2-噻吩乙醛酸 | 4075-59-6

• 物质功能分类: 医药中间体 - 杂环化合物 - 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: 2-噻吩乙醛酸
• 中文别名: 2-噻吩甲醯甲酸；噻吩-2-乙醛酸
• 英文名称: 2-thiopheneglyoxylic acid
• 英文别名: 2-oxo-2-(thiophen-2-yl)acetic acid；2-oxo-2-thiophen-2-ylacetic acid
• CAS: 4075-59-6
• 化学式: C₆H₄O₃S
• 分子量: 156.162
• InChiKey: GIWRVUADKUVEGU-UHFFFAOYSA-N

物化性质

• 熔点：
  88-91 °C (lit.)
• 沸点：
  250.38°C (rough estimate)
• 密度：
  1.404 (estimate)
• 稳定性/保质期：
  在常温常压下稳定，这是一种黄色结晶粉末，熔点为88-91℃。它易溶于二氧甲烷和乙酸乙酯，而不溶于石油醚和乙醚。

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  82.6
• 氢给体数：
  1
• 氢受体数：
  4

安全信息

• 危险等级：
  8
• 危险品标志：
  C
• 安全说明：
  S26,S27,S28,S36/37/39,S45
• 危险类别码：
  R34
• WGK Germany：
  3
• 海关编码：
  2934999090
• 危险品运输编号：
  UN 3261 8/PG 2
• 包装等级：
  III
• 危险类别：
  8
• 危险标志：
  GHS05
• 危险性描述：
  H314
• 危险性防范说明：
  P280,P305 + P351 + P338,P310
• 储存条件：
  请将药品存放在避光、通风干燥的地方，并密封保存。

SDS

Name:	2-Thiopheneglyoxylic acid 97% Material Safety Data Sheet
Synonym:	alpha-Oxo-2-thiopheneacetic acid
CAS:	4075-59-6

Section 1 - Chemical Product MSDS Name:2-Thiopheneglyoxylic acid 97% Material Safety Data Sheet
Synonym:alpha-Oxo-2-thiopheneacetic acid

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
4075-59-6	2-Thiopheneglyoxylic acid	97	223-794-2

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.Hygroscopic (absorbs moisture from the air).
Potential Health Effects
Eye:
Causes eye burns. May cause chemical conjunctivitis and corneal damage.
Skin:
Causes skin burns. May cause skin rash (in milder cases), and cold and clammy skin with cyanosis or pale color.
Ingestion:
Causes gastrointestinal tract burns. May cause perforation of the digestive tract. May cause cardiac disturbances. May cause central nervous system effects. May cause systemic effects.
Inhalation:
Inhalation of high concentrations may cause central nervous system effects characterized by nausea, headache, dizziness, unconsciousness and coma. Causes chemical burns to the respiratory tract. Aspiration may lead to pulmonary edema. May cause cardiac abnormalities. May cause systemic effects.
Chronic:
Effects may be delayed.

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Section 4 - FIRST AID MEASURES
Eyes: Get medical aid immediately. Do NOT allow victim to rub eyes or keep eyes closed. Extensive irrigation with water is required (at least 30 minutes).
Skin:
Get medical aid immediately. Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse. Destroy contaminated shoes.
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:
Get medical aid immediately. Remove from exposure and move to fresh air immediately. If breathing is difficult, give oxygen. 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.

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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. Contact with metals may evolve flammable hydrogen gas. 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 use water directly on fire. Use water spray to cool fire-exposed containers. Use foam, dry chemical, or carbon dioxide.

