(+)-1,2-双((2S,5S)-2,5-二甲基磷烷)苯 | 136735-95-0

• 物质功能分类: 医药中间体 - 杂环化合物 - 吡啶类化合物
• 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: (+)-1,2-双((2S,5S)-2,5-二甲基磷烷)苯
• 中文别名: (+)-1,2-双[(2S,5S)-2,5-二甲基磷]苯
• 英文名称: 1,2-bis((2S,5S)-2,5-dimethylphospholano)benzene
• 英文别名: (S,S)-Me-Duphos；(S,S)-Methyl-DUPHOS；(2S,5S)-1-[2-[(2S,5S)-2,5-dimethylphospholan-1-yl]phenyl]-2,5-dimethylphospholane
• CAS: 136735-95-0
• 化学式: C₁₈H₂₈P₂
• 分子量: 306.368
• InChiKey: AJNZWRKTWQLAJK-VGWMRTNUSA-N

物化性质

• 熔点：
  67-76 °C
• 比旋光度：
  D25 +476± 5° (c = 1 in hexane)
• 沸点：
  415.0±15.0 °C(Predicted)
• 稳定性/保质期：
  如果按照规格使用和储存，则不会分解，目前未有已知危险反应。

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 危险品标志：
  Xi
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 安全说明：
  S26
• 危险性防范说明：
  P280,P305+P351+P338
• 危险性描述：
  H302
• 储存条件：
  请将贮藏器密封保存，并存放在阴凉干燥处。同时，确保工作环境有良好的通风或排气设施。

SDS

Name:	(+)-1 2-Bis((2S 5S)-2 5-dimethylphospholano)benzene Material Safety Data Sheet
Synonym:	(S,S)-Me-DUPHOS
CAS:	136735-95-0

Section 1 - Chemical Product MSDS Name:(+)-1 2-Bis((2S 5S)-2 5-dimethylphospholano)benzene Material Safety Data Sheet
Synonym:(S,S)-Me-DUPHOS

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
136735-95-0	(+)-1,2-Bis((2S,5S)-2,5-dimethylphosph		unlisted

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

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Air sensitive.Moisture sensitive.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation. May be harmful if absorbed through the skin.
Ingestion:
May cause irritation of the digestive tract. May be harmful if swallowed.
Inhalation:
May cause respiratory tract irritation. May be harmful if inhaled.
Chronic:
Not available.

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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.
Ingestion:
Get medical aid. Wash mouth out with water.
Inhalation:
Remove from exposure and move to fresh air immediately.
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.
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.

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Section 7 - HANDLING and STORAGE
Handling:
Avoid breathing dust, vapor, mist, or gas. Avoid contact with skin and eyes.
Storage:
Store in a cool, dry place. Store in a tightly closed container.
Store under nitrogen.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 136735-95-0: Personal Protective Equipment Eyes: Not available.
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: Not available.
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: C18H28P2
Molecular Weight: 306.37

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Exposure to air, exposure to moist air or water.
Incompatibilities with Other Materials:
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# 136735-95-0 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
(+)-1,2-Bis((2S,5S)-2,5-dimethylphospholano)benzene - 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
Not regulated as a hazardous material.
IMO
Not regulated as a hazardous material.
RID/ADR
No information available.

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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# 136735-95-0: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 136735-95-0 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 136735-95-0 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

反应信息

• 作为反应物：
  描述：

  (+)-1,2-双((2S,5S)-2,5-二甲基磷烷)苯 在 过氧化脲素 、 C₄₀H₃₂InN₂O₄^(1-)*Na⁽¹⁺⁾ 作用下， 以 氘代氯仿 为溶剂， 反应 0.08h， 生成 C₁₈H₂₈O₂P₂
  参考文献：
  名称：

  31P NMR 光谱手性识别八面体铟配合物原位氧化膦氧化物

  摘要：

  在此，证明了八面体铟配合物对氧化膦的有效手性识别。通过31 P 核磁共振光谱有效地进行了使用膦和过氧化氢形成的原位制备的氧化膦的直接手性分析。一致地获得了足够的手性膦峰分辨率，从而能够可靠地确定绝对手性。已经提出了基于实验和密度泛函理论计算的合理的 1:1 绑定模型。

  DOI：

  10.1021/acs.orglett.1c02847
• 作为产物：
  描述：

  (2R,5R)-2,5-己二醇 在 ruthenium trichloride 、 sodium periodate 、 氯化亚砜 作用下， 生成 (+)-1,2-双((2S,5S)-2,5-二甲基磷烷)苯
  参考文献：
  名称：

  C2-symmetric bis(phospholanes) and their use in highly enantioselective hydrogenation reactions

  摘要：

  DOI：

  10.1021/ja00022a047
• 作为试剂：
  描述：

  4-(benzofuran-5-yl)benzaldehyde 在 二氢吡啶 、 2,4,5,6-四(9H-咔唑-9-基)异酞腈 、 三氟化硼乙醚 、 (+)-1,2-双((2S,5S)-2,5-二甲基磷烷)苯 、 N,N-二异丙基乙胺 、 cobalt(II) iodide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 72.0h， 生成 N-((R)-(4-(benzofuran-6-yl)phenyl)((1S,2S)-2-methyl-2-phenylcyclopropyl)methyl)-4-methylbenzene-sulfonamide
  参考文献：
  名称：

