(R,R)-(+)-1,2-双(叔丁基甲基膦)苯 | 919778-41-9

• 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: (R,R)-(+)-1,2-双(叔丁基甲基膦)苯
• 英文名称: (R,R)-(+)-1,2-bis(t-butylmethylphosphino)benzene
• 英文别名: 1,2-bis(tert-butyl(methyl)phosphino)benzene；1,2-di(t-butylmethylphosphino)benzene；1,2-bis(t-butylmethylphosphino)benzene；BenzP；Phosphine, 1,1'-(1,2-phenylene)bis[1-(1,1-dimethylethyl)-1-methyl-；tert-butyl-[2-[tert-butyl(methyl)phosphanyl]phenyl]-methylphosphane
• CAS: 919778-41-9
• 化学式: C₁₆H₂₈P₂
• 分子量: 282.346
• InChiKey: JFUWTGUCFKJVST-UHFFFAOYSA-N

物化性质

• 沸点：
  362.3±25.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

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
• 储存条件：
  存储条件为2-8°C，并需使用惰性气体保护。

SDS

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Section 1: Product Identification
Chemical Name: (R,R)-(+)-1,2-Bis(t-butylmethylphosphino)benzene (R,R)-BenzP*
CAS Registry Number: 919778-41-9
Formula: C16H28P2
EINECS Number: none
Chemical Family: phosphine ligand
Synonym: (R,R)-BenzP*

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 919778-41-9 100% no data no data

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Section 3: Hazards Identification
Emergency Overview: Irritating to skin, eyes and respiratory tract.
Primary Routes of Exposure: Ingestion, inhalation, eyes
Eye Contact: Causes slight to mild 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,
Handling and Storage:
well-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: white xtl.
Molecular Weight: 282.34
Melting Point: 125-126°
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, phosphorus 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：

  bis(1,5-cyclooctadiene)nickel (0) 、 (R,R)-(+)-1,2-双(叔丁基甲基膦)苯 以 四氢呋喃 为溶剂， 反应 18.0h， 生成 (BenzP)Ni(COD)
  参考文献：
  名称：

  α，β−不飽和カルボン酸の合成方法

  摘要：

  可以的，这段文字的中文翻译如下： 【课题】能够提高α，β-不饱和羧酸生成量的α，β-不饱和羧酸合成方法。【解决方法】一种α，β-不饱和羧酸的合成方法，包括在过渡金属配合物存在的情况下，在Lewis酸和碱存在的情况下，使烯烃和二氧化碳发生反应，形成具有特定结构的金属内酯化合物作为中间体，并使Lewis酸和碱作用于所述金属内酯化合物，其中碱的共轭酸的酸离解常数（pKa1）与α，β-不饱和羧酸的酸离解常数（pKa2）之间的关系为pKa1 < pKa2，这是一种α，β-不饱和羧酸的合成方法。【选择图】无

  公开号：

  JP2019156790A
• 作为产物：
  描述：

  1,2-双(二氯膦酰)苯 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 44.0h， 生成 (R,R)-(+)-1,2-双(叔丁基甲基膦)苯
  参考文献：
  名称：

  α，β−不飽和カルボン酸の合成方法

  摘要：

  可以的，这段文字的中文翻译如下： 【课题】能够提高α，β-不饱和羧酸生成量的α，β-不饱和羧酸合成方法。【解决方法】一种α，β-不饱和羧酸的合成方法，包括在过渡金属配合物存在的情况下，在Lewis酸和碱存在的情况下，使烯烃和二氧化碳发生反应，形成具有特定结构的金属内酯化合物作为中间体，并使Lewis酸和碱作用于所述金属内酯化合物，其中碱的共轭酸的酸离解常数（pKa1）与α，β-不饱和羧酸的酸离解常数（pKa2）之间的关系为pKa1 < pKa2，这是一种α，β-不饱和羧酸的合成方法。【选择图】无

