(S)-1-(二苯基膦基)-2-氨基-3-二甲基丁烷 | 286454-86-2

• 物质功能分类: 有机原料 - 有机膦化合物
• 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: (S)-1-(二苯基膦基)-2-氨基-3-二甲基丁烷
• 中文别名: (S)-1-(二苯基膦基)-3,3-二甲基丁烷-2-胺；()-1-(二苯基膦基)-3,3-二甲基丁烷-2-胺
• 英文名称: (S)-1-(diphenylphosphino)-3,3-dimethylbutan-2-amine
• 英文别名: (2S)-1-diphenylphosphanyl-3,3-dimethylbutan-2-amine
• CAS: 286454-86-2
• 化学式: C₁₈H₂₄NP
• 分子量: 285.369
• InChiKey: SGBNMEAXYLJQRV-QGZVFWFLSA-N

物化性质

• 沸点：
  384.5±25.0 °C(Predicted)
• 密度：
  1.0241 g/mL at 25 °C
• 闪点：
  >110℃

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

安全信息

• WGK Germany：
  3
• 包装等级：
  III
• 危险类别：
  8
• 危险性防范说明：
  P280,P305+P351+P338,P310
• 危险品运输编号：
  2735
• 危险性描述：
  H314
• 储存条件：
  存储条件：2-8℃，请密闭并保持干燥。

SDS

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Section 1: Product Identification
Chemical Name: (S)-1-(Diphenylphosphino)-2-amino-3,3-dimethylbutane, min. 97% (10wt% in hexanes)
CAS Registry Number: 286454-86-2
Formula: C18H24NP
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 286454-86-2 10% no data no data
Hexanes 73513-42-5 90% 50ppm 1800mg/m3

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Section 3: Hazards Identification
Extremely flammable liquid. Vapors irritating to skin, eyes and respiratory tract. Inhalation of vapors may
Emergency Overview:
depress central nervous system causing dizziness, headache and nausea.
Primary Routes of Exposure: Ingestion, inhalation
Eye Contact: Contact will cause irritation, redness and a burning sensation.
Skin Contact: Contact with skin can result in local irritation. May be absorbed through skin.
Inhalation of vapors may depress the central nervous system causing dizziness, difficulty in walking and
Inhalation:
irritation to the lungs.
Ingestion may cause gastrointestinal irritation, nausea, vomiting and headache. May cause lung damage if
Ingestion:
swallowed.
Irritating to skin, eyes and respiratory tract. Harmful by inhalation. Ingestion may cause gastrointestinal
Acute Health Affects:
irritation, nausea, vomiting and headache. Possible risk of harm to the unborn child.
Chronic Health Affects: No information on long-term chronic effects. Possible risk of impaired fertility.
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: -14.8°F (hexane)
Autoignition Temperature: no data
Explosion Limits: LEL(1.7%) UEL(7.7%) hexane
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 toxic and irritating fumes.
Decomposion Products:
Unusual Fire or Explosion Hazards: Highly flammable. Vapors can form explosive mixtures in air.

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SECTION 6: Accidental Release Measures
If spilled, all personnel must be immediately evacuated and the area sealed off. The material may self-ignite
Spill and Leak Procedures: releasing toxic and corrosive fumes of phosphorus pentoxide. Ventilation should be available. If entry into the
area is required, personnel should be fitted with a self-contained breathing apparatus.

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SECTION 7: Handling and Storage
Store in a tightly sealed container under an inert atmosphere of nitrogen or argon. Keep away from heat.
Handling and Storage:
Material should be transferred under an inert atmosphere of nitrogen or argon in an efficient fume hood.

