2,5-二氢噻吩-3-羧酸甲酯 | 67488-46-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢噻吩类
• 中文名称: 2,5-二氢噻吩-3-羧酸甲酯
• 中文别名: 2,5-二氢噻吩-3-甲酸甲酯；2,4-二氟吡啶
• 英文名称: methyl 2,5-dihydrothiophene-3-carboxylate
• 英文别名: 2,5-dihydrothiophene-1-carboxylic acid methyl ester；3-Carbomethoxy-2,5-dihydrothiophen；2,5-dihydro-thiophene-3-carboxylic acid methyl ester
• CAS: 67488-46-4
• 化学式: C₆H₈O₂S
• mdl: MFCD04038417
• 分子量: 144.194
• InChiKey: RDHSPSSFHQGPDS-UHFFFAOYSA-N

物化性质

• 熔点：
  34.0 to 38.0 °C
• 稳定性/保质期：
  在常温常压下稳定，应远离氧化剂。

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2934999090

SDS

Methyl 2,5-Dihydrothiophene-3-carboxylate Revision number: 6
SAFETY DATA SHEET

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Section 1. IDENTIFICATION
Product name: Methyl 2,5-Dihydrothiophene-3-carboxylate

Revision number: 6

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Section 2. HAZARDS IDENTIFICATION
GHS classification
PHYSICAL HAZARDS Not classified
Not classified
HEALTH HAZARDS
ENVIRONMENTAL HAZARDS Not classified
GHS label elements, including precautionary statements
Pictograms or hazard symbols None
No signal word
Signal word
Hazard statements None
None
Precautionary statements:

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Section 3. COMPOSITION/INFORMATION ON INGREDIENTS
Substance/mixture: Substance
Components: Methyl 2,5-Dihydrothiophene-3-carboxylate
Percent: >95.0%(GC)
CAS Number: 67488-46-4
Synonyms: 2,5-Dihydrothiophene-3-carboxylic Acid Methyl Ester
Chemical Formula: C6H8O2S

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Section 4. FIRST AID MEASURES
Inhalation: Remove victim to fresh air and keep at rest in a position comfortable for breathing.
Get medical advice/attention if you feel unwell.
Skin contact: Remove/Take off immediately all contaminated clothing. Rinse skin with
water/shower. If skin irritation or rash occurs: Get medical advice/attention.
Eye contact: Rinse cautiously with water for several minutes. Remove contact lenses, if present
and easy to do. Continue rinsing. If eye irritation persists: Get medical
advice/attention.
Ingestion: Get medical advice/attention if you feel unwell. Rinse mouth.
Protection of first-aiders: A rescuer should wear personal protective equipment, such as rubber gloves and air-
tight goggles.

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Section 5. FIRE-FIGHTING MEASURES
Suitable extinguishing Dry chemical, foam, water spray, carbon dioxide.
media:
Specific hazards arising Take care as it may decompose upon combustion or in high temperatures to
from the chemical: generate poisonous fume.
Methyl 2,5-Dihydrothiophene-3-carboxylate

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Section 5. FIRE-FIGHTING MEASURES
Precautions for firefighters: Fire-extinguishing work is done from the windward and the suitable fire-extinguishing
method according to the surrounding situation is used. Uninvolved persons should
evacuate to a safe place. In case of fire in the surroundings: Remove movable
containers if safe to do so.
Special protective When extinguishing fire, be sure to wear personal protective equipment.
equipment for firefighters:

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Section 6. ACCIDENTAL RELEASE MEASURES
Use personal protective equipment. Keep people away from and upwind of spill/leak.
Personal precautions,
protective equipment and Entry to non-involved personnel should be controlled around the leakage area by
emergency procedures: roping off, etc.
Environmental precautions: Prevent product from entering drains.
Methods and materials for Sweep dust to collect it into an airtight container, taking care not to disperse it.
containment and cleaning Adhered or collected material should be promptly disposed of, in accordance with
up: appropriate laws and regulations.