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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. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Use only in a well-ventilated area. Minimize dust generation and accumulation. Do not breathe dust, vapor, mist, or gas. Do not get in eyes, on skin, or on clothing. Keep container tightly closed. Do not ingest or inhale. Wash clothing before reuse. Discard contaminated shoes.
Storage:
Keep container closed when not in use. Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances. Corrosives area. 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 ventilation to keep airborne concentrations low.
Exposure Limits CAS# 4075-59-6: Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin:
Wear appropriate protective gloves and clothing 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: Powder
Color: yellow to green
Odor: None reported.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 88.00 - 91.00 deg C
Autoignition Temperature: Not applicable.
Flash Point: Not applicable.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C6H4O3S
Molecular Weight: 156.16

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

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 4075-59-6 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
2-Thiopheneglyoxylic acid - 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: CORROSIVE SOLID, ACIDIC, ORGANIC, N.O.S.*
Hazard Class: 8
UN Number: 3261
Packing Group: III
IMO
Shipping Name: CORROSIVE SOLID, ACIDIC, ORGANIC, N.O.S.
Hazard Class: 8
UN Number: 3261
Packing Group: III
RID/ADR
Shipping Name: CORROSIVE SOLID, ACIDIC, ORGANIC, N.O.S.
Hazard Class: 8
UN Number: 3261
Packing group: III

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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# 4075-59-6: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 4075-59-6 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 4075-59-6 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

制备方法与用途

用途

2-噻吩乙醛酸是一种制备2-噻吩乙酰氯的中间体，通常通过2-乙酰噻吩与亚硝酸钠/盐酸反应得到。

化学性质

2-噻吩乙醛酸为黄色结晶粉末，熔点在88-91℃之间。它易溶于二氧甲烷和乙酸乙酯，而不溶于石油醚和乙醚。

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  阿地杂质1	methyl 2-thienylglyoxylate	26878-13-7	C7H6O3S	170.189
  2-噻酚乙酯乙酸乙酯	ethyl 2-thienyl glyoxylate	4075-58-5	C8H8O3S	184.216
  2-乙酰基噻吩	2-Acetylthiophene	88-15-3	C6H6OS	126.179

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  阿地杂质1	methyl 2-thienylglyoxylate	26878-13-7	C7H6O3S	170.189
  2-噻酚乙酯乙酸乙酯	ethyl 2-thienyl glyoxylate	4075-58-5	C8H8O3S	184.216
  ——	allyl 2-thiopheneglyoxylate	135386-31-1	C9H8O3S	196.227
  ——	isopropyl-2-oxo-2-(thiophen-2-yl)acetate	——	C9H10O3S	198.243
  ——	tert-butyl 2-oxo-2-(thiophen-2-yl)acetate	57200-08-5	C10H12O3S	212.269
  ——	Benzyl 2-oxo-2-thiophen-2-ylacetate	887641-79-4	C13H10O3S	246.287
  ——	(1-methyl-4-piperidyl)methyl-2-oxo-2-(2-thienyl)acetate	——	C13H17NO3S	267.349
  ——	4-diethylamino-1-methyl-2-butynyl α-oxo-2-thiopheneacetate	129927-73-7	C15H19NO3S	293.387
  氧代(2-噻吩基)乙酰氯	oxo-thiophen-2-yl-acetyl chloride	4075-60-9	C6H3ClO2S	174.608
  ——	(+)-<(1S,2S,5R)-2-Isopropyl-5-methylcyclohexyl>-2-thienylglyoxylat	——	C16H22O3S	294.415

反应信息

• 作为反应物：
  描述：

  2-噻吩乙醛酸 在 草酰氯 作用下， 以 1,4-二氧六环 为溶剂， 反应 4.0h， 生成 氧代(2-噻吩基)乙酰氯
  参考文献：
  名称：

  三组分活化/炔基化/环缩合（AACC）合成增强的发射变色3-乙炔基喹喔啉

  摘要：

  可以通过三组分的连续活化-炔基化-环缩合（AACC）一锅法序列轻松合成2-取代的3-乙炔基喹喔啉生色团。与以前发表的从富电子的π-亲核试剂开始的四组分乙醛酸化作用相比，（杂）芳基乙醛酸的直接活化作用允许引入不能被乙醛化作用直接取代的取代基。通过引入N，N由于二甲基苯胺是2-位的强供体，因此3-乙炔基喹喔啉的发射溶剂变色性可以得到显着增强，以单个生色团在相对窄的极性窗口内覆盖从蓝绿色到深红色橙色的光谱范围。合成多组分反应概念的多样性导向性质使得可以通过Hammett相关性和Lippert-Mataga分析对结构-性质关系进行全面研究，并通过DFT阐明发射溶剂化变色π-共轭供体-受体系统的电子结构。具有PBEh1PBE功能的时间依赖性DFT计算可更好地再现最长波长吸收带的主要电荷转移特征。

