(S)-(+)-(2,6-二甲基-3,5-二氧-4-磷酸-环庚基[2,1-a | 185449-86-9

• 物质功能分类: 化学试剂 - 有机试剂 - 膦配体
• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 中文名称: (S)-(+)-(2,6-二甲基-3,5-二氧-4-磷酸-环庚基[2,1-a
• 中文别名: (S)-(+)-(2,6-二甲基-3,5-二氧-4-磷-环庚并[2,1-a;3,4-a']二萘-4-基)二甲胺；(S)-(+)-(2,6-二甲基-3,5-二氧-4-磷-环庚[2,1-A；(S)-(+)-(2,6-二甲基-3,5-二氧-4-磷-环庚[2,1-A:3,4-A']二萘-4-基)二甲胺
• 英文名称: O,O'-(1,1'-dinaphthyl-2,2'-diyl-3,3'-dimethyl)-N,N-dimethylphosphoramidite
• 英文别名: N,N,2,6-Tetramethyldinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine；N,N,10,16-tetramethyl-12,14-dioxa-13-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-amine
• CAS: 185449-86-9
• 化学式: C₂₄H₂₂NO₂P
• 分子量: 387.418
• InChiKey: MXASPZVRFOFONU-UHFFFAOYSA-N

物化性质

• 熔点：
  228-229°C
• 比旋光度：
  +636° (c 0.30, CH2Cl2)
• 沸点：
  571.0±53.0 °C(Predicted)
• 稳定性/保质期：

  遵照规定使用和储存，则不会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  28
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 危险品标志：
  Xn
• 危险类别码：
  R36/37/38,R
• 海关编码：
  2921499090
• 安全说明：
  S26
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  密封于阴凉干燥环境中

SDS

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Section 1: Product Identification
(S)-(+)-(2,6-Dimethyl-3,5-dioxa-4-phospha-cyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)dimethylamine, min. 98%
Chemical Name:
CAS Registry Number: 185449-86-9
Formula: C24H22NO2P
EINECS Number: none
Chemical Family: Phosphoramidite
Synonym: none

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title Compound 185449-86-9 100% no data no data

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Section 3: Hazards Identification
Emergency Overview: Irritating to the respiratory tract, skin and eyes. May be harmful if swallowed.
Primary Routes of Exposure: Ingestion, eyes, 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: May be harmful if swallowed. No specific information is available on the physiological effects of ingestion.
Acute Health Affects: Irritating to skin, eyes and respiratory tract.
Chronic Health Affects: No information available 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
Fire fighters should be equipped with a NIOSH approved positive pressure self-contained breathing apparatus
Special Fire Fighting Procedures:
and full protective clothing.
Hazardous Combustion and If involved in a fire this material may emit toxic organic fumes and vapors of phosphorus pentoxide.
Decomposion Products:
Unusual Fire or Explosion Hazards: No unusual fire or explosion hazards.

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SECTION 6: Accidental Release Measures
Small spills can be mixed with vermiculite, sodium carbonate or other suitable non combustible adsorbent and
Spill and Leak Procedures:
swept up.

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SECTION 7: Handling and Storage
Keep material in a tightly sealed container. Prolonged exposure to moisture will result in degradation of the
Handling and Storage:
product. Handle and store material under a dry atmosphere.

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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. Consult with glove manufacturer to determine the proper type of glove.
Ventilation: Material may form a fine dust. If possible, 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: Material may form a fine dust. If possible, 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: off-white pwdr.
Molecular Weight: 387.41
Melting Point: 228-229°
Boiling Point: no data
Vapor Pressure: not applicable
Specific Gravity: no data
Odor: none
Solubility in Water: reacts slowly with water

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SECTION 10: Stability and Reactivity
Stability: air stable, moisture sensitive
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: extended exposure to moisture and acids
Incompatibility: oxidizing agents
Decomposition Products: carbon monoxide, phosphorus pentoxide, nitrogen and nitrogen 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 federal, state, and local 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：

  bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 (S)-(+)-(2,6-二甲基-3,5-二氧-4-磷酸-环庚基[2,1-a 以 二氯甲烷 为溶剂， 生成 IrCl(1,5-cyclooctadiene)((CH₃)2NP(OC₁₀H₅CH₃)2)
  参考文献：
  名称：

