(S)-4-苯基噁唑烷-2-硫酮 | 190970-57-1

• 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)-4-苯基噁唑烷-2-硫酮
• 中文别名: (S)-4-苯基-1,3-恶唑烷-2-硫酮
• 英文名称: (S)-4-phenyloxazolidine-2-thione
• 英文别名: (S)-4-phenyl-1,3-oxazolidine-2-thione；4-phenyloxazolidine-2-thione；(4S)-4-phenyl-1,3-oxazolidine-2-thione
• CAS: 190970-57-1
• 化学式: C₉H₉NOS
• 分子量: 179.243
• InChiKey: LVIJIGQKFDZTNC-MRVPVSSYSA-N

物化性质

• 沸点：
  272.0±43.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  53.4
• 氢给体数：
  1
• 氢受体数：
  2

安全信息

• 危险品标志：
  Xi
• 储存条件：
  室温且干燥

SDS

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Section 1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product identifiers
Product name : (S)-4-Phenyloxazolidine-2-thione
CAS-No. : 190970-57-1
Relevant identified uses of the substance or mixture and uses advised against
Identified uses : Laboratory chemicals, Manufacture of substances

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Section 2. HAZARDS IDENTIFICATION
Classification of the substance or mixture
Not a hazardous substance or mixture according to Regulation (EC) No. 1272/2008.
This substance is not classified as dangerous according to Directive 67/548/EEC.
Label elements
Caution - substance not yet tested completely.
Other hazards - none

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Section 3. COMPOSITION/INFORMATION ON INGREDIENTS
Substances
Formula : C9H9NOS
Molecular Weight : 179,24 g/mol

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Section 4. FIRST AID MEASURES
Description of first aid measures
If inhaled
If breathed in, move person into fresh air. If not breathing, give artificial respiration.
In case of skin contact
Wash off with soap and plenty of water.
In case of eye contact
Flush eyes with water as a precaution.
If swallowed
Never give anything by mouth to an unconscious person. Rinse mouth with water.
Most important symptoms and effects, both acute and delayed
Indication of any immediate medical attention and special treatment needed
no data available

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Section 5. FIREFIGHTING MEASURES
Extinguishing media
Suitable extinguishing media
Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.
Special hazards arising from the substance or mixture
Carbon oxides, nitrogen oxides (NOx), Sulphur oxides
Advice for firefighters
Wear self contained breathing apparatus for fire fighting if necessary.
Further information
no data available

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Section 6. ACCIDENTAL RELEASE MEASURES
Personal precautions, protective equipment and emergency procedures
Avoid dust formation. Avoid breathing vapors, mist or gas.
Environmental precautions
Do not let product enter drains.
Methods and materials for containment and cleaning up
Sweep up and shovel. Keep in suitable, closed containers for disposal.
Reference to other sections
For disposal see section 13.

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Section 7. HANDLING AND STORAGE
Precautions for safe handling
Provide appropriate exhaust ventilation at places where dust is formed.Normal measures for preventive fire
protection.
Conditions for safe storage, including any incompatibilities
Store in cool place. Keep container tightly closed in a dry and well-ventilated place.
Store under inert gas. Air sensitive.
Specific end uses
no data available

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Section 8. EXPOSURE CONTROLS/PERSONAL PROTECTION
Control parameters
Components with workplace control parameters
Exposure controls
Appropriate engineering controls
General industrial hygiene practice.
Personal protective equipment
Eye/face protection
Use equipment for eye protection tested and approved under appropriate government standards
such as NIOSH (US) or EN 166(EU).
Skin protection
Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique
(without touching glove's outer surface) to avoid skin contact with this product. Dispose of
contaminated gloves after use in accordance with applicable laws and good laboratory practices.
Wash and dry hands.
The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and
the standard EN 374 derived from it.
Body Protection
Choose body protection in relation to its type, to the concentration and amount of dangerous
substances, and to the specific work-place., The type of protective equipment must be selected
according to the concentration and amount of the dangerous substance at the specific workplace.
Respiratory protection
Respiratory protection is not required. Where protection from nuisance levels of dusts are desired,
use type N95 (US) or type P1 (EN 143) dust masks. Use respirators and components tested and
approved under appropriate government standards such as NIOSH (US) or CEN (EU).

