(-)-1,2-双[(2R,5R)-2,5-二甲基磷]苯 | 147253-67-6

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物 - 芳香烃
• 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[(2R,5R)-2,5-二甲基磷]苯
• 中文别名: (-)-1,2-双((2R,5R)-2,5-二甲基磷)苯
• 英文名称: (R,R)-Me-DuPhos
• 英文别名: 1,2-bis[(2R,5R)-2,5-dimethylphospholano]benzene；(R,R)-DuPhos；methyl-DUPHOS；Me-Duphos；(2R,5R)-1-[2-[(2R,5R)-2,5-dimethylphospholan-1-yl]phenyl]-2,5-dimethylphospholane
• CAS: 147253-67-6
• 化学式: C₁₈H₂₈P₂
• 分子量: 306.368
• InChiKey: AJNZWRKTWQLAJK-KLHDSHLOSA-N

物化性质

• 熔点：
  66-76 °C
• 比旋光度：
  -476° (c 1, hexane)
• 沸点：
  415.0±15.0 °C(Predicted)

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

• WGK Germany：
  3
• 安全说明：
  S22,S24/25
• 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
• 储存条件：
  室温且干燥

SDS

Name:	(-)-1 2-Bis((2R 5R)-2 5-dimethylphospholano)benzene Material Safety Data Sheet
Synonym:	(R,R)-Me-DUPHO
CAS:	147253-67-6

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

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
147253-67-6	(-)-1,2-Bis((2R,5R)-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# 147253-67-6: 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:
Incompatible materials, 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# 147253-67-6 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
(-)-1,2-Bis((2R,5R)-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# 147253-67-6: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 147253-67-6 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 147253-67-6 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

轻吨染料

反应信息

• 作为反应物：
  描述：

  (-)-1,2-双[(2R,5R)-2,5-二甲基磷]苯 在 三乙烯二胺 、 dimethyl sulfide borane 、 双氧水 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 6.5h， 生成 1,2-双[(2R,5R)-2,5-二甲基磷]一氧化苯
  参考文献：
  名称：

  使用新型双（膦）一氧化物手性配体不对称催化合成 α-手性胺

  摘要：

  我们已经证明 Me-DuPHOS 一氧化 (BozPHOS) 在铜催化下将二烷基锌加成到 N-膦亚胺中是一种非常有效的配体，提供了获得 α-手性胺的途径。新配体对于添加反应性较低的二甲基锌特别有效。该方法的主要优点是收率高、底物范围广、对映选择性高、催化剂负载量低（3 mol%）。

  DOI：

  10.1021/ja038291+
• 作为产物：
  描述：

  2,5-己二酮 在 titanium(IV) isopropylate 、 sodium tetrahydroborate 、 氢气 、 碘 、 三溴化磷 、 magnesium 、 O,O'-dibenzoyl-L-tartaric acid 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 (-)-1,2-双[(2R,5R)-2,5-二甲基磷]苯
  参考文献：
  名称：

  双磷配体的制备方法

  摘要：

  本发明涉及一种双磷配体的制备方法，该双磷配体的制备方法中，将化合物(1)与金属镁进行格式反应，制备化合物(2)；将化合物(3)与五氯化磷进行第一取代反应，制备化合物(4)；然后将化合物(2)与化合物(4)进行第二取代反应，制备化合物(5)；最后将化合物(5)进行还原反应，就得到式(6)所示双磷配体：工艺简单，原料简单、易得，制备过程工艺条件易控，无需制备磷氢类中间体，在较为温和的工艺条件，就能制得双膦配体，有利于双膦配体的大规模生产。

  公开号：

  CN114835749A
• 作为试剂：
  描述：

  N,N-diphenyl methacrylamide 、 苯甲醛 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 氢气 、 (-)-1,2-双[(2R,5R)-2,5-二甲基磷]苯 作用下， 以 1,2-二氯乙烷 为溶剂， 生成 (+)-2-methyl-4-oxo-4,N,N-triphenylbutyramide 、 (+)-2-methyl-4-oxo-4,N,N-triphenylbutyramide
  参考文献：
  名称：

  1,1-二取代烯烃与未官能化醛的铑催化高对映选择性直接分子间加氢酰化

  摘要：

  我们已经确定，阳离子铑 (I)/(R,R)-QuinoxP* 复合物催化 α 取代丙烯酰胺与未官能化脂肪醛的高度对映选择性直接分子间加氢酰化反应，以高产率生成相应的 γ-酮酰胺，并具有优异的 ee 值.

