4-溴吡啶-2-甲酸甲酯 | 29681-42-3

• 物质功能分类: 医药中间体 - 吡啶类化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 中文名称: 4-溴吡啶-2-甲酸甲酯
• 中文别名: 4-溴吡啶甲酸甲酯；甲基4-溴吡啶-2-甲酸酯；2-甲酸甲酯-4-溴吡啶
• 英文名称: methyl 4-bromopyridine-2-carboxylate
• 英文别名: methyl 4-bromopicolinate；4-bromopyridine-2-carboxylic acid methyl ester
• CAS: 29681-42-3
• 化学式: C₇H₆BrNO₂
• mdl: MFCD07374897
• 分子量: 216.034
• InChiKey: JZFLATQBIPILFS-UHFFFAOYSA-N

物化性质

• 熔点：
  54-56
• 沸点：
  286.0±20.0 °C(Predicted)
• 密度：
  1.579±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.142
• 拓扑面积：
  39.2
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 危险等级：
  IRRITANT
• 危险品标志：
  Xi
• 安全说明：
  S26
• 危险类别码：
  R36
• 海关编码：
  2933399090
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  保持冷藏

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: Methyl 4-bromopicolinate
Synonyms: Methyl 4-bromo-2-pyridinecarboxylate

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Section 2. Hazards identification
Harmful by inhalation, in contact with skin, and if swallowed.
H319: Causes serious eye irritation
P305+P351+P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses if present
and easy to do – continue rinsing

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Section 3. Composition/information on ingredients.
Ingredient name: Methyl 4-bromopicolinate
CAS number: 29681-42-3

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Section 4. First aid measures
Skin contact: Immediately wash skin with copious amounts of water for at least 15 minutes while removing
contaminated clothing and shoes. If irritation persists, seek medical attention.
Eye contact: Immediately wash skin with copious amounts of water for at least 15 minutes. Assure adequate
flushing of the eyes by separating the eyelids with fingers. If irritation persists, seek medical
attention.
Inhalation: Remove to fresh air. In severe cases or if symptoms persist, seek medical attention.
Ingestion: Wash out mouth with copious amounts of water for at least 15 minutes. Seek medical attention.

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Section 5. Fire fighting measures
In the event of a fire involving this material, alone or in combination with other materials, use dry
powder or carbon dioxide extinguishers. Protective clothing and self-contained breathing apparatus
should be worn.

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Section 6. Accidental release measures
Personal precautions: Wear suitable personal protective equipment which performs satisfactorily and meets local/state/national
standards.
Respiratory precaution: Wear approved mask/respirator
Hand precaution: Wear suitable gloves/gauntlets
Skin protection: Wear suitable protective clothing
Eye protection: Wear suitable eye protection
Methods for cleaning up: Mix with sand or similar inert absorbent material, sweep up and keep in a tightly closed container
for disposal. See section 12.
Environmental precautions: Do not allow material to enter drains or water courses.

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Section 7. Handling and storage
Handling: This product should be handled only by, or under the close supervision of, those properly qualified
in the handling and use of potentially hazardous chemicals, who should take into account the fire,
health and chemical hazard data given on this sheet.
Storage: Store in closed vessels.

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Section 8. Exposure Controls / Personal protection
Engineering Controls: Use only in a chemical fume hood.
Personal protective equipment: Wear laboratory clothing, chemical-resistant gloves and safety goggles.
General hydiene measures: Wash thoroughly after handling. Wash contaminated clothing before reuse.

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Section 9. Physical and chemical properties
Appearance: Not specified
Boiling point: No data
Melting point: No data
Flash point: No data
Density: No data
Molecular formula: C7H6BrNO2
Molecular weight: 216.0

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Section 10. Stability and reactivity
Conditions to avoid: Heat, flames and sparks.
Materials to avoid: Oxidizing agents.
Possible hazardous combustion products: Carbon monoxide, nitrogen oxides, hydrogen bromide.