  公开号：

  JP2019156790A
• 作为试剂：
  描述：

  6-庚烯酸 在 N,N-二甲基丙烯基脲 、 正丁基锂 、 草酰氯 、 iron(III)-acetylacetonate 、 (R,R)-(+)-1,2-双(叔丁基甲基膦)苯 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 21.5h， 生成 2,3,3-trimethylbut-2-yl (S)-2-phenylhept-6-enoate 、 、 2,3,3-trimethylbut-2-yl (1S*,2R*)-2-benzylcyclopentanecarboxylate 、 2,3,3-trimethylbut-2-yl (1S*, 2S*)-2-benzylcyclopentanecarboxylate
  参考文献：
  名称：

  α-氯酯与芳基格氏试剂的铁催化对映选择性交叉偶联反应

  摘要：

  报道了第一个铁催化的有机金属化合物和有机亲电试剂之间的对映选择性交叉偶联反应。在催化量的铁盐和手性双膦配体存在下，合成通用的外消旋 α-氯代和 α-溴代链烷酸酯与芳基格利雅试剂偶联，得到高产率的产物，具有可接受和合成有用的对映选择性（高达 91 :9)。通过简单的脱保护/重结晶，产生的 α-芳基链烷酸酯很容易转化为相应的具有高光学富集（er 高达 >99:1）的 α-芳基链烷酸。自由基探针实验的结果与涉及形成烷基自由基中间体的机制一致，该中间体以分子间方式经历随后的对映聚合芳基化。

  DOI：

  10.1021/jacs.5b02277

文献信息

• 使用甲酸和炔烃合成α,β–不饱和酸的方法
  申请人：南开大学

  公开号：CN105693498B

  公开（公告）日：2018-07-03

  本发明涉及一种使用甲酸和炔烃合成a,b–不饱和酸的方法,具体是在镍催化剂作用下使用甲酸和炔烃合成a,b–不饱和酸的方法。催化剂用量为底物物质的量的0.01~2 mol%，酸酐用量为底物物质的量的3~30 mol%，乙炔气压力1~10 MPa，反应温度为25~100℃，反应时间为5~12小时。本发明克服了现有炔烃氢羧化的缺点，无需使用有毒的一氧化碳气体，整个过程反应条件温和、效率高、选择性好，是一条符合绿色化学并具有很好应用前景的制备a,b–不饱和酸的方法，具有很好的工业应用前景。
• Cobalt-Catalyzed Asymmetric Hydrogenation of α,β-Unsaturated Carboxylic Acids by Homolytic H₂ Cleavage
  作者：Hongyu Zhong、Michael Shevlin、Paul J. Chirik

  DOI：10.1021/jacs.9b13876

  日期：2020.3.18

  The asymmetric hydrogenation of α, β-unsaturated carboxylic acids using readily prepared bis(phosphine) cobalt(0) 1,5-cyclooctadiene precatalysts is described. Di-, tri- and tetra-substituted acrylic acid derivatives with various substitution patterns as well as dehydro-α-amino acid derivatives were hydrogenated with high yields and enantioselectivities, affording chiral carboxylic acids including

  描述了使用容易制备的双 (膦) 钴 (0) 1,5- 环辛二烯预催化剂对 α, β-不饱和羧酸进行不对称氢化。具有各种取代模式的二、三和四取代丙烯酸衍生物以及脱氢-α-氨基酸衍生物以高产率和对映选择性氢化，得到手性羧酸，包括萘普生、(S)-氟比洛芬和 D-多巴前体。经常观察到高达 200 的营业额。使用还原的钴 (0) 预催化剂观察到与常见有机官能团的相容性，并确定甲醇和异丙醇等质子溶剂是最佳的。合成了一系列双（膦）钴（II）双（新戊酸盐）配合物，它们是最先进的钌（II）催化剂的结构类似物，表征并证明具有催化能力。X 波段 EPR 实验显示双（膦）钴（II）双（羧酸盐）在催化反应中生成，并被确定为催化剂静止状态。从化学计量反应中分离和表征钴 (II)-底物复合物表明，在游离羧酸存在下，烯烃插入氢化钴中，产生与催化反应相同的烷烃对映异构体。氘标记研究确定了通过 Co(0) 和 H2（或 D2）顺式加成通过烯烃双键激活均裂
• METHOD FOR PRODUCING OPTICALLY ACTIVE 1,2-BIS(DIALKYLPHOSPHINO)BENZENE DERIVATIVE
  申请人：Tamura Ken

