(S)-3-羟基-3-苯基丙酸甲酯 | 36615-45-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 中文名称: (S)-3-羟基-3-苯基丙酸甲酯
• 中文别名: (s)-3-羟基-3-苯丙酸甲酯
• 英文名称: methyl (S)-3-hydroxy-3-phenylpropionate
• 英文别名: (S)-methyl 3-hydroxy-3-phenylpropanoate；methyl (S)-3-hydroxy-3-phenylpropanoate；methyl 3-hydroxy-3-phenylpropanoate；(S)-(-)-3-hydroxy-3-phenylpropionic acid methyl ester；methyl (3S)-3-hydroxy-3-phenylpropanoate
• CAS: 36615-45-9
• 化学式: C₁₀H₁₂O₃
• 分子量: 180.203
• InChiKey: VZHHCQFCDCJKIX-VIFPVBQESA-N

物化性质

• 沸点：
  300.9±22.0 °C(Predicted)
• 密度：
  1.147±0.06 g/cm3(Predicted)
• 稳定性/保质期：

  遵照规定使用和储存，则不会发生分解。

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

安全信息

• 海关编码：
  2918199090
• 安全说明：
  S24/25
• 储存条件：
  存放在阴凉干燥处。

SDS

Name:	Tosylmethyl Isocyanide 98% Material Safety Data Sheet
Synonym:	(p-Tolylsulfonyl)methyl isocyanide; TosMI
CAS:	36615-45-9

Section 1 - Chemical Product MSDS Name:Tosylmethyl Isocyanide 98% Material Safety Data Sheet
Synonym:(p-Tolylsulfonyl)methyl isocyanide; TosMI

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
36615-45-9	Tosylmethyl Isocyanide	ca100	unlisted

Hazard Symbols: T
Risk Phrases: 23/24/25

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Toxic by inhalation, in contact with skin and if swallowed.Moisture sensitive.
Potential Health Effects
Eye:
Causes eye irritation. May cause chemical conjunctivitis.
Skin:
Causes skin irritation. May be absorbed through the skin in harmful amounts. May be metabolized to cyanide which in turn acts by inhibiting cytochrome oxidase impairing cellular respiration.
Ingestion:
Harmful if swallowed. May cause gastrointestinal irritation with nausea, vomiting and diarrhea. May cause cardiac disturbances. May cause central nervous system depression. Ingestion may result in symptoms similar to cyanide poisoning which is characterized by asphyxiation.
Inhalation:
Causes respiratory tract irritation. May cause cardiac abnormalities. Contains cyanide. Can produce delayed pulmonary edema.
May be metabolized to cyanide which in turns act by inhibiting cytochrome oxidase impairing cellular respiration. Inhalation may result in symptoms similar to cyanide poisoning which include tachypnea, hyperpnea (abnormally rapid or deep breathing), and dyspnea (labored breathing) followed rapidly by respiratory depression. Pulmonary edema may occur. Inhalation at high concentrations may cause CNS depression and asphixiation.
Chronic:
May be metabolized to cyanide which in turn acts by inhibiting cytochrome oxidase impairing cellular respiration. Effects may be delayed. Chronic exposure to cyanide solutions may lead to the development of a "cyanide" rash, characterized by itching, and by macular, papular, and vesicular eruptions, and may be accompanied by secondary infections. Exposure to small amounts of cyanide compounds over long periods of time is reported to cause loss of appetite, headache, weakness, nausea, dizziness, and symptoms of irritation of the upper respiratory tract and eyes.

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Section 4 - FIRST AID MEASURES
Eyes: Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid.
Skin:
Get medical aid. Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes.
Wash clothing before reuse.
Ingestion:
Never give anything by mouth to an unconscious person. Get medical aid immediately. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water.
Inhalation:
Remove from exposure and move to fresh air immediately. If breathing is difficult, give oxygen. Get medical aid. Do NOT use mouth-to-mouth resuscitation. If breathing has ceased apply artificial respiration using oxygen and a suitable mechanical device such as a bag and a mask.
Notes to Physician:
Treat symptomatically and supportively. May be partially metabolized to cyanide in the body.
Antidote: Always have a cyanide antidote kit on hand when working with cyanide compounds. Get medical advice to use.