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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: colorless liquid
Molecular Weight: 285.36
Melting Point: no data
Boiling Point: 68°C (hexane)
Vapor Pressure: no data
Specific Gravity: no data
Odor: faint noxious odor
Solubility in Water: insoluble

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SECTION 10: Stability and Reactivity
Stability: air sensitive
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: contact with oxidizing agents, ignition sources and prolonged exposure to air
Incompatibility: strong oxidizing agents and halogens
Decomposition Products: carbon monoxide, carbon dioxide, phosphorous oxides and organic fumes

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SECTION 11: Toxicological Information
Title compound: No information available in the RTECS files. Hexane: Inhalation(humane); TCLo:
190ppm/8W. Inhalation(rat); LC50: 48000ppm/4H. Intraperitoneal(rat); LDLo: 9100mg/kg. Inhalation(mouse);
LCLo: 120g/m3. Intravenous(mouse); LDLo: 831mg/kg. Intravenous(rabbit); LDLo: 132mg/kg. Oral(rat); TDLo:
RTECS Data:
20000mg/kg. Oral(rat); LD50: 15840mg/kg. Inhalation(rat); TCLo: 1000ppm/4H/59W
(intermittent)-Tumorigenic-carcinogenic by RTECS criteria. Inhalation(rat); TCLo: 10000ppm/7H; female-1-18
days after conception-behavorial effects on newborn.
Carcinogenic Effects: Hexane: Insufficient data
Mutagenic Effects: Hexane: Possible mutagen
Tetratogenic Effects: Hexane: Possible reproductive effector

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SECTION 12: Ecological Information
Hexane is very toxic to aquatic organisms. May cause long-term adverse effects in the aquatic environment.
Ecological Information:
Avoid release to the environment.

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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): Flammable liquids, N.O.S.
Hazard Class (CFR): 3
Additional Hazard Class (CFR): NA
Packaging Group (CFR): I
UN ID Number (CFR): UN# 1993
Shipping Name (IATA): Flammable liquid, N.O.S.
Hazard Class (IATA): 3
Additional Hazard Class (IATA): NA
Packaging Group (IATA): I
UN ID Number (IATA): UN# 1993

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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: Hexane: Listed in the TSCA inventory. Reportable under SARA 313.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  (S)-1-(二苯基膦基)-2-氨基-3-二甲基丁烷 在 O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate 、 N,N-二异丙基乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 生成 (S)-2-(3-(3,5-bis(trifluoromethyl)phenyl)thioureido)-N-((S)-1-(diphenylphosphanyl)-3,3-dimethylbutan-2-yl)-2-phenylacetamide
  参考文献：
  名称：

  N保护基对三氟甲基酮亚胺在Strecker反应中通过离子对催化合成α-三氟甲基氨基腈的对映选择性的调节。

  摘要：

  已开发出一种对映选择性斯特雷克反应，该反应可利用有机膦双试剂催化剂与N-PMP和未探索的N-Boc三氟甲基酮亚胺构建三氟甲基化的季立体中心。可以通过使用不同的N保护基（N-PMP或N-Boc）来切换相应产物与相同催化剂的对映选择性。在短时间内以高收率和高对映选择性获得了三氟甲基氨基腈，并且可以容易地将其转化为多种有用的含三氟甲基的化合物。

  DOI：

  10.1039/c9cc09151c
• 作为产物：
  描述：

  在 二乙胺 作用下， 反应 6.0h， 生成 (S)-1-(二苯基膦基)-2-氨基-3-二甲基丁烷
  参考文献：
  名称：

  新型手性亚磺酰胺膦：手性β-氨基膦的有价值的前体

  摘要：

  从市售的醛和手性叔丁烷亚磺酰胺开始，通过两步缩合亲核加成法合成了一系列手性亚磺酰胺膦（Xiao-Phos）。在大多数情况下，亲核加成的Ñ -叔-butanesulfinyl亚胺与碳酸二苯甲基膦锂表现出较高的非对映选择性（DR> 20：1）与BF 3作为添加剂。除去手性助剂后，使用该方法以高收率获得了重要的一类配体，即手性β-氨基膦及其衍生物。

  DOI：

  10.1016/j.tet.2015.12.002

文献信息

• Asymmetric kinetic resolution of sulfides for the construction of unsymmetric sulfides and chiral 3,3-disubstituted oxindoles
  作者：Kaiye Wang、Yanan Xiang、Zhujun Shi、Hongyu Wang、Na Li、Bo Tang

  DOI：10.1039/c9ob01065c

  日期：——

  A range of 3,3-disubstituted oxindoles accessed using para-quinone methides derived from isatins with thiols were used for the formation of unsymmetrical disulfides, and 3,3-disubstituted oxindoles with a chiral quaternary carbon center and unsymmetric disulfides could also be directly obtained with high selectivities catalyzed by chiral phosphines in one step.

