(R,S)-Josiphos | 162291-02-3

• 物质功能分类: 化学试剂 - 有机试剂 - 膦配体
• 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: (R,S)-Josiphos
• 英文别名: (R,S_p)-Josiphos；(S,R)-Josiphos；cyclopenta-1,3-diene;dicyclohexyl-[(1S)-1-(2-diphenylphosphanylcyclopenta-1,4-dien-1-yl)ethyl]phosphane;iron(2+)
• CAS: 162291-02-3
• 化学式: C₃₆H₄₄FeP₂
• 分子量: 594.54
• InChiKey: REDWELITTWIEQG-WLOLSGMKSA-N

物化性质

• 比旋光度：
  +360° (c 0.5, CHCl3)

计算性质

• 辛醇/水分配系数(LogP)：
  9.77
• 重原子数：
  39
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 安全说明：
  S26,S36/37/39
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 海关编码：
  29319090
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335

SDS

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Section 1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product identifiers
Product name : (S)-1-[(RP)-2-
(Diphenylphosphino)ferrocenyl]ethyldicyclohexylpho
sphine
CAS-No. : 162291-02-3
Relevant identified uses of the substance or mixture and uses advised against
Identified uses : Laboratory chemicals, Manufacture of substances

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Section 2. HAZARDS IDENTIFICATION
Classification of the substance or mixture
Not a hazardous substance or mixture according to Regulation (EC) No 1272/2008
This substance is not classified as dangerous according to Directive 67/548/EEC.
Label elements
Caution - substance not yet tested completely.
Other hazards - none

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Section 3. COMPOSITION/INFORMATION ON INGREDIENTS
Substances
Synonyms : (S)-(R)-Josiphos
(2S)-1-[(1S)-1-(Dicyclohexylphosphino)ethyl]-2-
(diphenylphosphino)ferrocene (acc to CAS)
Josiphos SL-J001-2
Formula : C36H44FeP2·C2H5OH
Molecular Weight : 640,60 g/mol

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Section 4. FIRST AID MEASURES
Description of first aid measures
If inhaled
If breathed in, move person into fresh air. If not breathing, give artificial respiration.
In case of skin contact
Wash off with soap and plenty of water.
In case of eye contact
Flush eyes with water as a precaution.
If swallowed
Never give anything by mouth to an unconscious person. Rinse mouth with water.
Most important symptoms and effects, both acute and delayed
Indication of any immediate medical attention and special treatment needed
no data available

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Section 5. FIREFIGHTING MEASURES
Extinguishing media
Suitable extinguishing media
Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.
Special hazards arising from the substance or mixture
Carbon oxides, Oxides of phosphorus, Iron oxides
Advice for firefighters
Wear self contained breathing apparatus for fire fighting if necessary.
Further information
no data available

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Section 6. ACCIDENTAL RELEASE MEASURES
Personal precautions, protective equipment and emergency procedures
Avoid dust formation. Avoid breathing vapors, mist or gas.
Environmental precautions
Do not let product enter drains.
Methods and materials for containment and cleaning up
Sweep up and shovel. Keep in suitable, closed containers for disposal.
Reference to other sections
For disposal see section 13.

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Section 7. HANDLING AND STORAGE
Precautions for safe handling
Provide appropriate exhaust ventilation at places where dust is formed.Normal measures for preventive fire
protection.
Conditions for safe storage, including any incompatibilities
Store in cool place. Keep container tightly closed in a dry and well-ventilated place.
Specific end uses
no data available