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Section 7. HANDLING AND STORAGE
Precautions for safe handling
Handling is performed in a well ventilated place. Wear suitable protective equipment.
Technical measures:
Prevent dispersion of dust. Wash hands and face thoroughly after handling.
Use a local exhaust if dust or aerosol will be generated.
Advice on safe handling: Avoid contact with skin, eyes and clothing.
Conditions for safe storage, including any
incompatibilities
Storage conditions: Keep container tightly closed. Store in a refrigerator.
Store under inert gas.
Store away from incompatible materials such as oxidizing agents.
Heat-sensitive, Air-sensitive
Packaging material: Comply with laws.

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Section 8. EXPOSURE CONTROLS / PERSONAL PROTECTION
Install a closed system or local exhaust as possible so that workers should not be
Engineering controls:
exposed directly. Also install safety shower and eye bath.
Personal protective equipment
Respiratory protection: Dust respirator. Follow local and national regulations.
Hand protection: Protective gloves.
Eye protection: Safety glasses. A face-shield, if the situation requires.
Skin and body protection: Protective clothing. Protective boots, if the situation requires.

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Section 9. PHYSICAL AND CHEMICAL PROPERTIES
Physical state (20°C): Solid
Form: Crystal- Lump
White - Pale yellow
Colour:
Odour: No data available
pH: No data available
Melting point/freezing point:36°C
No data available
Boiling point/range:
Flash point: No data available
Flammability or explosive
limits:
No data available
Lower:
Upper: No data available
No data available
Relative density:
Solubility(ies):
No data available
[Water]
[Other solvents] No data available
Methyl 2,5-Dihydrothiophene-3-carboxylate

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Section 10. STABILITY AND REACTIVITY
Chemical stability: Stable under proper conditions.
Possibility of hazardous No special reactivity has been reported.
reactions:
Incompatible materials: Oxidizing agents
Hazardous decomposition Carbon monoxide, Carbon dioxide, Sulfur oxides
products:

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Section 11. TOXICOLOGICAL INFORMATION
Acute Toxicity: No data available
Skin corrosion/irritation: No data available
Serious eye No data available
damage/irritation:
Germ cell mutagenicity: No data available
Carcinogenicity:
IARC = No data available
No data available
NTP =
Reproductive toxicity: No data available

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Section 12. ECOLOGICAL INFORMATION
Ecotoxicity:
Fish: No data available
Crustacea: No data available
Algae: No data available
Persistence / degradability: No data available
Bioaccumulative No data available
potential(BCF):
Mobility in soil
No data available
Log Pow:
Soil adsorption (Koc): No data available
Henry's Law No data available
constant(PaM3/mol):

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Section 13. DISPOSAL CONSIDERATIONS
Recycle to process, if possible. Consult your local regional authorities. You may be able to dissolve or mix material
with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber system.
Observe all federal, state and local regulations when disposing of the substance.

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Section 14. TRANSPORT INFORMATION
Does not correspond to the classification standard of the United Nations
Hazards Class:
UN-No: Not listed

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Section 15. REGULATORY INFORMATION
Safe management ordinance of dangerous chemical product (State Council announces on January 26, 2002
and revised on February 16,2011): Safe use and production, the storage of a dangerous chemical, transport,
loading and unloading were prescribed.
Methyl 2,5-Dihydrothiophene-3-carboxylate

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  2,5-二氢噻吩-3-羧酸甲酯 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 生成 2,5-dihydrothiophene-1-carboxylic acid
  参考文献：
  名称：

  将非手性偶氮甲亚胺非对映选择性加成至环状α，β-不饱和N-烯酰基冰片烷磺酰胺

  摘要：

  非外消旋的双非对映选择性1,3-偶极环加成反应 甲亚胺盐进行了对五元和六元环状α，β-不饱和N-烯酰基冰片烷磺酰胺的合成。什么时候合适溶剂通过使用，以良好的非对映选择性获得了形成的稠合双环加合物。而且，改变了启动的绝对配置叶立德前体逆转了某些此类反应的非对映选择性。裂解所提供的环加合物的手性助剂氨基醇和β-氨基酯。后者被转化为抗菌化合物的已知前体。

