4-氧四氢噻酚-3-羧酸甲酯 | 2689-68-1

• 物质功能分类: 医药中间体 - 噻吩类化合物
• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 4-氧四氢噻酚-3-羧酸甲酯
• 中文别名: 4-氧代四氢噻酚-3-羧酸甲酯
• 英文名称: 4-methoxycarbonylthiolan-3-one
• 英文别名: methyl 4-oxotetrahydrothiophene-3-carboxylate；methyl 4-oxothiolane-3-carboxylate
• CAS: 2689-68-1
• 化学式: C₆H₈O₃S
• mdl: MFCD00052381
• 分子量: 160.194
• InChiKey: LEAKUJFYXNILRB-UHFFFAOYSA-N

物化性质

• 熔点：
  37-38 °C
• 沸点：
  95 °C
• 密度：
  1.309±0.06 g/cm3(Predicted)
• 溶解度：
  溶于氯仿

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.666
• 拓扑面积：
  68.7
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 危险等级：
  IRRITANT
• 危险品标志：
  Xi
• 安全说明：
  S26,S37/39
• 危险类别码：
  R36/37/38
• 海关编码：
  2934999090
• 储存条件：
  | 2~8℃ |

SDS

Name:	Methyl 4-oxotetrahydrothiophene-3-carboxylate 95+% Material Safety Data Sheet
Synonym:	Methyl tetrahydro-4-oxo-3-thenoat
CAS:	2689-68-1

Section 1 - Chemical Product MSDS Name:Methyl 4-oxotetrahydrothiophene-3-carboxylate 95+% Material Safety Data Sheet
Synonym:Methyl tetrahydro-4-oxo-3-thenoat

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
2689-68-1	Methyl 4-oxotetrahydrothiophene-3-carb	95+%	220-256-9

Hazard Symbols: XI
Risk Phrases: 36/37/38

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Irritating to eyes, respiratory system and skin.
Potential Health Effects
Eye:
Causes eye irritation.
Skin:
Causes skin irritation. May be harmful if absorbed through the skin.
Ingestion:
May cause irritation of the digestive tract. May be harmful if swallowed.
Inhalation:
Causes respiratory tract irritation. May be harmful if inhaled.
Chronic:
Not available.

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Section 4 - FIRST AID MEASURES
Eyes: 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. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes.
Ingestion:
Get medical aid. Wash mouth out with water.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician:
Treat symptomatically and supportively.

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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.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Vacuum or sweep up material and place into a suitable disposal container.

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Section 7 - HANDLING and STORAGE
Handling:
Avoid breathing dust, vapor, mist, or gas. Avoid contact with skin and eyes.
Storage:
Store in a cool, dry place. Store in a tightly closed container.

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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 ventilation to keep airborne concentrations low.
Exposure Limits CAS# 2689-68-1: Personal Protective Equipment Eyes: Not available.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure limits are exceeded or if irritation or other symptoms are experienced.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Solid
Color: colorless
Odor: pungent odor
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: 95 deg C @3.5mmHg
Freezing/Melting Point: Not available.
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C6H8O3S
Molecular Weight: 160

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not available.
Conditions to Avoid:
Incompatible materials.
Incompatibilities with Other Materials:
Oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, oxides of sulfur, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 2689-68-1 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Methyl 4-oxotetrahydrothiophene-3-carboxylate - 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
No information available.
IMO
No information available.
RID/ADR
No information available.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: XI
Risk Phrases:
R 36/37/38 Irritating to eyes, respiratory system
and skin.
Safety Phrases:
S 26 In case of contact with eyes, rinse immediately
with plenty of water and seek medical advice.
S 37/39 Wear suitable gloves and eye/face
protection.
WGK (Water Danger/Protection)
CAS# 2689-68-1: No information available.
Canada
CAS# 2689-68-1 is listed on Canada's DSL List.
CAS# 2689-68-1 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 2689-68-1 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

简介

4-氧四氢噻酚-3-羧酸甲酯是一种重要的有机中间体。它可用于制备2-(乙基硫基)噻吩并[3,4-d]嘧啶-4-(3H，5H，7H)-酮。该化合物可以通过丙烯酸甲酯与巯基乙酸甲酯的反应来合成。

