N,N-双-((S)-1-苯基乙基)二苯并[d,f][1,3,2]二氧杂膦-6-胺 | 376355-58-7

• 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: N,N-双-((S)-1-苯基乙基)二苯并[d,f][1,3,2]二氧杂膦-6-胺
• 中文别名: N,N-二[(1S)-1-苯基乙基]-二苯并[D,F][1,3,2]二氧杂磷杂卓-6-胺；N,N-双[(1S)-(-)-苯乙基]二苯并[D,F][1,3,2]二氧磷杂七环-6-胺；(S,S)-N-(5,7-二氧杂-6-磷杂二苯并[A,C]环庚烯-6-基)双(1-苯乙基)胺；O,O′-(2,2′-联苯二基)N,N-双[(S)-1-苯基乙基]亚磷酰胺
• 英文名称: N,N-bis-[(S)-1-phenylethyl]dibenzo[d,f][1,3,2]dioxaphosphepin-6-amine
• 英文别名: N,N-bis(1-phenylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-amine；(biphenyl-2,2'-diyldioxy){bis[(S)-1-phenylethyl]amino}phosphine；N,N-Bis((S)-1-phenylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-amine；N,N-bis[(1S)-1-phenylethyl]benzo[d][1,3,2]benzodioxaphosphepin-6-amine
• CAS: 376355-58-7
• 化学式: C₂₈H₂₆NO₂P
• 分子量: 439.494
• InChiKey: JISGHECLGYELKD-VXKWHMMOSA-N

物化性质

• 熔点：
  99-102 °C
• 沸点：
  578.4±53.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  32
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• WGK Germany：
  3
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335

SDS

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Section 1: Product Identification
Chemical Name: N,N-Bis[(1S)-(-)-phenylethyl]dibenzo[d,f][1,3,2]dioxaphosphepin-6-amine
CAS Registry Number: 376355-58-7
Formula: C28H26NO2P
EINECS Number: none
Chemical Family: phosphine-amine ligand
Synonym: (5,7-Dioxa-6-phospha-dibenzo[a,c]cyclohepten-6-yl)-bis-(1(S)-(-)--phenyl-ethyl)-amine

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 376355-58-7 100% 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
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. Dust may be irritating to 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: none
Autoignition Temperature: none
Explosion Limits: none
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
The material will degrade on prolonged exposure to moisture. Store under an inert atmosphere of nitrogen or
Handling and Storage:
argon.

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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 powder
Molecular Weight: 439.49
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: moisture sensitive
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: prolonged exposure to moisture
Incompatibility: oxidizing agents and halogens
Decomposition Products: carbon dioxide, carbon monoxide, organic fumes, phosphorus oxides.

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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): Title compound not listed
Second Ingredient: none

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  di-μ-chlorobis(norbornadiene)dirhodium(I) 、 N,N-双-((S)-1-苯基乙基)二苯并[d,f][1,3,2]二氧杂膦-6-胺 以 二氯甲烷 为溶剂， 以91%的产率得到
  参考文献：
  名称：

  RhCl（二烯）（亚磷酰胺）配合物的多核NMR，X射线和DFT研究

  摘要：

  对几种[RhCl（二烯）（亚磷酰胺）]配合物的NMR，X射线和DFT研究表明，电子和空间效应均会影响烯烃，氯和P-给体键合的性质。[RhCl（1,5-COD）（亚磷酰胺）]（亚磷酰胺=（Binol）PN（CH（CH 3）Ph）2）的X射线研究表明，在分子内的选择性是在C-烯烃反式与Cl配体的C键优先被延长。在环境温度下，在CD 2 Cl 2中检测到两种类型的动态过程2-D NOESY方法制备溶液：假定亚磷酰胺解离和二烯烃旋转。前者在1,5-COD和NBD中均可观察到。后者更具选择性，因为NBD类似物的分子内动力学相对较快，但1,5-COD化合物的分子内动力学几乎无法检测到。DFT计算表明，二烯烃的旋转在四面体过渡状态下进行，相对于类似的1,5-COD物质，NBD配合物的能垒较小。报道了两种形式为[Rh（1,5-COD）（亚磷酰胺）2 ] BF 4的双亚磷酰胺盐。