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Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Containers may explode when heated. Non-combustible, substance itself does not burn but may decompose upon heating to produce corrosive and/or toxic fumes. Runoff from fire control or dilution water may cause pollution.
Extinguishing Media:
Do NOT get water inside containers. Use water spray, dry chemical, carbon dioxide, or appropriate foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Clean up spills immediately, observing precautions in the Protective Equipment section. Sweep up, then place into a suitable container for disposal. Provide ventilation. Do not get water inside containers.

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Section 7 - HANDLING and STORAGE
Handling:
Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation. Use with adequate ventilation. Do not allow contact with water. Wash clothing before reuse. Keep from contact with moist air and steam.
Storage:
Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances. Keep refrigerated. (Store below 4C/39F.) Store protected from moisture.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate general or local exhaust ventilation to keep airborne concentrations below the permissible exposure limits.
Exposure Limits CAS# 36615-45-9: Personal Protective Equipment Eyes: Wear safety glasses and chemical goggles if splashing is possible.
Skin:
Wear appropriate protective gloves and clothing to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to minimize contact with skin.
Respirators:
Wear a NIOSH/MSHA or European Standard EN 149 approved full-facepiece airline respirator in the positive pressure mode with emergency escape provisions.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Crystalline powder
Color: slightly yellow
Odor: None reported.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 114.00 - 115.00 deg C
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: insoluble
Specific Gravity/Density:
Molecular Formula: C9H9NO2S
Molecular Weight: 195.24

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable at room temperature in closed containers under normal storage and handling conditions. May decompose on exposure to moist air or water.
Conditions to Avoid:
Incompatible materials, dust generation, moisture, excess heat.
Incompatibilities with Other Materials:
Moisture, oxidizing agents, strong acids.
Hazardous Decomposition Products:
Nitrogen oxides, carbon monoxide, oxides of sulfur, carbon dioxide, cyanide fumes, nitrogen.
Hazardous Polymerization: Has not been reported.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 36615-45-9 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Tosylmethyl Isocyanide - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION

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Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

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Section 14 - TRANSPORT INFORMATION

IATA
Shipping Name: TOXIC SOLID, ORGANIC, N.O.S.*
Hazard Class: 6.1
UN Number: 2811
Packing Group: III
IMO
Shipping Name: TOXIC SOLID, ORGANIC, N.O.S.
Hazard Class: 6.1
UN Number: 2811
Packing Group: III
RID/ADR
Shipping Name: TOXIC SOLID, ORGANIC, N.O.S.
Hazard Class: 6.1
UN Number: 2811
Packing group: III

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: T
Risk Phrases:
R 23/24/25 Toxic by inhalation, in contact with skin
and if swallowed.
Safety Phrases:
S 45 In case of accident or if you feel unwell, seek
medical advice immediately (show the label where
possible).
WGK (Water Danger/Protection)
CAS# 36615-45-9: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 36615-45-9 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 36615-45-9 is not listed on the TSCA inventory.
It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  (S)-3-羟基-3-苯基丙酸甲酯 在 sodium tetrahydroborate 作用下， 生成 (S)-1-苯基-1,3-丙二醇
  参考文献：
  名称：

  Elucidation of stereospecificity of a selenium-containing hydrogenase from methanococcus vannielii — syntheses of (R)- and (S)-[4-2H1] 3,4-dihydro-7-hydroxy-1-hydroxyethylquinolinone