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Section 8. EXPOSURE CONTROLS/PERSONAL PROTECTION
Control parameters
Components with workplace control parameters
Exposure controls
Appropriate engineering controls
General industrial hygiene practice.
Personal protective equipment
Eye/face protection
Use equipment for eye protection tested and approved under appropriate government standards
such as NIOSH (US) or EN 166(EU).
Skin protection
Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique
(without touching glove's outer surface) to avoid skin contact with this product. Dispose of
contaminated gloves after use in accordance with applicable laws and good laboratory practices.
Wash and dry hands.
The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and
the standard EN 374 derived from it.
Body Protection
Choose body protection in relation to its type, to the concentration and amount of dangerous
substances, and to the specific work-place., The type of protective equipment must be selected
according to the concentration and amount of the dangerous substance at the specific workplace.
Respiratory protection
Respiratory protection is not required. Where protection from nuisance levels of dusts are desired,
use type N95 (US) or type P1 (EN 143) dust masks. Use respirators and components tested and
approved under appropriate government standards such as NIOSH (US) or CEN (EU).

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Section 9. PHYSICAL AND CHEMICAL PROPERTIES
Information on basic physical and chemical properties
a) Appearance Form: powder
Colour: dark orange
b) Odour no data available
c) Odour Threshold no data available
d) pH no data available
e) Melting point/freezing no data available
point
f) Initial boiling point and no data available
boiling range
g) Flash point no data available
h) Evaporation rate no data available
i) Flammability (solid, gas) no data available
j) Upper/lower no data available
flammability or
explosive limits
k) Vapour pressure no data available
l) Vapour density no data available
m) Relative density no data available
n) Water solubility no data available
o) Partition coefficient: n- no data available
octanol/water
p) Autoignition no data available
temperature
q) Decomposition no data available
temperature
r) Viscosity no data available
s) Explosive properties no data available
t) Oxidizing properties no data available
Other safety information
no data available

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Section 10. STABILITY AND REACTIVITY
Reactivity
no data available
Chemical stability
no data available
Possibility of hazardous reactions
no data available
Conditions to avoid
no data available
Incompatible materials
Strong oxidizing agents
Hazardous decomposition products
Other decomposition products - no data available

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Section 11. TOXICOLOGICAL INFORMATION
Information on toxicological effects
Acute toxicity
no data available
Skin corrosion/irritation
no data available
Serious eye damage/eye irritation
no data available
Respiratory or skin sensitization
no data available
Germ cell mutagenicity
no data available
Carcinogenicity
IARC: No component of this product present at levels greater than or equal to 0.1% is identified as
probable, possible or confirmed human carcinogen by IARC.
Reproductive toxicity
no data available
Specific target organ toxicity - single exposure
no data available
Specific target organ toxicity - repeated exposure
no data available
Aspiration hazard
no data available
Potential health effects
Inhalation May be harmful if inhaled. May cause respiratory tract irritation.
Ingestion May be harmful if swallowed.
Skin May be harmful if absorbed through skin. May cause skin irritation.
Eyes May cause eye irritation.
Additional Information
RTECS: Not available

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Section 12. ECOLOGICAL INFORMATION
Toxicity
no data available
Persistence and degradability
no data available
Bioaccumulative potential
no data available
Mobility in soil
no data available
Results of PBT and vPvB assessment
no data available
Other adverse effects
no data available

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Section 13. DISPOSAL CONSIDERATIONS
Waste treatment methods
Product
Offer surplus and non-recyclable solutions to a licensed disposal company.
Contaminated packaging
Dispose of as unused product.

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Section 14. TRANSPORT INFORMATION
UN number
ADR/RID: - IMDG: - IATA: -
UN proper shipping name
ADR/RID: Not dangerous goods
IMDG: Not dangerous goods
IATA: Not dangerous goods
Transport hazard class(es)
ADR/RID: - IMDG: - IATA: -
Packaging group
ADR/RID: - IMDG: - IATA: -
Environmental hazards
ADR/RID: no IMDG Marine pollutant: no IATA: no
Special precautions for user
no data available

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Section 15. REGULATORY INFORMATION
This safety datasheet complies with the requirements of Regulation (EC) No. 1907/2006.
Safety, health and environmental regulations/legislation specific for the substance or mixture
no data available
Chemical Safety Assessment
no data available