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Section 9. PHYSICAL AND CHEMICAL PROPERTIES
Information on basic physical and chemical properties
a) Appearance Form: crystalline
Colour: white
b) Odour no data available
c) Odour Threshold no data available
d) pH no data available
e) Melting point/freezing no data available
point
f) Initial boiling point and no data available
boiling range
g) Flash point no data available
h) Evaporation rate no data available
i) Flammability (solid, gas) no data available
j) Upper/lower no data available
flammability or
explosive limits
k) Vapour pressure no data available
l) Vapour density no data available
m) Relative density no data available
n) Water solubility no data available
o) Partition coefficient: n- log Pow: 1,8
octanol/water
p) Autoignition no data available
temperature
q) Decomposition no data available
temperature
r) Viscosity no data available
s) Explosive properties no data available
t) Oxidizing properties no data available
Other safety information
no data available

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Section 10. STABILITY AND REACTIVITY
Reactivity
no data available
Chemical stability
no data available
Possibility of hazardous reactions
no data available
Conditions to avoid
no data available
Incompatible materials
Strong oxidizing agents
Hazardous decomposition products
Other decomposition products - no data available

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Section 11. TOXICOLOGICAL INFORMATION
Information on toxicological effects
Acute toxicity
no data available
Skin corrosion/irritation
no data available
Serious eye damage/eye irritation
no data available
Respiratory or skin sensitization
no data available
Germ cell mutagenicity
no data available
Carcinogenicity
IARC: No component of this product present at levels greater than or equal to 0.1% is identified as
probable, possible or confirmed human carcinogen by IARC.
Reproductive toxicity
no data available
Specific target organ toxicity - single exposure
no data available
Specific target organ toxicity - repeated exposure
no data available
Aspiration hazard
no data available
Potential health effects
Inhalation
May be harmful if inhaled. May cause respiratory tract irritation.
Ingestion May be harmful if swallowed.
Skin May be harmful if absorbed through skin. May cause skin irritation.
Eyes May cause eye irritation.
Additional Information
RTECS: Not available

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Section 12. ECOLOGICAL INFORMATION
Toxicity
no data available
Persistence and degradability
no data available
Bioaccumulative potential
no data available
Mobility in soil
no data available
Results of PBT and vPvB assessment
no data available
Other adverse effects
no data available

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Section 13. DISPOSAL CONSIDERATIONS
Waste treatment methods
Product
Offer surplus and non-recyclable solutions to a licensed disposal company.
Contaminated packaging
Dispose of as unused product.

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Section 14. TRANSPORT INFORMATION
UN number
ADR/RID: - IMDG: - IATA: -
UN proper shipping name
ADR/RID: Not dangerous goods
IMDG: Not dangerous goods
IATA: Not dangerous goods
Transport hazard class(es)
ADR/RID: - IMDG: - IATA: -
Packaging group
ADR/RID: - IMDG: - IATA: -
Environmental hazards
ADR/RID: no IMDG Marine pollutant: no IATA: no
Special precautions for user
no data available

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SECTION 15 - REGULATORY INFORMATION
N/A

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

用途

这种具有高度选择性和有效性的手性助剂，在与二异丁基氢化铝发生还原裂解反应后，可以直接还原生成相应的醛，并同时保留手性特性。

反应信息

• 作为反应物：
  描述：

  (S)-4-苯基噁唑烷-2-硫酮 在 sodium hydride 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 (S)-N-[(3R)-3-mercaptobutanoyl]-4-phenyloxazolidin-2-one
  参考文献：
  名称：

  布朗斯台德酸促进的 N-烯酰基恶唑烷-2-硫酮中的分子内硫转移。β-巯基羧酸的实际不对称合成及其机理研究

  摘要：

  证明了单独使用布朗斯台德酸有效促进 N-烯酰基恶唑烷-2-硫酮中的硫转移过程以产生 β-巯基羰基衍生物的能力。该反应对一系列烷基取代的 N-烯酰基恶唑烷-2-硫酮（dr 通常高于 98:2）进行了基本上完美的非对映控制，并且对大多数芳基取代的对应物（dr 通常高于 92:8）具有高选择性。重要的是，该反应在 β,β-二取代的 N-烯酰基恶唑烷-2-硫酮中也非常有效，产生选择性通常高于 95:5 的四元 CS 立体中心。评估了一系列酸（三氟乙酸、二氟乙酸、乙酸、三氟甲磺酸）的相对效率，显示 TFA 和 TfOH 是最有效的，而乙酸则是完全低效的反应促进剂。新程序在两个方面补充了我们小组先前描述的路易斯酸促进反应：首先，对路易斯酸或布朗斯台德酸促进的β，β-二取代烯酰基化合物的反应获得了立体发散结果。其次，虽然布朗斯台德酸促进的反应是立体有择的，在底物 E/Z 构型和产物立体化学之间提供了良好的相关性，但由路易斯酸

