N,N'-bis[o-(diphenylphosphino)benzylidene]-(1S,2S)-diaiminocyclohexane | 174677-83-9

• 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: N,N'-bis[o-(diphenylphosphino)benzylidene]-(1S,2S)-diaiminocyclohexane
• 英文别名: N,N'-bis[o-(diphenylphosphino)benzylidene]-1S,2S-diaminocyclohexane；(S,S)-N,N'-bis[o-(diphenylphosphino)benzyl]-1,2-diaminocyclohexane；(S,S)-N,N'-bis[o-diphenylphosphino]benzyl-1,2-diaminocyclohexane；N,N'-bis[2-(diphenylphosphino)benzyl]-1R,2R-diaminocyclo-hexane；1,2-Cyclohexanediamine, N1,N2-bis[[2-(diphenylphosphino)phenyl]methyl]-, (1S,2S)-；(1S,2S)-1-N,2-N-bis[(2-diphenylphosphanylphenyl)methyl]cyclohexane-1,2-diamine
• CAS: 174677-83-9
• 化学式: C₄₄H₄₄N₂P₂
• 分子量: 662.794
• InChiKey: OBHPYVNBXWUKNY-COCZKOEFSA-N

物化性质

• 熔点：
  54-56℃
• 沸点：
  749.8±60.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  48
• 可旋转键数：
  12
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  24.1
• 氢给体数：
  2
• 氢受体数：
  2

安全信息

• 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

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Section 1: Product Identification
Chemical Name: (1S,2S)-N,N-Bis[2-(diphenylphosphino)benzyl]cyclohexane-1,2-diamine, min. 97%
CAS Registry Number: 174677-83-9
Formula: C44H44N2P2
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 174677-83-9 100% no data no data

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Section 3: Hazards Identification
Emergency Overview: Irritating to skin, eyes and respiratory tract. May be harmful if swallowed.
Primary Routes of Exposure: Ingestion, inhalation
Eye Contact: Causes moderate irritation of the eyes.
Skin Contact: Causes slight to mild irritation of the 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: no data
Autoignition Temperature: no data
Explosion Limits: no data
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 unusual 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
Store in a tightly sealed container under an inert atmosphere of nitrogen or argon. Keep in a cool, dry, well
Handling and Storage:
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: yellow solid
Molecular Weight: 662.78
Melting Point: no data
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: none
Solubility in Water: Insoluble

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SECTION 10: Stability and Reactivity
Stability: air sensitive
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: prolonged exposure to air
Incompatibility: strong oxidizing agents
Decomposition Products: carbon monoxide, carbon dioxide, nitrogen oxides, phosphorous oxides and 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): Not reportable under 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：

  tris(triphenylphosphine)ruthenium(II) chloride 、 N,N'-bis[o-(diphenylphosphino)benzylidene]-(1S,2S)-diaiminocyclohexane 以 二氯甲烷 为溶剂， 生成 N,N'-bis[2-(diphenylphosphino)benzyl]-1R,2R-diaminocyclo-hexane
  参考文献：
  名称：

  Effect of CNTs on direct oxidation of cyclohexene catalyzed by ruthenium diaminodiphosphine complex

  摘要：

  trans-RuCl2 [kappa(3)-1R,2R-P(NH)(NH)P](PPh3) was synthesized and used in the oxidation of cyclohexene at 80-130degreesC by molecular oxygen with very high activity to the products including 2-cyclohexen-1-one, 2-cyclohexen-1-ol and 1,2-cyclohexandiol. The addition of carbon nanotubes (CNTs), which were synthesized by Fe-Cu/SiO2 catalyzed decomposition of ethylene at 550 degreesC, can enhance the activity of the Ru complex and the selectivity of 2-cyclohexen-1-ol. It was also better for the recycling of the Ru complex, the catalytic activity and selectivity of which still held at a high level after nine times using. (C) 2002 Published by Elsevier Science B.V.