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Section 11. Toxicological information
No data.

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Section 12. Ecological information
No data.

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Section 13. Disposal consideration
Arrange disposal as special waste, by licensed disposal company, in consultation with local waste
disposal authority, in accordance with national and regional regulations.

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Section 14. Transportation information
Non-harzardous for air and ground transportation.

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Section 15. Regulatory information
No chemicals in this material are subject to the reporting requirements of SARA Title III, Section
302, or have known CAS numbers that exceed the threshold reporting levels established by SARA
Title III, Section 313.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

合成方法

4-溴吡啶甲酸甲酯的合成步骤如下：

首先，用饱和碳酸氢钠水溶液（2 x 20 mL）洗涤4-溴吡啶的盐酸盐（595 mg，3.06 mmol）在二氯甲烷（20 mL）中的溶液。将水层和有机层分离后，使用无水硫酸镁干燥有机层并过滤。接下来，通过加入更多的二氯甲烷将滤液补充至45 mL，并添加3 mL的水、8.51 g（30.6 mmol）的七水合硫酸铁以及0.95 毫升（9.18 mmol）浓硫酸。

在另一个单独的烧瓶中，丙酮酸甲酯（4.15 mL，46 mmol）在-10°C下用3.5 mL（30.6 mmol，30%水溶液）过氧化氢处理。然后将该溶液加入到二氯甲烷/水混合物中，并于-10°C下剧烈搅拌15分钟。

反应完成后，将反应液用冰水（100 mL）稀释，再用二氯甲烷萃取四次。合并的二氯甲烷层使用无水硫酸镁干燥并过滤除去硫酸镁固体，最后减压蒸馏去除有机溶剂。残留物通过连续柱色谱法（梯度洗脱-10-40% EtOAc/庚烷和0.5%三乙胺，然后用0-20% EtOAc/庚烷和0.5%三乙胺重复）后得到目标化合物4-溴吡啶甲酸甲酯。

反应信息

• 作为反应物：
  描述：

  4-溴吡啶-2-甲酸甲酯 在 lithium hydroxide monohydrate 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 以87%的产率得到4-溴吡啶-2-羧酸
  参考文献：
  名称：

  芳杂环酰胺类化合物及其用途

  摘要：

  本发明提出了芳杂环酰胺类化合物及其用途，具体地，这类化合物可有效抑制ASK1激酶活性，其为式(I)至(III)所示化合物，或者式(I)至(III)所示化合物的互变异构体、立体异构体、水合物、溶剂化物、药学可接受的盐或前药：

  公开号：

  CN113831323A
• 作为产物：
  描述：

  丙酮酸甲酯 、 4-溴吡啶 在 硫酸 、 双氧水 、 iron(II) sulfate 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.25h， 生成 4-溴吡啶-2-甲酸甲酯
  参考文献：
  名称：

  WO2008/57497

  摘要：

  公开号：

文献信息

• Pd-Catalyzed Vinylation of Aryl Halides with Inexpensive Organosilicon Reagents Under Mild Conditions
  作者：Chu-Ting Yang、Jun Han、Jun Liu、Yi Li、Fan Zhang、Hai-Zhu Yu、Sheng Hu、Xiaolin Wang

  DOI：10.1002/chem.201802573

  日期：2018.7.20

  Pd‐catalyzed Hiyama vinylation reaction of non‐activated aryl chlorides and bromides under mild conditions was developed. The use of efficient vinyl donors and electron‐rich sterically hindered phosphine ligands was critical for the success of the reaction. The products of this transformation can be used for Am/Cm separation, an important challenge in nuclear fuel reprocessing. The substituent effect

