(ΑS)-Α-[(二苯基膦)甲基]苯甲胺 | 1103533-85-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: (ΑS)-Α-[(二苯基膦)甲基]苯甲胺
• 中文别名: (S)-2-(二苯基膦基)-1-苯基乙胺；(S)-2-二苯基膦基-1-苯基乙基胺；(S)-2-(二苯基膦基)-1-苯乙胺；(S)-2-二苯基膦基-1-苯基乙基胺, 97+%
• 英文名称: (S)-2-(diphenylphosphino)-1-phenylethylamine
• 英文别名: (S)-2-(diphenylphosphino)-1-phenylethanamine；(S)-2-(diphenylphosphanyl)-1-phenylethan-1-amine；(S)-2-(Diphenylphosphino)-1-phenylethanamine；(1S)-2-diphenylphosphanyl-1-phenylethanamine
• CAS: 1103533-85-2
• 化学式: C₂₀H₂₀NP
• 分子量: 305.359
• InChiKey: OTNYDYNCOCRMDG-HXUWFJFHSA-N

物化性质

• 沸点：
  445.3±38.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

安全信息

• 危险性防范说明：
  P261,P264,P271,P280,P302+P352,P304+P340,P305+P351+P338,P312,P362,P403+P233,P501
• 危险性描述：
  H315,H319,H335
• 储存条件：
  2-8°C

SDS

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Section 1: Product Identification
Chemical Name: (S)-2-(Diphenylphosphino)-1-phenylethylamine, min. 97%
CAS Registry Number: 1103533-85-2
Formula: C26H24NP
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 1103533-85-2 100% 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: white solid
Molecular Weight: 381.43
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：

  (ΑS)-Α-[(二苯基膦)甲基]苯甲胺 在 lithium aluminium tetrahydride 、 sodium sulfate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 43.5h， 生成
  参考文献：
  名称：

  铁PNP'和P-NH-P'不对称加氢催化剂的合成

  摘要：

  已知类型为mer，反式-[Fe（PNP'）（CO）2 Br] BF 4的配合物是酮和亚胺不对称直接加氢的前催化剂。采用相关配体的支架，我们成功地产生并测试了一系列的三个新的预催化剂的[Fe（PCY 2 CH 2 CH = NCH（R）CH 2 PPH 2）（CO）2 BR] BF 4与手性从（派生小号） -具有苯基，苄基和异丙基取代基（R）的氨基醇，可产生相当活泼和选择性的系统。用于将苯乙酮还原为（S）-1-苯基乙醇的周转频率长达920小时在50°C和5-25 atm的H 2下，获得了–1和高达74％的对映体过量。然而，我们发现，将这些大的基团R置于氮旁边被发现对催化活性有害。为了扩展配体结构的范围，我们从邻二苯基膦基苯甲醛和膦胺PPh 2 CHR 1 CHR 2 NH 2（R 1 = H，Ph ，CH 2 PH，用的iPr - [R 2 = H或R 1 = Me中，pH值- [R 2 =

  DOI：

  10.1021/om5008083
• 作为产物：
  描述：

  噁拉戈利杂质35 在 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (ΑS)-Α-[(二苯基膦)甲基]苯甲胺
  参考文献：
  名称：

  硫化物的不对称动力学拆分，用于构建不对称硫化物和手性3,3-二取代的羟吲哚。

  摘要：

  使用衍生自靛红与巯基的对醌甲基化物获得的一系列3,3-二取代的羟吲哚被用于形成不对称的二硫化物，也可以直接获得具有手性季碳中心和不对称的二硫化物的3,3-二取代的羟吲哚。一步被手性膦催化的高选择性。

  DOI：

  10.1039/c9ob01065c

文献信息

• β-Amino Phosphine Mn Catalysts for 1,4-Transfer Hydrogenation of Chalcones and Allylic Alcohol Isomerization
  作者：Vipulan Vigneswaran、Samantha N. MacMillan、David C. Lacy

  DOI：10.1021/acs.organomet.9b00692

  日期：2019.11.25

  selectively to the saturated ketone at short times and can be fully converted to the alcohol when reactions are prolonged. The mechanism of chalcone reduction was briefly considered. Allylic alcohols are not reactive in 2-propanol, but quantitative isomerization occurs in toluene. Thus, we suspect that the allylic alcohols are dehydrogenated and the resulting ketone is formed through a direct 1,4-hydrogenation

  带有氨基酸衍生的PN配体的Mn配合物用于酮和查尔酮底物在2-丙醇中温和加热的催化转移氢化（TH）。而且，查耳酮在短时间内选择性地还原成饱和酮，并且在反应延长时可以完全转化为醇。查尔酮减少的机制进行了简要考虑。烯丙醇在2-丙醇中不具有反应性，但是在甲苯中发生定量异构化。因此，我们怀疑烯丙基醇被脱氢，并且通过查耳酮的直接1，4-氢化形成了生成的酮。最后，探索了已在基于Mn的TH反应中使用的其他几种相关配体，以测试配体设计在促进化学选择性方面的可行性。
• <i>C1</i>-Symmetric PNP Ligands for Manganese-Catalyzed Enantioselective Hydrogenation of Ketones: Reaction Scope and Enantioinduction Model
  作者：Liyao Zeng、Huaxin Yang、Menglong Zhao、Jialin Wen、James H. R. Tucker、Xumu Zhang

