(S)-(-)-甲基对甲苯亚砜 | 5056-07-5

• 物质功能分类: 化学试剂 - 有机试剂 - 砜、亚砜类化合物
• 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)-(-)-甲基对甲苯亚砜
• 中文别名: (S)-(-)-甲基对甲苯砜
• 英文名称: (S)-methyl p-tolyl sulfoxide
• 英文别名: 1-methyl-4-(methylsulfinyl)benzene；methyl p-tolyl sulfoxide；1-methyl-4-[(S)-methylsulfinyl]benzene
• CAS: 5056-07-5
• 化学式: C₈H₁₀OS
• 分子量: 154.233
• InChiKey: FEVALTJSQBFLEU-JTQLQIEISA-N

物化性质

• 熔点：
  75-77 °C(lit.)
• 沸点：
  282.4±19.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)
• 稳定性/保质期：

  如果按照规定使用和储存，则不会分解，也未曾发生任何已知的危险。

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• WGK Germany：
  3
• 海关编码：
  2930909090
• 储存条件：
  请将药品存放在密闭、阴凉干燥的地方保存。

SDS

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Section 1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product identifiers
: (S)-(−)-Methyl p-tolyl sulfoxide
Product name
CAS-No. : 5056-07-5
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 : C8H10OS
Molecular Weight : 154,23 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, 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.
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 Melting point/range: 75 - 77 °C
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- no data available
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

反应信息

• 作为反应物：
  描述：

  (S)-(-)-甲基对甲苯亚砜 在 咪唑 、 正丁基锂 、 碘苯二乙酸 、 氨基甲酸铵 、 二异丙胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 92.17h， 生成 (S,E)-((tert-butyldiphenylsilyl)imino)(4-ethynylstyryl)(p-tolyl)-λ⁶-sulfanone
  参考文献：
  名称：

  乙烯基亚砜亚胺和磺酰亚胺酰胺的合成和构型分配

  摘要：

  乙烯基砜和磺胺类药物因其在共价蛋白抑制剂中用作亲电弹头而受到重视。相反，其 S(VI) 氮杂等排体，乙烯基亚砜亚胺和磺酰亚胺酰胺，研究较少，尚未应用于蛋白质生物偶联领域。在此，我们报告了一系列不同的合成方法，用于构建乙烯基亚砜和乙烯基磺酰亚胺结构，从而可以进入亲电化学空间的新领域。我们展示了如何将后期功能化应用于这些基序以结合炔标签，为未来的化学生物学应用生成完全功能化的探针。最后，

  DOI：

  10.1021/acs.joc.1c00373
• 作为产物：
  描述：

  4-甲基茴香硫醚 在 过氧化氢异丙苯 、 titanium BINOL derivative 作用下， 以 四氯化碳 为溶剂， 反应 72.0h， 以41.5%的产率得到(S)-(-)-甲基对甲苯亚砜
  参考文献：
  名称：

  用于对映选择性羰基烯和磺化氧化反应的自支撑多相钛催化剂。

  摘要：

  通过在不使用支持物的情况下通过桥联的多主题BINOL配体与[Ti（OiPr）4]的原位组装，开发了一种手性钛配合物异质化的新策略。组装的多相催化剂（自负载）在α-甲基苯乙烯与乙醛酸乙酯（最高98％ee）的羰基-烯反应和硫化物的氧化（最高> 99％ee）中均表现出优异的对映选择性。这些非均相催化体系的催化性能与同类均相催化剂相当或什至更高。在组装的催化剂中，配体的两个BINOL单元之间的间隔基对羰基-烯反应的对映选择性具有重要影响。这证明了组件的超分子结构对其催化行为的重要性。在亚砜氧化的催化中，自担载的多相钛催化剂非常稳定，可以方便地回收和再利用一个月（至少八个循环），而活性和对映选择性没有明显损失（最高ee> 99.9％）。这些自担载催化剂的特征，例如制备简便，固态催化剂的稳固手性结构，固体中催化活性单元的高密度以及易于回收和简单循环利用，对于开发用于制备方法的方法尤为重要。工业过程中光

  DOI：

  10.1002/chem.200500239
• 作为试剂：
  描述：

  苯丙醛 、 丙烯基三氯硅烷 在 (S)-(-)-甲基对甲苯亚砜 、 四丁基碘化铵 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 (S)-1-phenyl-5-hexen-3-ol 、 (R)-1-phenyl-hex-5-en-3-ol
  参考文献：
  名称：

  Chiral sulfoxides as activators of allyl trichlorosilanes in the stereoselective allylation of aldehydes

  摘要：

  手性芳基甲基亚砜在不对称烯丙基化醛与烯丙基三氯硅烷反应中被证明是有效的催化剂。对于电子贫穷的醛，发现了高的对映选择性。高水平的差向选择性及非线性效应的检测使得反应的一些机理方面得以阐明。

  DOI：

  10.1039/c002988b

文献信息

• Catalytic Enantioselective Oxidation of Bulky Alkyl Aryl Thioethers with H2O2 over Titanium-Salan Catalysts
  作者：Konstantin P. Bryliakov、Evgenii P. Talsi

  DOI：10.1002/ejoc.201100557

  日期：2011.8

  procedure for the oxidation of bulky (preferably aryl benzyl substituted) thioethers with hydrogen peroxide in good to high yields and enantioselectivities (up to 98.5 % ee) is reported. The high optical yields are achieved in a tandem stereoconvergent enantioselective oxidation and kinetic resolution process. A reasonable balance between the sulfoxide yield and enantioselectivity could be found by varying