  DOI：

  10.1021/ja0654027
• 作为产物：
  描述：

  (S)-4-苯基-2-恶唑烷酮 在 sulfur 作用下， 以 水 为溶剂， 反应 8.0h， 以91.6%的产率得到(S)-4-苯基噁唑烷-2-硫酮
  参考文献：
  名称：

  一种(S)-4-苯基-2-恶唑烷酮的制备方法

  摘要：

  本发明公开了一种合成(S)‑4‑苯基‑2‑恶唑烷酮的制备方法，属于有机合成技术领域。将N‑Boc‑L‑苯甘氨酸在硼烷试剂还原下得到N‑Boc‑L‑苯甘氨醇，随后在催化剂的作用下关环反应得到(S)‑4‑苯基‑2‑恶唑烷酮。该产品与硫粉和硫化铵或多硫化铵反应还可得到(S)‑4‑苯基恶唑烷‑2‑硫酮。该方法避免了具有细胞毒性试剂或溶剂的使用，具有原料易得，操作简便等优点，符合绿色化学，具备潜在的工业化放大前景。

  公开号：

  CN112500361B

文献信息

• Asymmetric transfer hydrogenation of ketones using Ru(0) nanoparticles modified by Chiral Thiones
  作者：Noor U. Din Reshi、Dineshchakravarthy Senthurpandi、Ashoka G. Samuelson

  DOI：10.1002/aoc.4885

  日期：2019.5

  The catalytic asymmetric transfer hydrogenation (ATH) of acetophenone in isopropanol by Ru(0) nanoparticles (NPs) obtained by the in‐situ reduction of Ru (II) half‐sandwich complexes of chiral 2‐oxazolidinethiones and 2‐thiozolidinethiones was examined and compared with the catalytic activity of Ru(0) NPs formed in‐situ by the reduction of [Ru(p‐cymene)(Cl)2]2 in presence of optically active ligands

  考察并比较了通过手性2-恶唑烷硫酮和2-硫唑烷硫酮的Ru（II）半三明治复合物原位还原得到的Ru（0）纳米颗粒（NPs）在异丙醇中对苯乙酮的催化不对称转移氢化（ATH）通过还原[Ru（对伞花烃）（Cl）2 ] 2原位形成Ru（0）NPs的催化活性（S）-4-异丁基噻唑烷-2-硫酮，（S）-4-异丙基-2-（-2-吡啶基）-2-恶唑啉，（8S，9R）-（-）-辛可尼定，（S）-亮氨酸，（S）-苯丙氨醇和（S）-亮氨酸。然后检查了三个最佳的催化体系中十三种具有不同电子和空间特性的芳族酮的ATH。使用苯乙酮TH中Ru（II）半三明治复合物与（S）-4-异丁基噻唑烷-2-硫酮的NP最多可得到24％ee。通过TEM和DLS测量来表征NP。动力学研究和中毒实验证实，该反应是由原位形成的手性NP催化的。还进行了复合物的完整表征，包括两个复合物的X射线晶体学表征。
• Synthesis of new C3 symmetric amino acid- and aminoalcohol-containing chiral stationary phases and application to HPLC enantioseparations
  作者：Jeongjae Yu、Daniel W. Armstrong、Jae Jeong Ryoo

  DOI：10.1002/chir.22766

  日期：2018.1

  We recently reported a new C3‐symmetric (R)‐phenylglycinol N‐1,3,5‐benzenetricarboxylic acid‐derived chiral high‐performance liquid chromatography (HPLC) stationary phase (CSP 1) that demonstrated better results as compared to a previously described N‐3,5‐dintrobenzoyl (DNB) (R)‐phenylglycinol‐derived CSP. Over a decade ago, (S)‐leucinol, (R)‐phenylglycine, and (S)‐leucine derivatives were used as