  DOI：

  10.1021/ja905908z

文献信息

• [EN] METHODS, PROCESSES AND INTERMEDIATES FOR PREPARING CHROMAN COMPOUNDS<br/>[FR] PROCÉDÉS, PROCESSUS ET INTERMÉDIAIRES POUR LA PRÉPARATION DE COMPOSÉS CHROMANE
  申请人：LUPIN LTD

  公开号：WO2021144814A1

  公开（公告）日：2021-07-22

  This disclosure describes an economical and scalable method and process to synthesize the Calcium sensing receptor (CaSR) modulating agent 2-methyl-5-((2R,4S)-2-((((R)-1-(naphthalen-1-yl)ethyl)amino)methyl)chroman-4-yl)benzoic acid, its intermediates and pharmaceutically acceptable salts therefor. Uses of said intermediates for synthesis of compounds which may be intermediates to the synthesis of 2-methyl-5-((2R,4S)-2-((((R)-1-(naphthalen-1-yl)ethyl)amino)methyl)chroman-4-yl)benzoic acid are also described herein.

  这份披露描述了一种经济且可扩展的方法和过程，用于合成钙感测受体（CaSR）调节剂2-甲基-5-((2R,4S)-2-((((R)-1-(萘-1-基)乙基)氨基)甲基)香豆素-4-基)苯甲酸，及其中间体和药用可接受的盐。还描述了所述中间体用于合成可能是2-甲基-5-((2R,4S)-2-((((R)-1-(萘-1-基)乙基)氨基)甲基)香豆素-4-基)苯甲酸合成中间体的化合物的用途。
• Oxidative addition of methylene chloride to Me-DuPhos complexes of palladium and rhodium
  作者：Perry M. Scheetz、Natalia F. Blank、Sarah K. Gibbons、David S. Glueck、Arnold L. Rheingold

  DOI：10.1016/j.ica.2018.08.007

  日期：2018.11

  Abstract Oxidative addition of methylene chloride to Pd((R,R)-Me-DuPhos)(L) (1–3; L = P(t-Bu)3, PCy3, or trans-stilbene) gave Pd((R,R)-Me-DuPhos)(CH2Cl)(Cl) (4). Treatment of [Rh(COD)(Cl)]2 with (R,R)-Me-DuPhos at low temperature in THF or CH2Cl2 afforded [Rh((R,R)-Me-DuPhos)(Cl)]2 (5). At room temperature, these reactions also gave the byproduct [Rh((R,R)-Me-DuPhos)2][Cl], which was prepared independently

  摘要在Pd（（R，R）-Me-DuPhos）（L）（1-3; L = P（t-Bu）3，PCy3或反式二苯乙烯）上氧化二氯甲烷而得到Pd（（R， R）-Me-DuPhos）（CH 2 Cl）（Cl）（4）。在THF或CH2Cl2中用（R，R）-Me-DuPhos于低温处理[Rh（COD）（Cl）] 2，得到[Rh（（R，R）-Me-DuPhos）（Cl）] 2（5 ）。在室温下，这些反应还得到副产物[Rh（（R，R）-Me-DuPhos）2] [Cl]，其独立制备为BF4盐6。当在CH2Cl2中生成5时，两者的氧化加成反应C Cl键产生桥联卡宾络合物（Rh（（R，R）-Me-DuPhos）（Cl））2（µ-Cl）2（µ-CH2）（8）。6和8均在晶体学上进行了表征。
• Chiral <i>cis</i>-Platinum Acetylide Complexes via Diphosphine Ligand Exchange: Effect of the Ligand
  作者：Amber L. Sadowy、Michael J. Ferguson、Robert McDonald、Rik R. Tykwinski