  DOI：

  10.1016/s1381-1169(02)00470-3
• 作为产物：
  描述：

  2-二苯基膦苯甲醛 在 sodium tetrahydroborate 、 sodium sulfate 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 48.0h， 生成 N,N'-bis[o-(diphenylphosphino)benzylidene]-(1S,2S)-diaiminocyclohexane
  参考文献：
  名称：

  New chiral cationic rhodium–aminophosphine complexes for asymmetric transfer hydrogenation of aromatic ketones

  摘要：

  The new chiral ligands (S,S)-N,N'-bis[o-(diphenylphosphino)benzylidene]1,2-diiminocyclohexane, [(S,S)-1] and (S,S)-N,N'-bis[o-diphenylphosphino]benzyl-1,2-diaminocyclohexane, [(S,S)-2] have been prepared. The interaction of [(S,S)-1] and [(S,S)-2] with [Rh(COD)Cl](2) afforded the corresponding cationic rhodium complexes [(S,S)-3][X] and [(S,S)-4][X] (X = PF6-, BF4- or ClO4-), respectively. [(S,S)-1], [(S,S)-2], [(S,S)-3][X] and [(S,S)-4][X] have been fully characterized by elemental analyses and spectroscopic methods. These chiral cationic rhodium complexes serve as catalytst precursors for the asymmetric transfer hydrogenation of acetophenone derivatives in 2-propanol and [(S,S)-4][PF6] acts as an excellent catalyst in the reduction of m-chloroacetophenone, giving the corresponding optical alcohols in 99% yield and up to 94% ee. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00565-3
• 作为试剂：
  描述：

  苯戊酮 在 sodium tetrahydroborate 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 双(三苯基正膦基)氯化铵 、 丙酮 、 potassium hydroxide 、 N,N'-bis[o-(diphenylphosphino)benzylidene]-(1S,2S)-diaiminocyclohexane 作用下， 以 乙醇 、 二氯甲烷 、 水 、 异丙醇 为溶剂， 反应 24.0h， 生成 (1R)-1-苯基戊-1-醇
  参考文献：
  名称：

  外消旋体的氧化动力学拆分 仲醇 在 水 用手性PNNP / Ir催化剂

  摘要：

  使用 水 作为 溶剂，广泛的外消旋体的氧化动力学拆分 仲醇 带有手性PNNP / Ir 催化剂被调查了。催化反应在温和条件下以优异的对映选择性（高达97％ee）顺利进行，为实现光学活性提供了环境友好的工艺酒类。

  DOI：

  10.1039/c2gc00028h

文献信息

• Ruthenium(II) Complexes with Chiral Tetradentate P₂N₂ Ligands Catalyze the Asymmetric Epoxidation of Olefins with H₂O₂
  作者：Robert M. Stoop、Stephan Bachmann、Massimiliano Valentini、Antonio Mezzetti

  DOI：10.1021/om000481v

  日期：2000.10.1

  2S)-diaminocyclohexane (1c), the aqua complex [RuCl(OH2)(1c-κ4P,N,N,P)]PF6 (5c) is obtained by reaction of Tl[PF6] with [RuCl2(PPh3)(1c-κ3P,N,N)] (4), which has been isolated and structurally characterized. The reactivity of the five-coordinate 2b with CO and oxygen donors such as water, Et2O, THF, and methanol is reported. Both 3 and 5 catalyze the asymmetric epoxidation of olefins with hydrogen peroxide as oxidant

  通过从[RuCl 2（PNNP）]中提取氯来制备[RuCl（PNNP）] PF 6类型的五配位络合物（PNNP =具有P 2 N 2供体的四齿配体）。Δ-的混合物的顺式-β-和Λ-顺-β-将[RuCl 2（1A -κ 4 P，N，N，P）]（2A ; 1A = N， “双[ ø - （二苯基膦基）亚苄基] -2,2'-二亚氨基-1,1'-（S）-联萘），是通过1a与[RuCl 2（PPh 3）3]，其中铊[PF发生反应6 ]，给五配位化合物[RuCl（1A -κ 4 P，N，N，P）] PF 6（图3a）。相关的反式-将[RuCl 2（1B -κ 4 P，N，N，P）]（2b中;图1b = N， “双[ ø - （二苯基膦基）亚苄基] - （1-小号，2小号）-diiminocyclohexane ）用铊[PF进行反应6 ]，得到将[RuCl（1B -κ 4 P，N，N，P）] PF 6（图3b）。与氨基配体N，N-
• Preparation of chiral diimino- and diaminodiphosphine ligands and their CuI and AgI complexes. X-ray crystal structures of [Cu(1S,2S-cyclohexyl-P2N2)][PF6] and [Ag(1R,2R-cyclohexyl-P2N2H4)][BF4]
  作者：Wai-Kwok Wong、Tat-Wai Chik、Kin-Ning Hui、Ian Williams、Xue Feng、Thomas C.W. Mak、Chi-Ming Che