  DOI：

  10.1039/b200579d
• 作为产物：
  描述：

  3-Hydroxy-4-methoxycarbonyl-tetrahydrothiophen 在 三乙胺 、 对甲苯磺酰氯 作用下， 以 二氯甲烷 为溶剂， 以378g的产率得到2,5-二氢噻吩-3-羧酸甲酯
  参考文献：
  名称：

  一种3-环丁烯砜-3-甲酸甲酯的制备方法

  摘要：

  本发明涉及一种3‑环丁烯砜‑3‑甲酸甲酯的制备方法，属于医药中间体开发应用的合成技术领域。包括如下步骤：以丙酮为溶剂，加入2,5‑二羟基‑1,4‑二噻烷、丙烯酸甲酯、无机碱，加完后开始室温搅拌反应；加入三乙胺后，冰水浴降温至0～10℃，加入对甲苯磺酰氯的二氯甲烷溶液，然后恢复至室温进行反应，得到中间体Ⅱ；将中间体Ⅱ加入到纯水中，加入催化剂钨酸钠，然后升温加热至50℃～60℃，加入30％双氧水溶液反应得3‑环丁烯砜‑3‑甲酸甲酯粗产品，最后重结晶，得3‑环丁烯砜‑3‑甲酸甲酯。本发明采用3步合成了3‑环丁烯砜‑3‑甲酸甲酯，HPLC纯度达到99％以上，总收率为70％以上。

  公开号：

  CN117551072A

文献信息

• The dimerisation of 2-methoxycarbonylbuta-1,3-diene: the importance of paralocalisation energy in assessing diene reactivity
  作者：Claude Spino、Jason Crawford、Yunping Cui、Melinda Gugelchuk

  DOI：10.1039/a708199e

  日期：——

  The dimerisation and competitive cycloaddition of 2-methoxycarbonylbuta-1,3-diene with electron-rich dienes has been investigated. Experimental results provide evidence that the enthalpy of the π-system significantly influences the energy of the transition state of cycloadditions of this type. This has been corroborated by ab initio calculations. We propose an early reorganisation of the π-electrons in such cycloadditions to explain the influence stated above.

  已研究了2-甲氧基羧基丁-1,3-二烯与富电子二烯的二聚化和竞争环加成反应。实验结果提供了证据，证明π系统的焓显著影响此类环加成反应的过渡态能量。这一结论已通过从头计算得到证实。我们提出在这种环加成反应中，π电子的早期重组可以解释上述影响。
• Bicyclic Pyrrolidines for Medicinal Chemistry via [3 + 2]-Cycloaddition
  作者：Vladimir I. Savych、Vladimir L. Mykhalchuk、Pavlo V. Melnychuk、Andrii O. Isakov、Taras Savchuk、Vadim M. Timoshenko、Sergiy A. Siry、Sergiy O. Pavlenko、Dmytro V. Kovalenko、Oleksandr V. Hryshchuk、Vitalii A. Reznik、Bohdan A. Chalyk、Vladimir S. Yarmolchuk、Eduard B. Rusanov、Pavel K. Mykhailiuk

  DOI：10.1021/acs.joc.1c01327

  日期：2021.10.1

  A general approach to bicyclic fused pyrrolidines via [3 + 2]-cycloaddition between nonstabilized azomethyne ylide and endocyclic electron-deficient alkenes was elaborated. “Push–pull” alkenes and CF3-alkenes did not react with the azomethyne ylide under the previously reported conditions, and we developed a superior protocol (LiF, 140 °C, no solvent). Among obtained products were medchem-relevant