  在铱催化的不对称氢化反应中，单个单齿亚磷酰胺配体诱导了高对映选择性。

  摘要：

  DOI：

  10.1002/anie.200603930
• 作为产物：
  描述：

  3,3'-dimethyl-2,2'-dimethoxy-1,1'-dinaphthyl 在 三溴化硼 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 3.0h， 生成 (S)-(+)-(2,6-二甲基-3,5-二氧-4-磷酸-环庚基[2,1-a
  参考文献：
  名称：

  使用铜-亚磷酰胺络合物的二烷基锌试剂的对映选择性催化共轭加成；配体变化和非线性效应

  摘要：

  合成了多种新的手性亚磷酰胺，并在铜催化的对乙基己烯酮和查耳酮的铜催化对映选择性共轭加成中进行了测试，以评估对立体控制至关重要的结构特征。空间要求高的胺部分对于达到高ee是必不可少的。发现查尔酮的对映选择性高达89％，环烯酮的对映选择性高达98％。对具有最佳配体的环己烯酮和查尔酮的非线性效应的研究表明，环状和非环状烯酮均具有明显的非线性效应。

  DOI：

  10.1016/s0040-4020(00)00142-3
• 作为试剂：
  描述：

  2-已烯醛 在 氢气 、 (S)-(+)-(2,6-二甲基-3,5-二氧-4-磷酸-环庚基[2,1-a 作用下， 90.0 ℃ 、200.0 kPa 条件下， 反应 18.0h， 生成 顺式-2-己烯醛
  参考文献：
  名称：

  一种α,β-不饱和羰基化合物的E-异构体制备 Z-异构体的方法

  摘要：

  本发明提供一种α,β‑不饱和羰基化合物的E‑异构体制备Z‑异构体的方法。所述方法使用手性含氮亚磷酸联萘二酚酯做催化剂，在温和的反应条件下，将α,β‑不饱和羰基化合物的E‑异构体高效转化为Z‑异构体。所述方法尤其适用于柠檬醛拆分剩余料中的部分香叶醛异构化制备橙花醛，重新得到香叶醛与橙花醛摩尔比接近1：1的柠檬醛可以再次对其进行拆分出橙花醛，提高原料利用率，降低成本。

  公开号：

  CN106256816B

文献信息

• [EN] TRISUBSTITUTED 3,4-DIHYDRO-1H-ISOQUINOLIN COMPOUND, PROCESS FOR ITS PREPARATION, AND ITS USE<br/>[FR] COMPOSÉ 3,4-DIHYDRO-1H-ISOQUINOLÉINE TRISUBSTITUÉE, MÉTHODE DE PRÉPARATION, ET SON UTILISATION
  申请人：ACTELION PHARMACEUTICALS LTD

  公开号：WO2009083903A1

  公开（公告）日：2009-07-09

  The present invention relates to the compound of formula (7*)acetate (see below), a process for its preparation, and its use.

  这项发明涉及到式（7*）醋酸盐（见下文）的化合物，以及其制备方法和用途。
• Method for the asymmetric hydrogenation of olefins utilising photoisomerisation
  申请人：DSM IP Assets B.V.

  公开号：EP2213638A1

  公开（公告）日：2010-08-04

  The present invention relates to a method for the preparation of a compound of formula (I), wherein R1 is different to R2; R3 is different to R4; and R1, R2, R3 and R4 are each a moiety other than hydrogen, which method comprises, i) photoirradiating at an intensity above ambient intensity a solution comprising a compound of formula (II), wherein R1, R2, R3 and R4 are as defined above, to form a solution of a mixture of compounds of formula (IIa) and (IIb), wherein R1, R2, R3and R4 are as defined above; and ii) contacting the mixture of compounds (IIa) and (IIb) with a hydrogen donating agent in the presence of an asymmetric hydrogenation catalyst, after initiation of i) and before termination of i).

