期：

  易被氧化，应在氮气或氩气保护下操作，并在通风橱中进行。

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  33
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• TSCA：
  No
• 危险品标志：
  Xi
• 危险类别码：
  R36/37/38
• 安全说明：
  S26,S36
• 危险性防范说明：
  P261,P280,P301+P312,P302+P352,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335

SDS

Name:	(2R 3R)-(-)-2 3-Bis(Diphenylphosphino)Bicyclo[2.2.1]Hept-5-ene Material Safety Data Sheet
Synonym:	(R,R)-NORPHOS
CAS:	71042-54-1

Section 1 - Chemical Product MSDS Name:(2R 3R)-(-)-2 3-Bis(Diphenylphosphino)Bicyclo[2.2.1]Hept-5-ene Material Safety Data Sheet
Synonym:(R,R)-NORPHOS

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
71042-54-1	(2R,3R)-(-)-2,3-Bis(Diphenylphosphino)	ca. 100	unlisted

Hazard Symbols: None Listed.
Risk Phrases: None Listed.

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Air sensitive.The toxicological properties of this material have not been fully investigated.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation.
Ingestion:
May cause irritation of the digestive tract. The toxicological properties of this substance have not been fully investigated.
Inhalation:
May cause respiratory tract irritation. The toxicological properties of this substance have not been fully investigated.
Chronic:
No information found.

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Section 4 - FIRST AID MEASURES
Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse.
Ingestion:
Never give anything by mouth to an unconscious person. Get medical aid. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water. Wash mouth out with water.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician:
Treat symptomatically and supportively.

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Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Vacuum or sweep up material and place into a suitable disposal container. Clean up spills immediately, observing precautions in the Protective Equipment section. Provide ventilation. Place under an inert atmosphere.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Avoid breathing dust, vapor, mist, or gas. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation. Handle under an inert atmosphere. Store protected from air.
Storage:
Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances. Do not expose to air. Store under an inert atmosphere.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 71042-54-1: 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:
Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure limits are exceeded or if irritation or other symptoms are experienced.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Crystals
Color: white
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 120 - 125 deg C
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: Insoluble.
Specific Gravity/Density:
Molecular Formula: C31H28P2
Molecular Weight: 462.52

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable at room temperature in closed containers under normal storage and handling conditions. Air sensitive.
Conditions to Avoid:
Incompatible materials, dust generation, exposure to air.
Incompatibilities with Other Materials:
Oxygen, oxidizing agents, halogens.
Hazardous Decomposition Products:
Carbon monoxide, oxides of phosphorus, carbon dioxide.
Hazardous Polymerization: Will not occur.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 71042-54-1 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
(2R,3R)-(-)-2,3-Bis(Diphenylphosphino)Bicyclo[2.2.1]Hept-5-ene - 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: Not regulated.
Hazard Class:
UN Number:
Packing Group:
IMO
Shipping Name: Not regulated.
Hazard Class:
UN Number:
Packing Group:
RID/ADR
Not regulated as a hazardous material.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: Not available.
Risk Phrases:
Safety Phrases:
S 24/25 Avoid contact with skin and eyes.
WGK (Water Danger/Protection)
CAS# 71042-54-1: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 71042-54-1 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 71042-54-1 is not listed on the TSCA inventory.
It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

制备方法

通过还原剂还原 (+)-trans-(2S,3S)-二(二苯基氧化膦)二环庚-5-烯制得。

用途简介

过渡金属与 (+)-NORPHOS 形成的配合物广泛用于不饱和官能团的催化加氢。由配合物 [Rh(diene)Cl]2 与 (+)-NORPHOS 反应得到的铑催化剂可用于催化加氢反应（式1）。Rh 与 (+)-NORPHOS 形成的配合物也可用于碳-氧双键（式2）和碳-氮双键（式3）的不对称加成，应用 (+)-NORPHOS 可获得更高产率的立体专一产物。在苄胺存在下，Rh 与 (–)-NORPHOS 形成的这种配合物对 α-酮酸进行氢化可得到立体专一性的 α-苄氨基酸（式4）。

不对称硼氢化反应 在 Rh 与 (+)-NORPHOS 形成的配合物催化下，环丙烯衍生物进行硼氢化反应，可获得高立体专一性产物（式5）。类 Diels-Alder 反应 使用乙酸钴/ (+)-NORPHOS 催化剂使降冰片二烯与单取代的炔烃加成，得到高立体专一性（大于 98% ee）的四环烯烃（式6）。

反应信息

• 作为反应物：
  描述：

  (η-1,5-cyclooctadiene)[3-hydroxymethylene-(1R)-campherato]rhodium(I) 、 (2R,3R)-(-)-2,3-Bis(diphenylphosphino)bicyclo[2.2.1]hept-5-ene 以 乙腈 为溶剂， 以62%的产率得到[(-)-norphos][3-hydroxymethylene-(1R)-campherato]rhodium(I)
  参考文献：
  名称：

  Asymmetrische katalyse 104. Doppelte stereoselektion in rhodium-katalysatoren bei der enantioselektiven hydrierung von

  摘要：

  Optically active rhodium catalysts with double stereoselection were prepared from the optically active chelating phosphanes Diop and Norphos and eta-1,5-cyclooctadiene rhodium complexes which contain the anions of optically active 1,3-diketones and 1,3-ketoimines based on camphor. Use of these complexes in the homogeneous enantioselective hydrogenation of (Z)-alpha-N-acetamidocinnamic acid to N-acetylphenylalanine gave optical inductions up to 90.7% and 92.3% ee for Diop and Norphos complexes, respectively. These results exceed those obtained with the corresponding phosphane-rhodium systems without additional optically active coligands.