  DOI：

  10.1021/om800082c
• 作为产物：
  描述：

  双((S)-1-苯乙基)胺 在 三乙胺 、 三氯化磷 作用下， 以 四氢呋喃 为溶剂， 生成 N,N-双-((S)-1-苯基乙基)二苯并[d,f][1,3,2]二氧杂膦-6-胺
  参考文献：
  名称：

  关于使用亚磷酰胺配体与三烷基铝试剂在铜催化的不对称转化中的应用。

  摘要：

  [反应：见正文]基于BINOL的亚磷酰胺容易与三甲基铝在“非配位”溶剂中反应，产生相应的氨基膦，该氨基膦是铜催化的不对称转化中的真正配体。该伪影解释了使用二烷基锌或三烷基铝试剂作为亲核试剂的中观双环肼的不对称开环的实验差异。

  DOI：

  10.1021/ol061471e
• 作为试剂：
  描述：

  3-甲酰基吲哚酸-1-羧酸 t-丁基酯 在 4-二甲氨基吡啶 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 potassium osmate(VI) dihydrate 、 N-甲基吗啉氧化物 、 N,N-双-((S)-1-苯基乙基)二苯并[d,f][1,3,2]二氧杂膦-6-胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 、 甲苯 、 乙腈 为溶剂， 反应 10.0h， 生成
  参考文献：
  名称：

  Trigolutes中心核心的一种简洁方法：Trigolute B和3- epi- trigolute B及其类似物的全合成

  摘要：

  已经开发出一种简明的方法，该方法包括Pd或Ir催化的Tsuji-Trost烯丙基化和烯烃二羟基化/酸催化的内酯化的组合，以构建具有必要官能团的三甲酚的中央螺内酯核心。已经合成了大量三水甘油三酯的类似物。此外，（±）-Trigolute B和（±）-3-epi-trigolute B的合成已从易于获得的构建基块以4-5个步骤完成。

  DOI：

  10.1016/j.tet.2016.12.074

文献信息

• Copper-Catalyzed Asymmetric Conjugate Addition of Trialkylaluminium Reagents to Trisubstituted Enones: Construction of Chiral Quaternary Centers
  作者：Magali Vuagnoux-d'Augustin、Alexandre Alexakis

  DOI：10.1002/chem.200701001

  日期：2007.11.26

  vinylalane species undergo enantioselective conjugate addition to a wide range of 2- or 3-substituted enones (cyclopent-2-enones, cyclohex-2-enones, 3-methyl cyclohept-2-enone) in the presence of catalytic amount of copper salt (copper thiophene carboxylate, [Cu(CH3CN)4]BF4 or [CuOTf]2C6H6) and tropos-phosphoramidite-based ligand. Thus, chiral quaternary centers can be built, with up to 98% ee after rigorous

  在催化作用下，Me3Al，Et3Al和乙烯基丙烷类物质进行对映选择性共轭加成，生成各种2-或3-取代的烯酮（环戊-2-烯酮，环己-2-烯酮，3-甲基环庚-2-烯酮）铜盐（噻吩羧酸铜，[Cu（CH3CN）4] BF4或[CuOTf] 2C6H6）和基于对位亚磷酰胺的配体。因此，经过严格优化实验条件后，可以建立具有高达98％ee的手性四元中心。结果表明，主要的重要参数是试剂引入的顺序。然后，将生成的对映体富集的烯醇铝和手性共轭加合物官能化并用于随后的反应。
• Novel Biphenol Phosphoramidite Ligands for the Enantioselective Copper-Catalyzed Conjugate Addition of Dialkyl zincs
  作者：Alexandre Alexakis、Stéphane Rosset、Janik Allamand、Sébastien March、Frédéric Guillen、Cyril Benhaim

  DOI：10.1055/s-2001-16791

  日期：——

  Phosphoramidite ligands, based on a chiral amine and atropoisomerically flexible biphenols, induce high enantioselectivities (ee's up to 98%) in the copper-catalyzed conjugate addition of dialkyl zinc reagents to a variety of Michael acceptors.