  详细阐述了通过不稳定的偶氮甲炔叶立德和环内缺电子烯烃之间的 [3 + 2]-环加成来制备双环稠合吡咯烷的一般方法。在先前报道的条件下，“推拉”烯烃和 CF 3 -烯烃不与偶氮甲炔叶立德反应，我们开发了一种优越的方案（LiF，140 °C，无溶剂）。获得的产品包括与医药相关的双环砜、单氟、二氟和三氟甲基取代的吡咯烷。这种方法不仅允许制备新分子，而且显着简化了现有分子（例如，sofnicline）的合成。
• Rapid Assembly of Tetrasubstituted Furans via Pummerer-Type Rearrangement
  作者：Franz-Lucas Haut、Christoph Habiger、Lukas A. Wein、Klaus Wurst、Maren Podewitz、Thomas Magauer

  DOI：10.1021/jacs.0c12194

  日期：2021.1.20

  as exceptionally versatile intermediates and were shown to participate in a series of valuable postmodifications. The fate of the initial sulfonium intermediate was investigated by mechanistic experiments, and computational studies revealed the existence of an unprecedented Pummerer-type rearrangement. The potential for organic synthesis is highlighted by the total synthesis of bisabolene sesquiterpenoids

  尽管可用于合成呋喃的方法有很多，但能够定制组装完全取代的呋喃的方法却很少。在这里，我们报告了一种在温和反应条件下快速构建四取代、正交功能化呋喃的强大方案。所开发的方法涉及容易获得的 2,5-二氢噻吩的区域选择性开环，然后氧化环化以提供杂环。N-氯代琥珀酰亚胺作为一种廉价的试剂促进了硫的选择性氧化，并在环境温度下30分钟内以高产率进行。所获得的呋喃作为用途广泛的中间体，并被证明可以参与一系列有价值的后修饰。通过机械实验研究了初始锍中间体的命运，计算研究揭示了前所未有的普默勒型重排的存在。红没药烯倍半萜类化合物（侧耳素 A、B 和 D）的全合成凸显了有机合成的潜力。
• A Practical Large-Scale Synthesis of 3-Carbomethoxy-3-sulfolene
  作者：John Leonard、Andrew B. Hague、Martin F. Jones、Richard A. Ward

  DOI：10.1055/s-2000-6367

  日期：——

  A simple, efficient one-flask procedure for the large-scale preparation of 3-carbomethoxy-3-sulfolene from trimethylphosphonoacetate is described. The procedure incorporates a cheap and simple sulfide to sulfone oxidation using Oxone®. No chromatography or intermediate purification steps are involved and the product is isolated by crystallisation.

  描述了一种简单、有效的单瓶程序，用于从三甲基膦酰基乙酸酯大规模制备 3-甲氧基-3-环丁砜。该过程采用了使用 Oxone® 的廉价且简单的硫化物氧化为砜的方法。不涉及色谱或中间纯化步骤，并且通过结晶分离产物。
• Process for preparing 3-substituted thiophene
  申请人：Matsushita Akio

  公开号：US20090137822A1

  公开（公告）日：2009-05-28

  The present invention relates to a process for preparing a 3-substituted thiophene represented by the formula (2): wherein R represents a cyano group, a formyl group, a carboxyl group, a hydrocarbyloxycarbonyl group which may have a substituent(s) or an acyl group which may have a substituent(s), which comprises reacting a vinyl compound represented by the formula (1): RCH═CHY  (1) wherein R has the same meaning as defined above, and Y represents a leaving group, and an α-mercaptoacetaldehyde or a multimer thereof.

  本发明涉及一种制备式（2）的3-取代噻吩的方法，其中R代表氰基、甲酰基、羧基、可具有取代基的烃氧羰基基团或可具有取代基的酰基基团；所述方法包括将式（1）表示的乙烯化合物与α-巯基乙醛或其多聚体反应，式（1）中R的含义与上述定义相同，Y表示离去基团。