  我们最近报道了一种新的C3对称（R）-苯基甘氨醇N -1,3,5-苯三甲酸衍生的手性高效液相色谱（HPLC）固定相（CSP 1），与先前描述的结果相比具有更好的结果N -3,5-二硝基苯甲酰（DNB）（R）-苯基甘氨醇衍生的CSP。十多年前，（S）-亮氨酸，（R）-苯甘氨酸和（S）-亮氨酸衍生物被用作基于3,5-DNB的Pirkle型CSP的手性分离原料。在这项研究中，通过结合上述想法和结果，准备了三个新的C3对称CSP（CSP 2、3和4）。在这里，我们描述了新的C3对称CSP（CSP 2–CSP 4）的合成程序和应用。
• <i>N</i>-(Diazoacetyl)oxazolidin-2-thiones as Sulfur-Donor Reagents: Asymmetric Synthesis of Thiiranes from Aldehydes
  作者：Israel Cano、Enrique Gómez-Bengoa、Aitor Landa、Miguel Maestro、Antonia Mielgo、Iurre Olaizola、Mikel Oiarbide、Claudio Palomo

  DOI：10.1002/anie.201204771

  日期：2012.10.22

  Sulfur tyranny: Thiiranes, instead of oxiranes, can be obtained in a highly stereoselective manner through the cycloaddition reaction of N‐acyl oxazolidine tethered diazo thione compounds with aldehydes catalyzed by RhII. Thus, this reaction provides versatile adducts S functionalized at both the α and β position, with concomitant generation of two contiguous stereocenters.

  硫暴：通过N-酰基恶唑烷系链的重氮硫酮化合物与Rh II催化的醛类的环加成反应，可以以高度立体选择性的方式获得噻烷类而不是肟类。因此，该反应提供了在α和β位置均被官能化的通用加合物S，并伴随产生两个连续的立体中心。
• Thiocarbonyl Surrogate via Combination of Sulfur and Chloroform for Thiocarbamide and Oxazolidinethione Construction
  作者：Wei Tan、Jianpeng Wei、Xuefeng Jiang

  DOI：10.1021/acs.orglett.7b00819

  日期：2017.4.21

  An efficient and practical thiocarbonyl surrogate via combination of sulfur and chloroform has been developed. A variety of thiocarbamides and oxazolidinethiones have been established, including chiral thiourea catalysts and chiral oxazolidinethione auxiliaries with high selectivity. Meanwhile, pesticides Diafenthiuron (an acaricide), ANTU (a rodenticide), and Chloromethiuron (an insecticide) were

  已经开发了通过硫和氯仿的组合的有效和实用的硫代羰基替代物。已经建立了多种硫代脲和恶唑烷硫酮，包括具有高选择性的手性硫脲催化剂和手性恶唑烷硫酮助剂。同时，实际上通过克方法通过该方法合成了杀虫剂DiafeNThiuron（一种杀螨剂），ANTU（一种灭鼠剂）和Chloromethiuron（一种杀虫剂）。通过卡宾捕集控制实验进一步确认了作为主要中间体的双氯卡宾。
• Next-Generation Total Synthesis of Vancomycin
  作者：Maxwell J. Moore、Shiwei Qu、Ceheng Tan、Yu Cai、Yuzo Mogi、D. Jamin Keith、Dale L. Boger

  DOI：10.1021/jacs.0c07433

  日期：2020.9.16

  A next-generation total synthesis of vancomycin aglycon is detailed that was achieved in 17 steps (longest linear sequence, LLS) from the constituent amino acid subunits with kinetically controlled diastereoselective introduction of all three elements of atropisomerism. In addition to new syntheses of three of the seven amino acid subunits, highlights of the approach include a ligand-controlled atroposelective

  详细介绍了万古霉素苷元的下一代全合成，该合成通过 17 个步骤（最长线性序列，LLS）从组成氨基酸亚基实现，并通过动力学控制非对映选择性引入所有三种阻转异构元素。除了七个氨基酸亚基中三个的新合成外，该方法的亮点包括配体控制的 atroposelective one-pot Miyaura 硼酸化-Suzuki 偶联序列，用于引入 AB 联芳基手性轴 (>20:1 dr)，几乎没有竞争性差向异构化 (>30:1 dr) 的 AB 环系统的基本瞬时和可扩展的大环内酰胺化，以及用于连续 CD (8:1 dr) 和 DE 环闭合的两个室温 atroposelective 分子内 SNAr 环化 (14: 1 dr）受益于预先形成的 AB 环系统的预组织和微妙的取代基效应。结合万古霉素苷元的无保护基两步酶促糖基化，这提供了万古霉素的 19 步全合成。该方法为大规模合成制备口袋修饰万古霉素类似物铺平了