  亚磷酰胺配体基于手性胺和阻转异构柔性双酚，在铜催化的二烷基锌试剂与各种迈克尔受体的共轭加成中诱导高对映选择性（ee 高达 98%）。
• [EN] SYNTHESIS OF CHROMANE COMPOUNDS AND THEIR DERIVATIVES BY A COPPER-CATALYZED CONJUGATE ADDITION REACTION<br/>[FR] SYNTHÈSE DE COMPOSÉS DE CHROMANE ET DE LEURS DÉRIVÉS PAR UNE RÉACTION D'ADDITION CONJUGUÉE CATALYSÉE PAR DU CUIVRE
  申请人：DSM IP ASSETS BV

  公开号：WO2015059129A1

  公开（公告）日：2015-04-30

  The present invention relates to the preparation of chromane compounds and their derivatives by a copper-catalyzed conjugate addition reaction. It has been observed that in highly stereoselective manner a methyl group can be introduced to the 2 position of chromane ring by reaction of a chromenone with Al(CH3)3 in the presence of a Cu(I) salt and specific chiral phosphoramidites. The compounds obtained are important intermediates particularly for the synthesis of chiral tocopherols.

  本发明涉及通过铜催化的共轭加成反应制备色满化合物及其衍生物。观察到，在高度立体选择性的方式下，通过色满酮与三甲基铝在铜(I)盐和特定手性磷酰胺的存在下反应，可以将甲基引入到色满环的2位。所得到的化合物是重要的中间体，特别适用于合成手性生育酚。
• Rh-Catalyzed Asymmetric Hydrogenation of Prochiral Olefins with a Dynamic Library of Chiral TROPOS Phosphorus Ligands
  作者：Chiara Monti、Cesare Gennari、Umberto Piarulli、Johannes G. de Vries、André H. M. de Vries、Laurent Lefort

  DOI：10.1002/chem.200500464

  日期：2005.11.4

  A library of 19 chiral tropos phosphorus ligands, based on a flexible (tropos) biphenol unit and a chiral P-bound alcohol (11 phosphites) or secondary amine (8 phosphoramidites), was synthesized. These ligands were screened, individually and as a combination of two, in the rhodium-catalyzed asymmetric hydrogenation of dehydro-alpha-amino acids, dehydro-beta-amino acids, enamides and dimethyl itaconate

  合成了一个基于柔性（对位）双酚单元和一个手性P结合醇（11个亚磷酸盐）或仲胺（8个亚磷酰胺）的19个手性对位磷配体的文库。在铑催化的脱氢α-氨基酸，脱氢β-氨基酸，酰胺和衣康酸二甲酯的铑催化的不对称氢化中，分别或以两种的组合筛选这些配体。通过使用配体，亚磷酸酯[4-P（O）2O]和亚磷酰胺[13-P（O）2N]的最佳组合，可以得到高达98％的脱氢α-氨基酸ee值。与单个配体以及亚磷酸酯[4-P（O）2O]和亚磷酰胺[13-P（O）2N]组合反应的动力学研究表明，亚磷酸酯尽管对映选择性较低，与相同的亚磷酸酯与亚磷酰胺的混合物相比，促进2-乙酰氨基丙烯酸甲酯和2-乙酰氨基doc酸甲酯的氢化速度更快，而仅亚磷酰胺的活性低得多。这样，通过降低亚磷酸酯/亚磷酰胺的比率（最佳比率为0.25当量的亚磷酸酯/1.75当量的亚磷酰胺）来优化反应，从而改善了产物对映体过量。还提出了一个简单的数学模型，以更好地
• Enantioselective conjugate addition of phenylboronic acid to enones catalysed by a chiral tropos/atropos rhodium complex at the coalescence temperature
  作者：Chiara Monti、Cesare Gennari、Umberto Piarulli

  DOI：10.1039/b508832a

  日期：——

  A highly enantioselective rhodium-catalysed conjugate addition of phenylboronic acid to cyclic enones has been achieved using a dynamic library of chiral phosphorus ligands; the tropos/atropos nature of the ligands in the rhodium complex has been characterised via 31P-NMR.

  使用手性磷配体的动态库已经实现了苯基硼酸向环烯酮的高对映选择性铑催化的共轭加成反应。铑配合物中配体的对位/对位性质已通过31 P-NMR进行了表征。