制备方法 步骤1

将99.2 mL（1.1 mmol）丙烯酸甲酯缓慢加入到含有91 mL（1.0 mmol）巯基乙酸甲酯和2.0 mL（0.02 mol）哌啶的溶液中，同时保持反应混合物温度在50℃。搅拌2小时后，将过量的丙烯酸甲酯和哌啶通过高真空蒸出，得到目标产物3-((甲氧基羰基)甲硫基)丙酸甲酯（185 g，96%）。采用LC-MS (方法A)：(ES+) 193，RT = 4.29分钟。

步骤2

在250 mL的甲苯中，室温下用甲醇处理金属锂（2.12 g，0.30 mol）。所有锂完全溶解后，在70℃搅拌半小时加入3-((甲氧基羰基)甲硫基)丙酸甲酯。随后将反应温度升高至110℃并维持18小时以除去甲醇。所得混合物含有所需产物和3-氧代四氢噻吩-2-甲酸甲酯的混合物。冷却后，通过过滤收集固体，并使用1N HCl溶液酸化，然后用DCM萃取有机相。浓缩后的剩余物通过柱色谱法纯化，用EtOAc/石油醚（2%至10%）洗脱以除去任何残留的3-氧代四氢噻吩-2-甲酸甲酯。最终从第二洗脱馏分获得4-氧四氢噻酚-3-羧酸甲酯（14.7 g，33%）。

反应信息

• 作为反应物：
  描述：

  4-氧四氢噻酚-3-羧酸甲酯 在 吡啶 、 盐酸 、 氯化亚砜 、 水 、 sodium hydrogensulfite 、 溶剂黄146 、 1-butyl-3-methylimidazolium Tetrafluoroborate 、 三氯氧磷 作用下， 以 甲醇 、 水 、 苯 为溶剂， 反应 44.0h， 生成 cantharidin
  参考文献：
  名称：

  一种斑蝥素的合成工艺

  摘要：

  本发明涉及一种在常压条件下制备斑蝥素的绿色环保合成工艺，属于药物合成与制备领域。所述工艺包括以下步骤：采用NaCN水溶液制备3‑氰基‑3‑羟基‑4‑甲酸甲酯‑2,5‑四氢噻吩；在噻吩中加入苯与吡啶、POCl3，制备3‑氰基‑4‑甲酸甲酯‑2,5‑二氢噻吩；再加入乙酸、浓盐酸进行回流反应，制得2,5‑二氢噻吩‑3,4‑二羧酸粉末；将制得的二羧酸与二氯亚砜搅拌回流，制备2,5‑二氢噻吩‑3,4‑二羧酸酐；按二羧酸酐∶呋喃∶离子液体的固液比为＝1mg∶3.5～6μl∶2～4μl进行加热反应，萃取，Raney‑Ni回流，即得斑蝥素。本工艺不需要超高压的条件和设备，在20～50℃过夜反应即可，条件十分温和，转化率高，且斑蝥素收率高，为斑蝥素的工业化生产提供了十分有利的条件。

  公开号：

  CN106674248B
• 作为产物：
  描述：

  3-[(2-甲氧基-2-乙氧基)硫醇]甲基丙酸 在 甲醇 、 sodium 作用下， 反应 1.0h， 以38%的产率得到4-氧四氢噻酚-3-羧酸甲酯
  参考文献：
  名称：

  通过 X 射线结构测定合理化竞争反应性模式：异构（苄氧基噻吩基）恶唑啉与碱的反应

  摘要：

  三个异构体（benzyloxythienyl）恶唑啉9，11和13已被制备并发现，当治疗用强碱，接受对恶唑啉函数要么维蒂希重排或苄基阴离子的分子内攻击，得到从最初裂解衍生的产物形成3-氨基噻吩并产物。这种反应模式与通过 X 射线衍射确定的两个反应基团之间的距离直接相关，11 个中的最大距离导致唯一的 Wittig 重排，13 个中的最短距离仅提供环化衍生产物，中间体距离在9导致这两个过程都被观察到。在两种情况下也获得了相应的N-丁基酰胺，其中一种经过有效的 Wittig 重排，产生了噻吩并 [2,3- c ] 吡咯酮产物。