  DOI：10.1021/om800633h

  日期：2008.12.8

  Chiral, bidentate phosphine ligands (R,R-CHIRAPHOS, R-PROPHOS, S,S-BDPP, R,R-Me-DUPHOS, R,R-NORPHOS) react with trans-platinum acetylide complexes 1a and 1b, (Ph3P)2Pt(C≡CR)2 (R = TIPS, p-MeC6H4), via ligand exchange to generate chiral platinum acetylide complexes. The corresponding cis-platinum complexes are formed in all cases except for the reaction of 1b with S,S-BDPP, where the dimeric complex

  手性二齿膦配体（R，R -CHIRAPHOS，R- PROPHOS，S，S- BDPP，R，R- Me-DUPHOS，R，R- NORPHOS）与反铂乙炔化物络合物1a和1b（Ph 3 P）2 Pt（C≡CR）2（R = TIPS，p -MeC 6 H 4），通过配体交换产生手性的乙炔铂络合物。在所有情况下均形成相应的顺铂络合物，但1b与S，S- BDPP的反应除外，其中二聚体络合物4d'是产品。相反，1a和1b与配体S，S -DIOP，R -BINAP和R -SYNPHOS的反应未能以可观的收率得到所需的产物。圆二色光谱用于检查手性配体对乙炔铂骨架的手性的影响。报道了非手性络合物1a和手性衍生物4e的X射线晶体学分析。
• Combinatorial Approach to Chiral Tris-ligated Carbophilic Platinum Complexes: Application to Asymmetric Catalysis
  作者：Alexandre Pradal、Serafino Gladiali、Veronique Michelet、Patrick Y. Toullec

  DOI：10.1002/chem.201304794

  日期：2014.6.2

  the synthesis of libraries of chiral tris‐ligated cationic platinum complexes and their in situ evaluation as asymmetric carbophilic catalysts in a model domino hydroarylation/cyclization reaction of a 1,6‐enyne was developed. A catalyst‐generation process based on a combination of a monodentate and a bidentate phosphorus ligand allowed the formation of 108 chiral complexes. One‐pot screening of the stereoinduction

  开发了一种简单的方法，用于合成手性三连接阳离子铂络合物的文库，并在1,6-烯炔的模型多米诺加氢化/环化反应中作为不对称嗜碳催化剂进行原位评估。基于单齿和双齿磷配体的催化剂生成过程可以形成108个手性络合物。用该库在多米诺加成/环化反应测试中对立体诱导进行一锅法筛选，验证了该方法的有效性，并强调了单齿配体伙伴在获得高对映选择性方面所起的关键作用。在两种具有挑战性的底物/亲核试剂组合的情况下，组合方法导致对映选择性的显着提高。
• Efficient approach for the design of effective chiral quaternary phosphonium salts in asymmetric conjugate additions
  作者：Seiji Shirakawa、Atsuyuki Kasai、Takashi Tokuda、Keiji Maruoka

  DOI：10.1039/c3sc22130j

  日期：——

  approach for the design of chiral quaternary phosphonium bromides as chiral phase-transfer catalysts was demonstrated. A catalyst library of phosphonium salts with various structures was readily constructed using commercially available chiral phosphines as catalyst precursors, and an optimized catalyst was successfully applied to highly enantioselective conjugate additions under base-free phase-transfer

  证明了一种设计手性季chi溴化物作为手性相转移催化剂的有效方法。使用市售的手性膦作为催化剂前体可以轻松构建具有各种结构的phospho盐的催化剂库，并且在无催化剂的低相转移条件下，将优化的催化剂成功应用于高对映选择性共轭物的加成。