  DOI：

  10.1002/chem.201800079
• 作为产物：
  描述：

  2-(4-dimethylamino-phenylimino)-3-oxo-3-[2]thienyl-propionitrile 在 盐酸 作用下， 生成 2-噻吩乙醛酸
  参考文献：
  名称：

  Kroehnke, Chemische Berichte, 1947, vol. 80, p. 298,310

  摘要：

  DOI：
• 作为试剂：
  描述：

  2-噻酚乙酯乙酸乙酯 、 盐酸 在 2-噻吩乙醛酸 、 2-噻酚乙酯乙酸乙酯 、 二氯甲烷 作用下， 以 丙酮 、 水 为溶剂， 反应 4.0h， 生成 2-噻吩乙醛酸
  参考文献：
  名称：

  Thiophenyl triazol-3-one derivatives as smooth muscle relaxants

  摘要：

  本发明提供了一种新型的[1,2,4]三唑-3-酮衍生物，其具有一般式(I)，其中：Q为，R1、R2、R3、R4、R5和R6如本文所定义，或其无毒药学上可接受的盐或溶剂，它们是平滑肌松弛剂，并且在治疗对平滑肌松弛有反应的疾病，如哮喘、肠易激综合征、男性勃起功能障碍和尿失禁方面有用。

  公开号：

  US06613786B2

文献信息

• Reductive Amination of Ketonic Compounds Catalyzed by Cp*Ir(III) Complexes Bearing a Picolinamidato Ligand
  作者：Kouichi Tanaka、Takashi Miki、Kunihiko Murata、Ayumi Yamaguchi、Yoshihito Kayaki、Shigeki Kuwata、Takao Ikariya、Masahito Watanabe

  DOI：10.1021/acs.joc.9b01565

  日期：2019.9.6

  Cp*Ir complexes bearing a 2-picolinamide moiety serve as effective catalysts for the direct reductive amination of ketonic compounds to give primary amines under transfer hydrogenation conditions using ammonium formate as both the nitrogen and hydrogen source. The clean and operationally simple transformation proceeds with a substrate to catalyst molar ratio (S/C) of up to 20,000 at relatively low

  带有2-吡啶甲酸酰胺部分的Cp * Ir配合物可作为有效的催化剂，用于在酮的转移氢化条件下，使用甲酸铵作为氮源和氢源，对酮类化合物进行直接还原胺化，从而生成伯胺。清洁且操作简单的转化过程是在相对较低的温度下以高达20,000的底物与催化剂的摩尔比（S / C）进行的，并且对伯胺表现出出色的化学选择性。
• Primary Amines by Transfer Hydrogenative Reductive Amination of Ketones by Using Cyclometalated Ir^IIICatalysts
  作者：Dinesh Talwar、Noemí Poyatos Salguero、Craig M. Robertson、Jianliang Xiao

  DOI：10.1002/chem.201303541

  日期：2014.1.3

  Cyclometalated iridium complexes are found to be versatile catalysts for the direct reductive amination (DRA) of carbonyls to give primary amines under transfer‐hydrogenation conditions with ammonium formate as both the nitrogen and hydrogen source. These complexes are easy to synthesise and their ligands can be easily tuned. The activity and chemoselectivity of the catalyst towards primary amines

  已发现环金属化铱配合物是通用的催化剂，用于羰基的直接还原胺化（DRA），在转移加氢条件下以甲酸铵作为氮源和氢源生成伯胺。这些复合物易于合成，其配体易于调节。催化剂对伯胺的活性和化学选择性极好，底物与催化剂之比（S / C）为1000是可行的。芳族和脂族伯胺均以高收率获得。此外，对于β-酮醚已经实现了均相催化的转移加氢DRA的第一个实例，从而产生了相应的β-氨基醚。此外，通过这种方法还可以以极高的收率获得非天然α-氨基酸。
• K₂S₂O₈ activation by glucose at room temperature for the synthesis and functionalization of heterocycles in water
  作者：Joydev K. Laha、Mandeep Kaur Hunjan