  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。
• Versatile Chiral Bidentate Ligands Derived from α-Amino Acids:  Synthetic Applications and Mechanistic Considerations in the Palladium-Mediated Asymmetric Allylic Substitutions
  作者：Akihito Saitoh、Kazuo Achiwa、Kiyoshi Tanaka、Toshiaki Morimoto

  DOI：10.1021/jo991615l

  日期：2000.7.1

  to other amino groups in the amidine skeleton and the production of other types of ligands, are possible using the precursor compounds of 7a. Thus, novel chiral ligands 7c,d, 8, 11, and 13, which provide sterically and electronically different chiral circumstances, were prepared and used for the palladium-mediated asymmetric allylic substitutions of both acyclic and cyclic compounds. In these reactions

  新型的手性am-膦杂化配体7a，b很容易从相应的α-氨基酸获得。需要构建新的配体的多功能性，由此可以应用各种反应和底物。实际上，使用7a的前体化合物可以进行多种修饰，例如与to骨架中其他氨基的交换反应和产生其他类型的配体。因此，制备了提供空间和电子不同手性情况的新型手性配体7c，d，8、11和13，并将其用于钯介导的无环和环状化合物的不对称烯丙基取代。在这些反应中，两种底物均实现了高水平的不对称诱导。通过检查新系列的手性PN和SN杂配体8和11中的电子取代基效应，在钯催化的1,3-二苯基丙烯-2-基新戊酸酯14a的钯催化的不对称烯丙基化中，反应性和对映选择性显着提高。证明了有关对映体区分步骤，其中讨论了新颖的Pr / Mr概念与烯丙基化产物的绝对构型之间的良好相关性，以预测对映体选择方向。研究了乙烯酮甲硅烷基缩醛作为亲核试剂的使用，并将其与相应的较硬的阴离子碳亲核试剂进行了比较。在14a的
• Modified Amino Acid-Derived Phosphine-Imine Ligands for Palladium-Catalyzed Asymmetric Arylation of Cyclic <i>N</i> -Sulfonyl Imines
  作者：Bo Zhou、Kaizhi Li、Chunhui Jiang、Yixin Lu、Tamio Hayashi

  DOI：10.1002/adsc.201700003

  日期：2017.6.6

  A series of chiral phosphine‐imine ligands were synthesized starting with α‐amino acids and examined for palladium‐catalyzed asymmetric addition of arylboronic acids to cyclic N‐sulfonyl imines. High catalytic activities (up to 99% yield) and high enantioselectivities (up to 98% ee) were achieved for cyclic N‐sulfonyl aldimines and ketimines with five and six‐membered ring structures.

  从α-氨基酸开始，合成了一系列手性膦-亚胺配体，并检查了钯催化不对称地将芳基硼酸加成到环状N-磺酰基亚胺上。具有五元和六元环结构的环状N-磺酰基醛亚胺和酮亚胺实现了高催化活性（高达99％的收率）和高对映选择性（高达98％ee）。
• 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。
• Enantioselective Copper-Catalyzed 1,4-Addition of Dialkylzincs to Enones Followed by Trapping with Allyl Iodide Derivatives
  作者：Kenjiro Kawamura、Hitomi Fukuzawa、Masahiko Hayashi

  DOI：10.1246/bcsj.20110035

  日期：2011.6.15

  Enantioselective copper-catalyzed 1,4-addition of dialkylzincs to enones proceeded in the presence of 0.1 mol % of Cu(OTf)2 and 0.25 mol % of an N,N,P-ligand containing a quinoline moiety to afford...

  在 0.1 mol% 的 Cu(OTf)2 和 0.25 mol% 的含有喹啉部分的 N,N,P-配体存在下，对映选择性铜催化二烷基锌与烯酮的 1,4-加成反应，得到...