  在温和条件下开发了钯催化未活化的芳基氯和溴化物的Hiyama乙烯基化反应。有效的乙烯基供体和富含电子的位阻膦配体的使用对于反应成功至关重要。这种转化的产物可用于Am / Cm分离，这是核燃料后处理中的一项重要挑战。还获得了取代基对Am / Cm分离选择性的影响，这可能有助于开发用于分离Am和Cm的新型色谱材料。
• [EN] IMIDAZO[1,2-A]PYRIDINE DERIVATIVES AS HISTONE DEMETHYLASE INHIBITORS<br/>[FR] DÉRIVÉS D'IMIDAZO[1,2-A]PYRIDINE UTILISÉS EN TANT QU'INHIBITEURS D'HISTONE DÉMÉTHYLASE
  申请人：CHRYSALIS INC

  公开号：WO2017214413A1

  公开（公告）日：2017-12-14

  This disclosure relates, inter alia, to compounds that inhibit histone demethylase activity. In particular, the disclosure relates to compounds that inhibit histone lysine demethylase KDM5B, pharmaceutical compositions and methods of use, such as methods of treating cancer using the compounds and pharmaceutical compositions disclosed herein.

  这份披露涉及抑制组蛋白去甲基化酶活性的化合物等内容。具体而言，该披露涉及抑制组蛋白赖氨酸去甲基化酶KDM5B的化合物，药物组合物和使用方法，例如使用本文披露的化合物和药物组合物治疗癌症的方法。
• [EN] MODULATORS OF THE INTEGRATED STRESS PATHWAY<br/>[FR] MODULATEURS DE LA VOIE DE RÉPONSE INTÉGRÉE AU STRESS
  申请人：CALICO LIFE SCIENCES

  公开号：WO2017193063A1

  公开（公告）日：2017-11-09

  Provided herein are compounds, compositions, and methods useful for modulating the integrated stress response (ISR) and for treating related diseases; disorders and conditions.

  本文提供了用于调节综合应激反应（ISR）并治疗相关疾病、疾患和症状的化合物、组合物和方法。
• [EN] ARYL-BIPYRIDINE AMINE DERIVATIVES AS PHOSPHATIDYLINOSITOL PHOSPHATE KINASE INHIBITORS<br/>[FR] DÉRIVÉS D'AMINE ARYL-BIPYRIDINE UTILISÉS EN TANT QU'INHIBITEURS DE LA PHOSPHATIDYLINOSITOL PHOSPHATE KINASE
  申请人：PETRA PHARMA CORP

  公开号：WO2019126733A1

  公开（公告）日：2019-06-27

  The invention relates to inhibitors of PI5P4K inhibitors useful in the treatment of cancers, neurodegenerative diseases, inflammatory disorders, and metabolic diseases, having the Formula (I): wherein A, X, Y, Z, Q, R1, R2, R3, R4, R5, and n are described herein.

  这项发明涉及PI5P4K抑制剂，用于治疗癌症、神经退行性疾病、炎症性疾病和代谢性疾病，其化学式为（I）：其中A、X、Y、Z、Q、R1、R2、R3、R4、R5和n如本文所述。
• [EN] 2-CYANOISOINDOLINE DERIVATIVES FOR TREATING CANCER<br/>[FR] DÉRIVÉS DE 2-CYANOISOINDOLINE POUR LE TRAITEMENT DU CANCER
  申请人：MISSION THERAPEUTICS LTD

  公开号：WO2017158388A1

  公开（公告）日：2017-09-21

  The invention relates to novel compounds of formula I which are inhibitors of deubiquitylating enzymes (DUBs) and/or desumoylating enzymes. In particular, the invention relates to the inhibition of ubiquitin C-terminal hydrolase 7 or ubiquitin specific peptidase 7 (USP7). The invention further relates to methods for the preparation of these compounds and to their use in the treatment of cancer.

  这项发明涉及公式I的新化合物，这些化合物是去泛素化酶（DUBs）和/或去泛素化酶的抑制剂。具体来说，该发明涉及抑制泛素C端水解酶7或泛素特异性肽酶7（USP7）。该发明还涉及这些化合物的制备方法以及它们在癌症治疗中的应用。

表征谱图