  报道了一种用过氧化氢以良好至高产率和对映选择性（高达 98.5% ee）氧化大体积（优选芳基苄基取代）硫醚的简单有效的催化程序。在串联立体会聚对映选择性氧化和动力学拆分过程中实现了高光学产率。通过改变浓度和温度可以找到亚砜产率和对映选择性之间的合理平衡。报道了用于制备更具立体选择性的催化剂的钛-salan 催化剂的改进合成。
• An Efficient Stereoselective Synthesis of Penaresidin A from (<i>E</i>)-2-Protected Amino-3,4-unsaturated Sulfoxide
  作者：Sadagopan Raghavan、V. Krishnaiah

  DOI：10.1021/jo9022638

  日期：2010.2.5

  asymmetric synthesis of penaresidin A is disclosed. A β-protected amino-γ,δ-unsaturated sulfoxide was prepared by stereoselective addition of the lithio anion of (R)-methyl p-tolyl sulfoxide to an unsaturated sulfinylimine. The pendant sulfoxide group was used as an intramolecular nucleophile to functionalize an alkene regio- and stereoselectively to furnish a bromohydrin, which was employed as the key intermediate

  公开了一种高效，模块化，非对称的对虾青素A合成。通过将（R）-甲基对甲苯基亚砜的硫代阴离子立体选择性地加成到不饱和的亚磺酰亚胺中，制备了β-保护的氨基-γ，δ-不饱和亚砜。亚侧链亚砜用作分子内亲核试剂，对烯烃进行区域选择性和立体选择性官能化，以提供溴代醇，该溴代醇用作制备Penaresidin A的氮杂环丁烷亚基的关键中间体。介绍了侧链的立体中心通过环氧化物的区域选择性开放。Julia-Kocienski烯化用于偶联氮杂环丁烷和侧链亚基。本文公开的方法学也可用于合成核糖-和阿拉伯-植物鞘氨醇和具有氨基醇部分的化合物。
• Organocatalytic Asymmetric Synthesis of Sulfoxides from Sulfenic Acid Anions Mediated by a <i>Cinchona</i>-Derived Phase-Transfer Reagent
  作者：Fabien Gelat、Jayadevan Jayashankaran、Jean-François Lohier、Annie-Claude Gaumont、Stéphane Perrio

  DOI：10.1021/ol2010962

  日期：2011.6.17

  Preliminary results concerning a conceptually novel route to chiral sulfoxides based on the asymmetric alkylation of sulfenate salts with alkyl halides mediated by a chiral phase-transfer catalyst are described. As a representative example, o-anisyl methyl sulfoxide was produced in 96% yield and with an enantiomeric excess of 58% using commercial cinchonidinium derivative 2a.

  本文描述了有关手性亚砜在手性相转移催化剂介导的亚磺酸盐与烷基卤化物的不对称烷基化的基础上获得手性亚砜的新颖方法的初步结果。作为代表性的例子，ö -anisyl甲基亚砜，96％收率和58％对映体过量使用商业金鸡尼丁衍生物制备2A。
• Asymmetric Hydroxylative Phenol Dearomatization through In Situ Generation of Iodanes from Chiral Iodoarenes and<i>m</i>-CPBA
  作者：Stéphane Quideau、Gildas Lyvinec、Mélanie Marguerit、Katell Bathany、Aurélie Ozanne-Beaudenon、Thierry Buffeteau、Dominique Cavagnat、Alain Chénedé

  DOI：10.1002/anie.200901039

  日期：2009.6.8

  ′I′ is all the hype: A twofold excess of iodoarene in the title reaction leads to ortho‐quinols in good yields, whereas organocatalytic versions of this reaction enable subsequent epoxidation in a regio‐ and diastereoselective fashion. Chiral iodobiarenes led to enantioselectivities up to 50 % ee. m‐CPBA=meta‐chloroperoxybenzoic acid.

  “ I”全是炒作：标题反应中碘芳烃的两倍过量导致邻喹啉收率高，而该反应的有机催化形式使得随后的环氧化反应可以进行区域选择性和非对映选择性。手性碘伏二烯导致对映体选择性高达ee的50％  。m -CPBA =间-氯过氧苯甲酸。
• Copper-Catalyzed Asymmetric Oxidation of Sulfides
  作者：Graham E. O’Mahony、Alan Ford、Anita R. Maguire

  DOI：10.1021/jo2026178

  日期：2012.4.6

  Copper-catalyzed asymmetric sulfoxidation of aryl benzyl and aryl alkyl sulfides, using aqueous hydrogen peroxide as the oxidant, has been investigated. A relationship between the steric effects of the sulfide substituents and the enantioselectivity of the oxidation has been observed, with up to 93% ee for 2-naphthylmethyl phenyl sulfoxide, in modest yield in this instance (up to 30%). The influence

  研究了使用过氧化氢水溶液作为氧化剂的铜催化的芳基苄基和芳基烷基硫化物的不对称硫氧化反应。已经观察到硫化物取代基的空间效应与氧化的对映选择性之间的关系，其中2-萘甲基甲基苯基亚砜的ee高达93％，在这种情况下产率适中（高达30％）。检查了溶剂和配体结构变化的影响，然后使用优化的条件氧化了许多芳基烷基和芳基苄基硫化物，在大多数情况下以极好的收率（高达92％）产生亚砜，并且在室温下具有良好的对映体纯度。某些情况下（高达ee的84％）。