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Section 16. OTHER INFORMATION
Further information
Copyright 2012 Co. LLC. License granted to make unlimited paper copies for internal use
only.
The above information is believed to be correct but does not purport to be all inclusive and shall be
used only as a guide. The information in this document is based on the present state of our knowledge
and is applicable to the product with regard to appropriate safety precautions. It does not represent any
guarantee of the properties of the product. Corporation and its Affiliates shall not be held
liable for any damage resulting from handling or from contact with the above product. See
and/or the reverse side of invoice or packing slip for additional terms and conditions of sale.

制备方法与用途

用途

(S)-(+)-1-[(R)-2-(二苯基膦)二茂铁]乙基二环已基膦是一种Josiphos类手性二茂铁膦配体，是一类非常实用和重要的配体。其开拓性仅次于BINAP配体，广泛应用于烯烃不对称氢胺化、Michael加成等不对称有机合成反应中，并在工业生产中得到广泛应用，在许多药物和精细化学品的合成中发挥着重要作用。

反应信息

• 作为反应物：
  描述：

  copper(I) bromide dimethylsulfide complex 、 (R,S)-Josiphos 以 甲基叔丁基醚 为溶剂， 反应 0.5h， 生成 (S,R(Fe))-Josiphos/CuBr
  参考文献：
  名称：

  格氏试剂与烯酮的催化对映选择性1,2-加成反应中的不对称扩增。

  摘要：

  在将格氏试剂添加到烯酮中时，观察到源自对映纯和外消旋催化剂之间溶解度差异的大的不对称扩增。该行为不是反应或催化剂特有的，并且对于广泛用于不对称催化的各种手性二膦配体的金属配合物观察到了。

  DOI：

  10.1039/c3cc41892h
• 作为产物：
  描述：

  (S)-N,N-dimethyl-1-[(R)-2-(diphenylphosphino)-ferrocenyl]ethylamine 、 二环己基膦 在 溶剂黄146 作用下， 生成 (R,S)-Josiphos
  参考文献：
  名称：

  带有Josiphos配体的铑（III）一元氢化物配合物催化的芳基全氟烷基酮的不对称加氢。

  摘要：

  2，2，2-三氟苯乙酮和芳基全氟烷基酮的不对称氢化反应是使用独特的，定义明确的带有Josiphos型二膦配体的氯桥联二核铑（III）络合物开发的。这些配合物是由[RhCl（cod）] 2，Josiphos配体和盐酸制备的。作为催化剂的前体，它们允许具有全氟烷基的手性仲醇的有效和对映选择性合成（最高99％ee）。该系统不需要用于2,2,2-三氟苯乙酮氢化的活化碱。另外，首次报道了2-苯基-3-（卤代乙酰基）吲哚的对映选择性C ＝ O氢化，这是药物化学中的一类特权结构。

  DOI：

  10.1002/chem.201902585
• 作为试剂：
  描述：

  2-(1,2,6,7-tetrahydro-8H-indeno[5,4-b]furan-8-ylidene)acetonitrile 在 (R,S)-Josiphos 、 二苯基硅烷 、 copper diacetate 、 叔丁醇 作用下， 以 甲苯 为溶剂， 生成 (S)-2-(2,6,7,8-四氢-1H-茚并[5,4-b]呋喃-8-基)乙腈
  参考文献：
  名称：

  PROCESS FOR THE PREPARATION OF RAMELTEON

  摘要：

  描述了一种工业规模制备N-[2-(8S)-1,6,7,8-四氢-2H-茚并[5,4-b]呋喃-8-基]乙基]丙酰胺，拉莫特嗪，具有下图所示结构的过程。

  公开号：

  US20100234622A1

文献信息

• [EN] BENZO[H]QUINOLINE LIGANDS AND COMPLEXES THEREOF<br/>[FR] LIGANDS DE BENZO[H]QUINOLÉINE ET COMPLEXES DE CEUX-CI
  申请人：JOHNSON MATTHEY PLC

  公开号：WO2016193761A1

  公开（公告）日：2016-12-08

  The present invention provides substituted tridentate benzo[h]quinoline ligands and complexes thereof. The invention also provides the preparation of the ligands and the respective complexes, as well as to processes for using the complexes in catalytic reactions.