  公开号：US20130172597A1

  公开（公告）日：2013-07-04

  An industrially advantageous method for producing an optically active 1,2-bis(dialkylphosphino)benzene derivative of the present invention is provided. The method is characterized in that a phosphine-borane compound represented by the following general formula (1) is subjected to a deboronation reaction, followed by lithiation, then the reaction product is subjected to reaction with an alkyldihalogenophosphine represented by R a PX′ 2 , and thereafter the reaction product is subjected to reaction with a Grignard reagent represented by R b MgX″ to produce an optically active 1,2-bis(dialkylphosphino)benzene derivative (A). R 1 and R 2 respectively represent an alkyl group having 1 to 8 carbon atoms, and the number of carbon atoms is different between R 1 and R 2 . R a is either R 1 or R 2 and R b is the other of R 1 and R 2 . X, X′, and X″ each represent a halogen atom.

  本发明提供了一种在工业上具有优势的生产光学活性1,2-双(二烷基膦基)苯衍生物的方法。该方法的特征在于，将由下述一般式（1）表示的膦硼烷化合物进行脱硼反应，然后进行锂化反应，然后将反应产物与由RaPX′2表示的烷基二卤代膦烷发生反应，然后将反应产物与由RbMgX″表示的格氏试剂发生反应，以产生光学活性的1,2-双(二烷基膦基)苯衍生物（A）。R1和R2分别表示具有1至8个碳原子的烷基基团，且R1和R2之间的碳原子数不同。R为R1或R2中的一个，R为R1和R2中的另一个。X、X′和X″分别表示一个卤素原子。
• 2,3-BISPHOSPHINOPYRAZINE DERIVATIVE, METHOD FOR PRODUCING SAME, TRANSITION METAL COMPLEX, ASYMMETRIC CATALYST, AND METHOD FOR PRODUCING ORGANIC BORON COMPOUND
  申请人：Nippon Chemical Industrial Co., Ltd.

  公开号：US20210047351A1

  公开（公告）日：2021-02-18

  Provided is a 2,3-bisphosphinopyrazine derivative represented by the following general formula (1), wherein R 1 , R 2 , R 3 , and R 4 represent an optionally substituted straight-chain or branched alkyl group having 1 to 10 carbon atoms, an optionally substituted cycloalkyl group, an optionally substituted adamantyl group, or an optionally substituted phenyl group, R 5 represents an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group, each R 5 may be the same group or a different group, R 6 represents a monovalent substituent, n denotes an integer of 0 to

  给出一个由以下通用公式（1）表示的2,3-双磷酸吡嗪衍生物，其中R1、R2、R3和R4代表一个可选择取代的直链或支链烷基，其碳原子数为1至10，一个可选择取代的环烷基，一个可选择取代的金刚烷基或一个可选择取代的苯基，R5代表一个可选择取代的碳原子数为1至10的烷基或一个可选择取代的苯基，每个R5可以是相同的基团或不同的基团，R6代表一个一价取代基，n表示0至的整数。
• COPPER CATALYZED HALOGENATON AND REACTION PRODUCTS
  申请人：Wisconsin Alumni Research Foundation

  公开号：US20140371480A1

  公开（公告）日：2014-12-18

  A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring a halogen from an sp 2 to a benzylic carbon with good enantioselectivity and concomitant borylation of the Ar-halo bond. The resulting enantio-enriched benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom or carbon-carbon bond while maintaining high ee. The reaction can be used to efficiently prepare novel compounds and intermediates for the preparation of therapeutics and ligands for catalysis.

  一种Cu(I)催化的1,3-卤迁移反应有效地通过将卤素从sp2转移到苄基碳来循环利用一个活化基团，具有良好的对映选择性并伴随Ar-卤键的硼化反应。所得的对映富集的苄基卤化物可以在同一容器中在各种条件下反应，形成额外的碳-杂原子或碳-碳键，同时保持高的ee。该反应可用于高效制备新型化合物和制备治疗剂和催化剂配体的中间体。