  摘要：

  DOI：

  10.1016/s0040-4039(01)80815-7
• 作为产物：
  描述：

  3-羟基-3-苯基丙酸甲酯 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 、 magnesium chloride 、 磷脂酶B 作用下， 以 二氯甲烷 、 异丙醚 、 水 为溶剂， 反应 24.0h， 生成 (S)-3-羟基-3-苯基丙酸甲酯
  参考文献：
  名称：

  Candida Rugosa lipase-catalyzed kinetic resolution of β-hydroxy-β-arylpropionates and δ-hydroxy-δ-aryl-β-oxo-pentanoates

  摘要：

  A simple and convenient method was reported for the preparation of optically active beta-hydroxy-beta-arylpropionates, delta-hydroxy-delta-aryl-beta-oxo-pentanoates and their butyryl derivatives via CRL-catalyzed hydrolysis. The optically active products are potential precursors of some chiral pharmaceuticals and natural products. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.12.059

文献信息

• Development of Chiral Spiro P-N-S Ligands for Iridium-Catalyzed Asymmetric Hydrogenation of β-Alkyl-β-Ketoesters
  作者：Deng-Hui Bao、Hui-Ling Wu、Chao-Lun Liu、Jian-Hua Xie、Qi-Lin Zhou

  DOI：10.1002/anie.201502860

  日期：2015.7.20

  The chiral tridentate spiro P‐N‐S ligands (SpiroSAP) were developed, and their iridium complexes were prepared. Introduction of a 1,3‐dithiane moiety into the ligand resulted in a highly efficient chiral iridium catalyst for asymmetric hydrogenation of β‐alkyl‐β‐ketoesters, producing chiral β‐alkyl‐β‐hydroxyesters with excellent enantioselectivities (95–99.9 % ee) and turnover numbers of up to 355 000

  研发了手性三齿螺旋螺-N‐S配体（SpiroSAP），并制备了其铱配合物。在配体中引入1,3-二硫杂环丁烷部分产生了高效的手性铱催化剂，用于β-烷基-β-酮酸酯的不对称加氢，生成具有出色对映选择性（95-99.9％ee的手性β-烷基-β-羟基酯）），营业额高达355 000。
• 2,2‘,5,5‘-Tetramethyl-4,4‘-bis(diphenylphoshino)-3,3‘-bithiophene:  A New, Very Efficient, Easily Accessible, Chiral Biheteroaromatic Ligand for Homogeneous Stereoselective Catalysis
  作者：Tiziana Benincori、Edoardo Cesarotti、Oreste Piccolo、Franco Sannicolò

  DOI：10.1021/jo991533x

  日期：2000.4.1

  C2-symmetry chelating ligand for transition metals, is described, starting from 2,5-dimethylthiophene. The complexes of this electron-rich diphosphine with Ru(II) and Rh(I) were used as catalysts in some homogeneous hydrogenation reactions of prostereogenic carbonyl functions of alpha- and beta-ketoesters, of prostereogenic carbon-carbon double bonds of substituted acrylic acids, and of N-acetylenamino

  对映纯（+）-和（-）-2,2'，5,5'-四甲基-4,4'-双-（二苯基膦基）-3,3'-联噻吩（tetraMe-BITIOP的四步直接合成），描述了一种新的C2对称的过渡金属螯合配体，从2,5-二甲基噻吩开始。这种富电子的二膦与Ru（II）和Rh（I）的配合物在α-和β-酮酸酯的酯基羰基官能团，取代丙烯酸的酯基碳-碳双键的均相加氢反应中用作催化剂和N-乙酰基氨基酸。发现在所有实验中对映体过量都非常好，并且与文献报道的在相同实验条件下进行的相同反应的最佳结果相当，
• Asymmetric Synthesis of .BETA.-Hydroxy Acid via Stereoselective Dirhodium(II)-Catalyzed C-H Insertion of .ALPHA.-Alkoxydiazoketone.
  作者：Takayuki Yakura、Takeshi Tanaka、Masazumi Ikeda、Jun'ichi Uenishi