  本发明提供了取代的三齿苯并[h]喹啉配体及其配合物。该发明还提供了配体和相应配合物的制备方法，以及使用配合物进行催化反应的过程。
• Complexes of Ruthenium with 2-(Aminomethyl)Pyridines and Phosphines, their Preparation and Use as Catalysts
  申请人：Baratta Walter

  公开号：US20080249308A1

  公开（公告）日：2008-10-09

  The invention relates to a new class of ruthenium (II) complexes containing as ligands 2-(aminomethyl)pyridines and phosphines, proven to be extremely active catalysts in the reduction of ketones to alcohols via hydrogen transfer. By using 2-propanol as the hydrogen source with the ruthenium complexes, high yields of the corresponding alcohol can be rapidly obtained starting from linear and cyclic alkyl aryl, dialkyl and diaryl ketones. The conversion of ketones to alcohols can reach 100% if operating in a gaseous hydrogen atmosphere (2-3 atm). Where the phosphines used are optically active, starting from prochiral ketone compounds various types of optically active alcohols can be produced, being important intermediates in the pharmaceutical industry, in the agrochemical industry and for fine chemicals generally.

  该发明涉及一类新型的钌(II)络合物，其中配体为2-(氨甲基)吡啶和膦，被证明在通过氢转移将酮还原为醇的过程中具有极高的催化活性。通过使用2-丙醇作为氢源与钌络合物，可以从直链和环烷基芳基、二烷基和二芳基酮中迅速获得相应醇的高收率。如果在气态氢气氛围（2-3大气压）下操作，酮转化为醇的收率可以达到100%。如果使用的膦是光学活性的，从拟手性酮化合物出发，可以生产各种类型的光学活性醇，这些醇是制药工业、农药工业和精细化工等领域的重要中间体。
• [EN] COMPLEXES OF RUTHENIUM WITH 2-(AMINOMETHYL)PYRIDINES AND PHOSPHINES, THEIR PREPARATION AND USE AS CATALYSTS<br/>[FR] COMPLEXES DE RUTHENIUM CONTENANT DES 2-(AMINOMETHYL)PYRIDINES ET DES PHOSPHINES, LEUR PREPARATION ET LEUR UTILISATION COMME CATALYSEURS
  申请人：UNIV DEGLI STUDI UDINE

  公开号：WO2005105819A1

  公开（公告）日：2005-11-10

  The patent describes a new class of ruthenium (II) complexes containing as ligands 2-(aminomethyl)pyridines and phosphines, proven to be extremely active catalysts in the reduction of ketones to alcohols via hydrogen transfer. By using 2-propanol as the hydrogen source with said ruthenium complexes, high yields of the corresponding alcohol can be rapidly obtained starting from linear and cyclic alkyl aryl, dialkyl and diaryl ketones. The conversion of ketones to alcohols can reach 100% if operating in a gaseous hydrogen atmosphere (2 - 3 atm). Where the phosphines used are optically active, starting from prochiral ketone compounds various types of optically active alcohols can be produced, being important intermediates in the pharmaceutical industry, in the agrochemical industry and for fine chemicals generally.