  DOI：

  10.3390/molecules26247690

文献信息

• Easy One-Pot Synthesis of Fused Heterocycles from 1,2-Diaza-1,3-dienes
  作者：Orazio A. Attanasi、Luca Bianchi、Lucia De Crescentini、Gianfranco Favi、Fabio Mantellini

  DOI：10.1002/ejoc.201100340

  日期：2011.6

  o-4,5,6,6a-tetra-hydropyrrolo[3,4-b]pyrrole-3,3a(1H)-dicarboxylates, and 5-benzyl-7a-hydroxy-1,4,5,6,7,7a-hexahydro-3aH-pyrrolo-[3,2-c]pyridine-3,3a-dicarboxylates starting from diazadienes and heterocycles containing an activated methine group has been developed. This transformations proceeds by Michael addition/5-exo cyclization sequence.

  6a-羟基-6,6a-dihydro-1H-thieno[3,4-b]pyrrole-3,3a(4H)-dicarboxylates, 5-(2-furylmethyl)-6a​​-hydroxy-的碱促进化学选择性合成6-oxo-4,5,6,6a-四氢吡咯并[3,4-b]pyrrole-3,3a(1H)-dicarboxylates, and 5-benzyl-7a-hydroxy-1,4,5,6, 7,7a-六氢-3aH-pyrrolo-[3,2-c]pyridine-3,3a-dicarboxylates 从二氮杂二烯和含有活化次甲基的杂环开始被开发出来。这种转化是通过迈克尔加成/5-外环化序列进行的。
• Synthesis of [<i>b</i>]-Condensed Alkyl 3-Hydroxythiophene-2-carboxylates
  作者：R. Donoso、P. Jordán de Urríes、J. Lissavetzky

  DOI：10.1055/s-1992-26152

  日期：——

  A simple modification of the Fiesselmann procedure for the synthesis of bicyclic alkyl 3-hydroxythiophene-2-carboxylates allow higher yields in only two steps.

  对合成双环烷基3-羟基噻吩-2-羧酸酯的Fiesselmann方法进行简单改进，只需两步即可提高产率。
• ANTI-CANCER DRUGS AND USES RELATING THERETO FOR METASTATIC MALIGNANT MELANOMA AND OTHER CANCERS
  申请人：Gokaraju Ganga Raju

  公开号：US20100068178A1

  公开（公告）日：2010-03-18

  The present invention discloses triazene analogs of the general formula (I) and formula (II), their tautomeric forms, stereoisomers, polymorphs, hydrates, solvates, and pharmaceutically acceptable salts thereof for the metastatic malignant melanoma and other cancers including but not limited to lymphomas, sarcomas, carcinomas, and gliomas. The invention further discloses a process for the preparation of the above said triazene analogs of formula (I) and formula (II), and their pharmaceutically acceptable compositions.

  本发明公开了一般式(I)和式(II)的三氮烯类似物，其互变异构体、立体异构体、多晶形态、水合物、溶剂合物及其在转移性恶性黑色素瘤和其他癌症，包括但不限于淋巴瘤、肉瘤、癌瘤和胶质瘤中的药用可接受盐。该发明还公开了制备上述式(I)和式(II)的三氮烯类似物以及其药用可接受组合物的方法。
• Thiophene-2-carboxamidotetrazoles and pharmaceutical use thereof
  申请人：Warner-Lambert Company

  公开号：US05464855A1

  公开（公告）日：1995-11-07

  Thiophene-2-carboxamidotetrazoles inhibit the Mac-1 integrin and are thus useful for treating diseases mediated by Mac-1 adhesion, including inflammatory disorders.

  噻吩-2-甲酰胺四唑可以抑制Mac-1整合素，因此对于治疗由Mac-1粘附介导的疾病，包括炎症性疾病，是有用的。
• N-ureidoheterocycloalkyl-piperidines as modulators of chemokine receptor activity
  申请人：——

  公开号：US20030032654A1

  公开（公告）日：2003-02-13

  The present application describes modulators of CCR3 of formula (I): 1 or pharmaceutically acceptable salt forms thereof, useful for the prevention of asthma and other allergic diseases.

  本申请描述了CCR3的调节剂，其化学公式为(I)： 1 或其药用可接受的盐形式，用于预防哮喘和其他过敏性疾患。

表征谱图