  DOI：10.1248/cpb.51.471

  日期：——

  A new methodology for the asymmetric synthesis of beta-hydroxy acid was developed. Dirhodium(II)-catalyzed C-H insertion of alpha-alkoxydiazoketone (3), which was prepared from primary alkyl halide (1) and readily available chiral alpha-hydroxy acid (2), gave stereoselectively 2,5-cis-disubstituted 3(2H)-furanone (4). The Baeyer-Villiger reaction of 4 followed by treatment with an acid afforded chiral

  开发了一种不对称合成β-羟基酸的新方法。由伯烷基卤化物（1）和易于获得的手性α-羟基酸（2）制备的二烷基吡啶鎓（II）催化CH插入的α-烷氧基重氮酮（3），产生了立体选择性的2,5-顺式二取代的3（2H） ）-呋喃酮（4）。4的Baeyer-Villiger反应，然后用酸处理，得到具有高光学纯度的手性β-羟基酸（6）。
• Development of an axially chiral sp3P/sp3NH/sp2N-combined linear tridentate ligand—fac-selective formation of Ru(II) complexes and application to ketone hydrogenation
  作者：Tomoya Yamamura、Satoshi Nakane、Yuko Nomura、Shinji Tanaka、Masato Kitamura

  DOI：10.1016/j.tet.2016.02.007

  日期：2016.6

  A newly developed chiral linear tridentate ligand, R-PN(H)N (R=H or Ph), possesses Ph2P and PyCH2NH groups at C(2) and C(2′) positions of the 1,1′-binaphthyl skeleton without or with a C(3)-Ph substituent. The steric effect of C(3)-Ph and the electronic effect of the DMSO co-ligand realize the facial selective generation of fac-RuCl2(Ph-PN(H)N)(dmso) and fac-[Ru(H-PN(H)N)(dmso)3](BF4)2, respectively

  一种新开发的手性线性三齿配体R-PN（H）N（R = H或Ph），在1,1'的C（2）和C（2'）位置具有Ph 2 P和PyCH 2 NH基团-具有或没有C（3）-Ph取代基的-萘基骨架。C（3）-Ph的空间效应和DMSO共配体的电子效应实现了fac -RuCl 2（Ph-PN（H）N）（DMSO）和fac- [Ru（H- PN（H）N）（DMSO）3 ]（BF 4）2。H-Ru advantageoussp 3 N-H反应位点负责给体-受体双功能催化剂（DACat）和围栏/平面手性环境，均通过以下优点构建：i）sp3 P，sp 3 N和sp 2 N的连接原子具有不同的电子性质；ii）DMSO反式至sp 3 N与Ru强烈配位，并被PyC（6）H = O S氢键固定 iii）单个NH功能简化了DACat反应位点。协同作用已成功地实现了对空间需求的酮的不对称氢化。还研究了R-PN（H）N第一行过渡金属配合物的结构特征。
• A Chiral 6-Membered <i>N</i>-Heterocyclic Carbene Copper(I) Complex That Induces High Stereoselectivity
  作者：Jin Kyoon Park、Hershel H. Lackey、Matthew D. Rexford、Kirill Kovnir、Michael Shatruk、D. Tyler McQuade

  DOI：10.1021/ol1021756

  日期：2010.11.5

  A chiral 6-membered annulated N-heterocyclic (6-NHC) copper complex that catalyzes β-borylations with high yield and enantioselectivity was developed. The chiral 6-NHC copper complex is easy to prepare on the gram scale and is very active, showing 10 000 turnovers at 0.01 mol % of catalyst without significant decrease of enantioselectivity and with useful reaction rates.

  开发了一种手性的六元环状N-杂环（6-NHC）铜络合物，它以高收率和对映选择性催化β-硼化。手性6-NHC铜络合物易于按克规模制备，并且非常活泼，在0.01 mol％的催化剂下显示出1万的周转率，而对映选择性没有显着降低，并且具有有用的反应速率。