  DOI：10.1039/d1cc03777c

  日期：——

  sulfate radical anion, the utilization of this protocol in organic synthesis is rarely demonstrated. We reinvestigated selected K2S2O8-mediated known organic reactions that invariably require higher temperatures and an organic solvent. A diverse, mild functionalization and synthesis of heterocycles using the inexpensive oxidant K2S2O8 in water at room temperature is reported, demonstrating the sustainability

  虽然在室温下使用葡萄糖进行过硫酸盐活化主要集中在硫酸根阴离子的动力学研究上，但很少证明该协议在有机合成中的应用。我们重新研究了选定的 K 2 S 2 O 8介导的已知有机反应，这些反应总是需要更高的温度和有机溶剂。据报道，在室温下，使用廉价的氧化剂 K 2 S 2 O 8在水中对杂环进行了多样化、温和的功能化和合成，证明了该方法的可持续性和广泛的范围。与用于过硫酸盐活化的传统方法不同，当前方法使用天然丰富的葡萄糖作为 K 2S 2 O 8活化剂，避免使用高温、紫外线、过渡金属或碱。
• Iron-Facilitated Oxidative Radical Decarboxylative Cross-Coupling between α-Oxocarboxylic Acids and Acrylic Acids: An Approach to α,β-Unsaturated Carbonyls
  作者：Qing Jiang、Jing Jia、Bin Xu、An Zhao、Can-Cheng Guo

  DOI：10.1021/acs.joc.5b00267

  日期：2015.4.3

  The first Fe-facilitated decarboxylative cross-coupling reaction between α-oxocarboxylic acids and acrylic acids in aqueous solution has been developed. This transformation is characterized by its wide substrate scope and good functional group compatibility utilizing inexpensive and easily accessible reagents, thus providing an efficient and expeditious approach to an important class of α,β-unsaturated

  已经开发出水溶液中α-氧代羧酸与丙烯酸之间的第一个铁促进的脱羧交叉偶联反应。该转化的特征在于其底物范围宽和使用廉价且易于获得的试剂的良好官能团相容性，从而为生物活性化合物中常见的重要一类α，β-不饱和羰基化合物提供了一种有效而快捷的方法。在随后的官能化反应中也证明了偶联产物的合成潜力。初步的机理研究表明，该过程涉及自由基途径：
• Asymmetric Organocatalytic Direct Aldol Reactions of Ketones with α-Keto Acids and Their Application to the Synthesis of 2-Hydroxy-γ-butyrolactones
  作者：Xiao-Ying Xu、Zhuo Tang、Yan-Zhao Wang、Shi-Wei Luo、Lin-Feng Cun、Liu-Zhu Gong

  DOI：10.1021/jo701868t

  日期：2007.12.1

  of organocatalysts for the asymmetric direct aldol reactions of ketones with α-keto acids were designed on the basis of molecular recognition and prepared from proline and aminopyridines. The organic molecule 8e, derived from proline and 6-methyl-2-amino pyridine, was the best catalyst, affording excellent enantioselectivities (up to 98% ee) for the direct aldol reactions of acetone or 2-butanone with

  在分子识别的基础上，设计了多种有机催化剂，用于酮与α-酮酸的不对称直接羟醛直接反应，并由脯氨酸和氨基吡啶制备。有机分子8e衍生自脯氨酸和6-甲基-2-氨基吡啶的最佳催化剂，对丙酮或2-丁酮与各种α-酮酸和用于各种无环脂族酮与3-（2-硝基苯基）-2-氧代丙酸的反应。通过非对映选择性还原和内酯化的反应序列可以将羟醛加成物转化为2-羟基-γ-丁内酯。对过渡态的实验和理论研究表明，有机催化剂的酰胺N和吡啶N分别与α-酮酸的酮氧基和羧酸羟基选择性地形成氢键。这两个氢键相互作用对于直接不对称羟醛缩合的反应性和对映选择性很重要。

表征谱图