  DOI：10.1016/0277-5387(96)00196-9

  日期：1996.9

  tetradentate ligand undergoes rapid dissociation to form a tridentate ligand. The interaction of AgBF4 with 1 equiv. of otpically pure L 4 [ L 4 = (R,R)- I , (S,S)- I , (R,R)- II and (S,S)- II gave the corresponding optically pure [AgL4][BF4] complexes, VII–X VII L 4 = (R,R)- I ; VIII , L 4 = (S,S)- I ; IX ,L 4 = (R,R)- II ; X, L 4 = (S,S)- II ] , in good yield. For the AgI complexes, the L4 ligand acted

  摘要光学纯的1R，2R-二铵环己烷单-（酒石酸）酒石酸盐与1S，2S-二铵环己烷单-（-）-酒石酸盐的当量相互作用。在2当量存在下的邻-（二苯基膦基）苯甲醛 回流的乙醇/水混合物中加碳酸钾得到光学纯的缩合产物N，N′-双[邻-（（二苯基膦基）亚苄基] -1R，2R-二亚氨基环己烷[1R，2R-环己基-P 2 N 2，（R ，R）-I]和N，N′-双[邻-（（二苯基膦基）亚苄基] -1S，2S-二亚氨基环己烷[1S，2S-环己基-P 2 N 2，（S，S）-I]，产量高。在乙醇中用NaBH4还原光学纯的（R，R）-I和（S，S）-I，得到光学纯的还原产物N，N'-双[o-（（二苯基膦基）亚苄基] -1R，2R-二氨基环己烷[ 1R，2R-环己基-P2N2H4，（R，R）-II]和N，N′-双[邻-二苯基膦）亚苄基] -1S，分别以良好的收率得到2S-二氨基环己烷[1S，2S-环己基-P 2 N
• Process for polymerizing olefins with non-metallocene catalysts
  申请人：Schulte L. Joerg

  公开号：US20060135352A1

  公开（公告）日：2006-06-22

  Nonmetallocenes, process for preparing them and their use for the polymerization of olefins. The present invention describes a novel group of specific transition metal compounds, referred to as nornmetallocene compounds, and catalyst systems prepared therefrom. These catalyst systems which have become obtainable for the first time are suitable for the polymerization of olefins.

  非金属茂金属化合物，其制备方法及其用于烯烃聚合的用途。本发明描述了一种新型的特定过渡金属化合物组，称为非金属茂金属化合物，以及从中制备的催化剂体系。这些催化剂体系首次可获得，并适用于烯烃聚合。
• Non-metallocenes, method for the production thereof and use thereof in the polymerization of olefins
  申请人：Schulte L. Jorg

  公开号：US20050037918A1

  公开（公告）日：2005-02-17

  The present invention describes a novel group of specific transition metal compounds, referred to as nonmetallocene compounds, and catalyst systems prepared therefrom. These catalyst systems which have become obtainable for the first time are suitable for the polymerization of olefins.

  本发明描述了一种新型的特定过渡金属化合物群，称为非金属环化合物，以及从中制备的催化剂系统。这些催化剂系统是首次可获得的，适用于烯烃的聚合。
• A Ruthenium(II) Complex with a <i>C</i>₂-Symmetric Diphosphine/Diamine Tetradentate Ligand for Asymmetric Transfer Hydrogenation of Aromatic Ketones
  作者：Jing-Xing Gao、Takao Ikariya、Ryoji Noyori

  DOI：10.1021/om950833b

  日期：1996.2.20

  The trans-(RuCl2)-Cl-II complexes with structurally similar N,N'-bis[o-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine and N,N'-bis[o-(diphenylphosphino)-benzyl]cyclohexane-1,2-diamine ligands have been synthesized, and their molecular structures have been determined. The C-2-symmetric diphosphine/diamine-based Ru complex acts as an excellent catalyst precursor in asymmetric transfer hydrogenation of acetophenone in a 0.1 M 2-propanol solution, leading to 2-phenylethanol in 97% ee and in 93% yield after 7 h at 45 degrees C. This transfer hydrogenation is characterized by low reversibility under these conditions.