  DOI：

  10.1016/s0022-328x(96)06456-x

文献信息

• Axially Asymmetric Phosphorus Compound and Production Method Thereof
  申请人：Tanaka Ken

  公开号：US20090227805A1

  公开（公告）日：2009-09-10

  Problem to be Solved: To provide an axially asymmetric optically active biarylphosphorus compound that can easily produced without the step of optical resolution which was almost indispensable in conventional methods. Solution: A method for producing an axially asymmetric phosphorus compound represented by the general formula (1), comprising a cycloaddition reaction of a compound having a triple bond with the use of a catalyst containing rhodium metal and an optically active bisphosphine. (In the formula, J is an oxygen atom, a sulfur atom or BH 3 ; R 1 and R 2 independently are an alkyl, cycloalkyl, aryl, alkoxy and aryloxy group; a1 and a2 independently are 0 or 1; R 3 to R 10 independently are an alkyl, cycloalkyl, aryl, alkoxy and aryloxy group; two among R 3 to R 10 may form a ring; and * is axial asymmetry.)

  要解决的问题：提供一种轴向不对称的光学活性联苯磷化合物，可以在传统方法中几乎不可或缺的光学分辨步骤之外轻松生产。 解决方案：一种生产由通式（1）表示的轴向不对称磷化合物的方法，包括使用含有铑金属和光学活性双膦的催化剂进行含有三键化合物的环加成反应。 （在公式中，J是氧原子、硫原子或BH3；R1和R2独立地是烷基、环烷基、芳基、烷氧基和芳氧基；a1和a2独立地为0或1；R3到R10独立地是烷基、环烷基、芳基、烷氧基和芳氧基；R3到R10中的两个可能形成环；*表示轴向不对称。）
• [EN] PROCESS FOR THE HYDROGENATION OF IMINES<br/>[FR] PROCÉDÉ D'HYDROGÉNATION D'IMINES
  申请人：CHEMINOVA AS

  公开号：WO2010094164A1

  公开（公告）日：2010-08-26

  A process is provided for the hydrogenation of imines with hydrogen under elevated pressure in the presence of iridium complexes as catalysts and one or more co-catalysts selected among compounds comprising a carbon-halogen bond. Further provided are novel ligands and metal complexes thereof useful for the catalytic hydrogenation of imines with hydrogen. The novel ligands are compounds of the formula (VII) or formula (VIII) in the form of racemates, mixtures of stereoisomers or optically pure stereoisomers, wherein the radicals are as defined in the specification.

  提供了一种在铱络合物存在下，在高压下利用氢气对亚胺进行加氢的方法，其中选择的一个或多个辅催化剂为包含碳-卤素键的化合物。还提供了用于催化亚胺与氢气加氢的新型配体和金属络合物。这些新型配体是根据式（VII）或式（VIII）的化合物，以外消旋体、立体异构体混合物或光学纯立体异构体的形式存在，其中基团如规范中所定义。
• PROCESS FOR THE HYDROGENATION OF IMINES
  申请人：Saaby Steen

  公开号：US20110077418A1

  公开（公告）日：2011-03-31

  A process is provided for the hydrogenation of imines with hydrogen under elevated pressure in the presence of iridium complexes as catalysts and one or more co-catalysts selected among compounds comprising a carbon-halogen bond. Further provided are novel ligands and metal complexes thereof useful for the catalytic hydrogenation of imines with hydrogen. The novel ligands are compounds of the formula (VII) or formula (VIII) in the form of racemates, mixtures of stereoisomers or optically pure stereoisomers wherein the radicals are as defined in the specification.

  提供了一种在铱络合物存在下，在高压下利用氢气对亚胺进行加氢的方法，并选择一种或多种在其中的协同催化剂，所述协同催化剂选自包含碳-卤素键的化合物。还提供了用于催化亚胺与氢气加氢的新型配体和金属络合物。这些新型配体是根据式（VII）或式（VIII）的化合物，以外消旋体、立体异构体混合物或光学纯立体异构体的形式存在，其中基团如规范中所定义。
• [EN] INTERMOLECULAR C-H SILYLATION OF UNACTIVATED ARENES<br/>[FR] SILYLATION C-H INTERMOLÉCULAIRE D'ARÈNES INACTIVÉS
  申请人：UNIV CALIFORNIA

  公开号：WO2015035325A1

  公开（公告）日：2015-03-12

  Reaction mixtures for silvlating arene substrates and methods of using such reaction mixtures to silyiate the arene substrates are provided. Exemplary reaction mixtures include the arene substrate, a liganded metal catalyst, a hydrogen acceptor and an organic solvent. The reaction conditions allow for diverse substituents on the arene substrate.

  提供了用于硅基化芳烃底物的反应混合物以及使用这种反应混合物来硅基化芳烃底物的方法。示例反应混合物包括芳烃底物、配体化金属催化剂、氢受体和有机溶剂。反应条件允许芳烃底物上具有多样的取代基。
• METHOD FOR PRODUCING ALCOHOL COMPOUND
  申请人：Shimizu Hideo

  公开号：US20110201819A1

  公开（公告）日：2011-08-18

  Disclosed is a practical method for efficiently producing an alcohol compound by hydrogenating an aldehyde by using a homogeneous copper catalyst which is an easily-available low-cost metal species. Specifically disclosed is a method for producing an alcohol compound, which is characterized in that a hydrogenation reaction of an aldehyde compound is performed in the presence of a homogeneous copper catalyst and a diphosphine compound.

  本文揭示了一种实用的方法，通过使用易获得的低成本金属种类——均相铜催化剂，通过氢化醛类化合物高效产生醇类化合物。具体揭示了一种产生醇类化合物的方法，其特点在于在均相铜催化剂和二膦化合物存在下进行醛类化合物的氢化反应。