  协同光氧化还原和钴催化环丙烯与亚胺的去对称加成反应

  摘要：

  在此，我们利用光氧化还原和不对称钴催化之间的协同作用，设计了一种环丙烯去对称加成反应。该方案促进了一系列具有高产率、对映选择性和非对映选择性的手性官能化环丙烷的合成（44 个实例，产率高达 93% 且 >99% ee）。提出了一种可能的反应机制，涉及 Co-H 物种的环丙烯去对称化和 Co-烷基物种的亚胺加成。这项研究为重要的手性环丙烷提供了一条新途径，并扩展了不对称金属光氧化还原催化的前沿。

  DOI：

  10.1021/jacs.4c07096

文献信息

• General and Selective Copper-Catalyzed Reduction of Tertiary and Secondary Phosphine Oxides: Convenient Synthesis of Phosphines
  作者：Yuehui Li、Shoubhik Das、Shaolin Zhou、Kathrin Junge、Matthias Beller

  DOI：10.1021/ja301764m

  日期：2012.6.13

  Novel catalytic reductions of tertiary and secondary phosphine oxides to phosphines have been developed. Using tetramethyldisiloxane (TMDS) as a mild reducing agent in the presence of copper complexes, PO bonds are selectively reduced in the presence of other reducible functional groups (FGs) such as ketones, esters, and olefins. Based on this transformation, an efficient one pot reduction/phosphination

  已经开发了将叔和仲氧化膦新型催化还原为膦的方法。在铜配合物的存在下使用四甲基二硅氧烷 (TMDS) 作为温和的还原剂，PO 键在其他可还原的官能团 (FG) 的存在下被选择性还原，例如酮、酯和烯烃。基于这种转化，有效的一锅还原/膦化多米诺序列允许以良好的产率合成各种官能化的芳族和脂肪族膦。
• Synthesis and Hydrogenation Activity of Iron Dialkyl Complexes with Chiral Bidentate Phosphines
  作者：Jordan M. Hoyt、Michael Shevlin、Grant W. Margulieux、Shane W. Krska、Matthew T. Tudge、Paul J. Chirik

  DOI：10.1021/om500329q

  日期：2014.10.27

  metathesis methods. Each of the isolated organometallic iron complexes was established as a tetrahedral and hence high-spin ferrous compound, as determined by Mössbauer spectroscopy, magnetic measurements, and, in many cases, X-ray diffraction. One example containing a Josiphos-type ligand, (SL-J212-1)Fe(CH2SiMe3)2, proved more active than other isolated iron dialkyl precatalysts. Filtration experiments

  已评估了双（膦）铁二烷基络合物对烯烃的不对称氢化的活性。高通量实验被用来确定合适的铁-膦组合，利用吡啶从py 2 Fe（CH 2 SiMe 3）2中置换出吡啶以形成前催化剂。还使用配体取代和盐复分解方法实现了双（膦）二烷基铁二烷基铁配合物的制备规模合成。通过Mössbauer光谱，磁测量以及在许多情况下，通过X射线衍射测定，每种分离的有机金属铁络合物均被确定为四面体，因此是高自旋的亚铁化合物。包含Josiphos型配体（SL-J212-1）Fe（CH2 SiMe 3）2，被证明比其他分离的二烷基铁预催化剂更具活性。过滤实验和观察到的对映体选择性的缺乏支持了膦配体在被二氢激活并形成催化活性多相铁时解离。据信较大的六元螯合物会降低膦对铁中心的配位亲和力，从而能够形成金属颗粒。
• COBALT PHOSPHINE ALKYL COMPLEXES FOR THE ASYMMETRIC HYDROGENATION OF ALKENES
  申请人：The Trustees of Princeton University

  公开号：US20130281747A1

  公开（公告）日：2013-10-24

  Disclosed herein are manganese, iron, nickel, or cobalt compounds having a bidentate ligand and the use of these compounds for the hydrogenation of alkenes, particularly the asymmetric hydrogenation of prochiral olefins.

  本文披露了具有双齿配体的锰、铁、镍或钴化合物，以及这些化合物在烯烃的加氢反应中的应用，特别是对前手性烯烃的不对称加氢。
• RHODIUM CATALYST AND METHOD FOR PRODUCING AMINE COMPOUND
  申请人：TAKEDA PHARMACEUTICAL COMPANY LIMITED

  公开号：US20150051416A1

  公开（公告）日：2015-02-19

  [Problem] Provision of a superior rhodium catalyst and a production method of amine compound. [Solving Means] A rhodium complex coordinated with a compound represented by the formula

  提供一种优质的铑催化剂和胺化合物的生产方法。采用与公式表示的化合物配位的铑络合物。
• PHOSPHACYCLE COMPOUND AND PROCESS FOR PRODUCTION THEREOF
  申请人：Dow Global Technologies LLC

  公开号：US20180291048A1

  公开（公告）日：2018-10-11

  The invention relates to oligomerization of olefins, such as ethylene, to higher olefins, such as a mixture of 1-hexene and 1-octene, using a catalyst system that comprises a) a source of chromium b) one or more activators and c) a phosphacycle-containing ligating compound. Additionally, the invention relates to a phosphacycle-containing ligating compound and a process for making said compound.

  该发明涉及将烯烃（如乙烯）寡聚化为更高级别的烯烃（如1-己烯和1-辛烯）的方法，使用包括a）铬源b）一个或多个活化剂和c）含有膦环结构的配位化合物的催化剂体系。此外，该发明还涉及一种含有膦环结构的配位化合物和制备该化合物的方法。