  该专利描述了一种新的钌(II)配合物类，其含有2-(氨甲基)吡啶和膦作为配体，已被证明是在氢转移还原酮为醇反应中极为活性的催化剂。通过使用2-丙醇作为氢源与该钌配合物，可以从线性和环烷基芳基、双烷基和双芳基酮中快速得到相应的醇高收率。如果在氢气气氛下(2-3大气压)操作，酮到醇的转化率可以达到100%。如果使用的膦是光学活性的，则可以从原始手性酮化合物中生产各种类型的光学活性醇，这些醇是制药工业、农化工业和精细化学品通常的重要中间体。
• 2-(Aminomethyl)pyridine−Phosphine Ruthenium(II) Complexes:  Novel Highly Active Transfer Hydrogenation Catalysts
  作者：Walter Baratta、Eberhardt Herdtweck、Katia Siega、Micaela Toniutti、Pierluigi Rigo

  DOI：10.1021/om0491701

  日期：2005.3.1

  been found to be highly efficient transfer hydrogenation catalysts. With the complexes cis-RuCl2(PP)(ampy) a large number of ketones (dialkyl, diaryl, and alkyl-aryl) can be quantitatively reduced to alcohols in 2-propanol and in the presence of NaOH (ketone/Ru/NaOH = 2000/1/40) with remarkably high TOF values (up to 400 000 h-1 at 50% conversion). The derivatives containing chiral diphosphines afforded

  通过反应高产率地制备了复合物反，顺-RuCl 2（PPh 3）2（ampy）（1）和反-RuCl 2 [Ph 2 P（CH 2）4 PPh 2 ]（ampy）（2）。在室温下用2-（氨基甲基）吡啶（ampy）对RuCl 2（PPh 3）3和RuCl 2（PPh 3）[Ph 2 P（CH 2）4 PPh 2 ]进行PPh 3的分析移位。在回流的甲苯中加热化合物1导致异构体cis，cis -RuCl 2（PPh 3）2（ampy）（3），已被证明是制备顺式-RuCl 2（PP）配合物的良好前体。（ampy）[PP =（S，S）-Chiraphos，4 ; pH值2 P（CH 2）3 PPH 2，5 ; （S，S）-Skewphos，6 ; pH值2 P（CH 2）4PPH 2，7 ; （R，R）-Diop，8 ]，用适当的二膦置换两个PPh 3。衍生物顺式-RuCl 2（PP）（ampy）[PP
• Synthesis, Characterization, and Application in Asymmetric Hydrogenation Reactions of Chiral Ruthenium(II) Diphosphine Complexes
  作者：Nadia C. Zanetti、Felix Spindler、John Spencer、Antonio Togni、Grety Rihs

  DOI：10.1021/om9506781

  日期：1996.1.23

  Four new complexes of the type [Ru(CF3CO2)2(X)2(PP)] 7 (X = methanol or ethanol, PP = chiral diphosphine) have been synthesized from the reaction of PP with [Ru2(CF3CO2)4(H2O)(COD)2] and characterized by both NMR spectroscopy and single-crystal X-ray diffraction studies. A common feature of these complexes is a pseudooctahedral geometry for ruthenium, an unusual monodentate ligation mode for the mutually

  从PP与[Ru 2（CF ）的反应中，合成了四种新的[Ru（CF 3 CO 2）2（X）2（PP）] 7类型的络合物（X =甲醇或乙醇，PP =手性二膦）。3 CO 2）4（H 2 O）（COD）2 ]，并通过NMR光谱学和单晶X射线衍射研究对其进行表征。这些配合物的共同特征是钌的伪八面体几何形状，相互反式三氟乙酸酯基团的不寻常的单齿连接方式以及两个相互顺式配位的溶剂分子位置（MeOH表示7a和7b，EtOH表示7c）。7a（PP =（2 S， 4 S）-BDPP）属于正交P 2 1 2 1 2 1 1空间群，Z = 4，a = 9.896（1）Å，b = 19.099（3）Å，c = 19.689（2）Å。7b（PP =（4 S， 5 S）-DIOP）也在正交P 2 1 2 1 2 1 1空间群中结晶，Z = 4，a = 12.679（1）Å，b = 16.744（2）Å，c = 18.944（2）Å。7c（PP