  本发明涉及一种制备化合物(I)的方法，其中R1不同于R2；R3不同于R4；且R1、R2、R3和R4各自是除氢之外的基团，该方法包括，i) 在高于环境强度的光照强度下光照含有化合物(II)的溶液，其中R1、R2、R3和R4如上定义，以形成化合物(IIa)和(IIb)的混合物的溶液，其中R1、R2、R3和R4如上定义；和ii) 在i)启动后且i)终止前，将化合物(IIa)和(IIb)的混合物与氢捐体在不对称氢化催化剂存在下接触。
• PHOSPHORAMIDITE LIGAND AND PRODUCTION METHOD OF ALLYLIC AMINE USING THE SAME
  申请人：CARREIRA Erick M.

  公开号：US20090054689A1

  公开（公告）日：2009-02-26

  The present invention provides a production method of an allylic amine represented by the formula (III): wherein R 3 is as defined in the specification, which comprises reacting by an allylic alcohol represented by the formula (II): wherein R 3 is as defined in the specification, with sulfamic acid, in the presence of a phosphoramidite ligand represented by the formula (I): wherein each symbol is as defined in the specification, and an iridium complex. According to the present invention, a primary allylic amine can be produced directly from an allylic alcohol, without use of an activator for an allylic alcohol and conversion of an allylic alcohol into an activated compound thereof.

  本发明提供了一种制备烯丙胺的生产方法，烯丙胺的化学式为(III)，其中R3如规范中定义，该方法包括使用磷酰胺配体(I)和铱配合物，在磺酸的存在下，将烯丙醇(II)与磺酸反应。根据本发明，可以直接从烯丙醇中生产出主要的烯丙胺，而无需使用烯丙醇的活化剂，也无需将烯丙醇转化为其活化化合物。
• Light-Induced Enantioselective Hydrogenation Using Chiral Derivatives of Casey’s Iron–Cyclopentadienone Catalyst
  作者：Albrecht Berkessel、Sebastian Reichau、Adrian von der Höh、Nicolas Leconte、Jörg-M. Neudörfl

  DOI：10.1021/om200459s

  日期：2011.7.25

  reaction could be avoided. Instead, the catalytic cycle is accessed from air-stable carbonyl precursors. In the hydridic form of the phosphoramidite–carbonyl catalysts, the iron atom itself becomes a stereocenter. NMR spectroscopy confirmed the generation of two hydride diastereomers. With the MonoPhos iron dicarbonyl complex, moderate enantioselectivity (up to 31% ee) was achieved in the hydrogenation of

  我们在此报告了使用均相铁（II）-环戊二烯酮-三羰基体系的手性改性衍生物（称为Casey催化剂）进行不对称酮氢化的第一个例子。为了合成手性改性催化剂，将三个羰基配体之一交换为手性亚磷酰胺。为此，应用使用三甲胺-N-氧化物的氧化脱羰或光解。还使用光解作用将三羰基铁预催化剂（以及类似地，二羰基亚磷酰胺络合物）转化为配位不饱和的二羰基（分别为单羰基）络合物，它们是酮加氢催化循环中的中间体。后一种物质的氢吸收提供了“负载”的氢化物，如1所示。1 H NMR光谱。因此，可以避免通过通常低产率的希伯反应制备敏感的氢化铁。相反，从空气稳定的羰基前体进入催化循环。在亚磷酰胺-羰基催化剂的氢化形式中，铁原子本身成为立体中心。NMR光谱证实了两种氢化物非对映异构体的产生。使用MonoPhos二羰基铁络合物，在苯乙酮的氢化过程中实现了中等对映选择性（高达31％ee）。
• Influence of Phosphoramidites in Copper-Catalyzed Conjugate Borylation Reaction
  作者：Cristina Sole、Amadeu Bonet、André H. M. de Vries、Johannes G. de Vries、Laurent Lefort、Henrik Gulyás、Elena Fernández

  DOI：10.1021/om300194k

  日期：2012.11.26

  Copper(I) has become the preferred metal to catalyze the beta-boration of alpha,beta-unsaturated carbonyl compounds, and now we demonstrate that easily accessible monodentate chiral ligands, such as phosphoramidites and phosphites, can be convenient alternative ligands to induce asymmetry in the enantioselective version of this reaction, particularly in the beta-boration of alpha,beta-unsaturated imines.