  DOI：10.1021/acscatal.0c04206

  日期：2020.12.4

  ferrocene-based chiral PNP ligands is reported. These tridentate ligands were successfully applied in Mn-catalyzed asymmetric hydrogenation of ketones, giving high enantioselectivities (92%∼99% ee for aryl alkyl ketones) as well as high efficiencies (TON up to 2000). In addition, dialkyl ketones could also be hydrogenated smoothly. Manganese intermediates that might be involved in the catalytic cycle were analyzed

  报道了基于二茂铁的手性PNP配体家族。这些三齿配体已成功应用于锰催化的酮的不对称加氢反应中，具有很高的对映选择性（芳基烷基酮的ee为92％〜99％ee）以及高效率（TON高达2000）。另外，二烷基酮也可以平稳地氢化。分析了可能参与催化循环的锰中间体。进行了DFT计算以帮助理解手性诱导模型。Mn / PNP催化剂可通过柔性5元环中的膦部分变形来区分具有不同空间特性的两个基团。
• α-Functionalization of 2-Vinylpyridines via a Chiral Phosphine Catalyzed Enantioselective Cross Rauhut–Currier Reaction
  作者：Cong Qin、Yonghai Liu、Yang Yu、Yiwei Fu、Hao Li、Wei Wang

  DOI：10.1021/acs.orglett.8b00008

  日期：2018.3.2

  Herein, 2-vinylpyridines as a new type of electron-poor system for the asymmetric cross Rauhut–Currier reaction are reported. 2-Vinylpyridines are chemo- and enantioselectively activated by a newly designed chiral phosphine catalyst. The new reaction provides a powerful synthetic tool for accessing structurally diverse, highly valued chiral pyridine building blocks in good yields and with high enantioselectivities

  在此，据报道2-乙烯基吡啶是一种用于不对称交叉Rauhut-Currier反应的新型电子贫乏系统。2-乙烯基吡啶被新设计的手性膦催化剂化学和对映选择性活化。新的反应为以高收率和高对映选择性获得结构多样的，高价值的手性吡啶构件提供了强大的合成工具。初步的机理研究表明，催化剂中的两个NH质子对于底物的协同活化和控制该反应的立体选择性至关重要。
• Tunable Bifunctional Phosphine-Squaramide Promoted Morita-Baylis-Hillman Reaction of<i>N</i>-Alkyl Isatins with Acrylates
  作者：Ze Dong、Chao Yan、Yongzhi Gao、Chune Dong、Guofu Qiu、Hai-Bing Zhou

  DOI：10.1002/adsc.201500110

  日期：2015.6.15

  was applied successfully in the synthesis of chiral cyclic spiropyrrolizidineoxindole and γ‐butyrolactone derivatives without enantioselectivity deterioration. The possible mechanism of this MBH reaction was also investigated by 31P NMR, ESI‐MS and KIE studies. The KIE experiments show that the electrophilic addition of N‐methyl isatin to the complex of acrylate ester and phophine‐squaramide is the rate‐determing

  从廉价且可商购的β-氨基醇中以中等收率合成了一系列高度可调的双功能膦-方酸-甲酰胺H键供体有机催化剂6。催化剂6 F可有效地促进的不对称森田-的Baylis-希尔曼（MBH）反应ñ -烷基靛红与丙烯酸酯在提供良好的产率和对映选择性（高达93％的产率和手性3-取代的3-羟基-2-羟吲哚95％ee），其中具有挑战性的丙烯酸叔丁酯9 d提供了最佳ee迄今为止的价值。此外，该方法已成功地用于手性环状螺吡咯并咪唑恶唑和γ-丁内酯衍生物的合成，而对映选择性不降低。MBH反应的可能机理还通过31 P NMR，ESI-MS和KIE研究进行了研究。KIE实验表明，在丙烯酸酯和膦-方酸酰胺的配合物中亲电添加N-甲基伊斯廷丁是不对称MBH反应的决定速率的步骤。
• Unsymmetrical Iron P-NH-P′ Catalysts for the Asymmetric Pressure Hydrogenation of Aryl Ketones
  作者：Samantha A. M. Smith、Paraskevi O. Lagaditis、Anne Lüpke、Alan J. Lough、Robert H. Morris

  DOI：10.1002/chem.201701254

  日期：2017.5.29

  β‐aminophosphines is a new, versatile route to unsymmetrical tridentate (pincer) ligands P‐NH‐P′. Four new ligands PR2CH2CH2NHCHR′CHR′′PPh2 (R=iPr, Cy, R′=Ph, CH(CH3)2, R′′=Ph, H) prepared in this way are used to make the iron(II) complexes mer‐FeCl2(CO)(P‐NH‐P′) and mer‐FeCl(H)(CO)(P‐NH‐P′). The hydride complex with the rigid ligand with R′=R′′=Ph is an efficient and highly enantioselective homogeneous asymmetric

  α-二烷基膦乙醛与对映体纯的β-氨基膦的还原胺化反应是一条新的通用路线，可用于制备不对称的三齿（钳形）配体P-NH-P'。使用以这种方式制备的四个新的配体PR 2 CH 2 CH 2 NHCHR'CHR''PPh 2（R = i Pr，Cy，R'= Ph，CH（CH 3）2，R''= Ph，H）制备铁（II）配合物mer- FeCl 2（CO）（P-NH-P'）和mer-FeCl（H）（CO）（P-NH-P'）。具有R'= R''= Ph的刚性配体的氢化物配合物是一种高效且高对映选择性的均相不对称压力氢化（APH）催化剂。前手性芳基酮在温和条件下（THF，0.1 mol％催化剂，1 mol％KO t Bu，5-10 bar，50°C）还原为（S）-醇，通常对映体过量（ee）大于90 ％。DFT计算为对映体确定氢化物转移步骤提供了过渡态结构。