5-溴-2-乙氧基砒啶-4-硼酸 | 612845-46-2

• 物质功能分类: 医药中间体 - 杂环化合物 - 吡啶类化合物
• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 5-溴-2-乙氧基砒啶-4-硼酸
• 中文别名: 5-溴-2-乙氧基吡啶-4-硼酸
• 英文名称: 3-bromo-6-ethoxy-4-pyridylboronic acid
• 英文别名: 5-Bromo-2-ethoxypyridine-4-boronic acid；(5-bromo-2-ethoxypyridin-4-yl)boronic acid
• CAS: 612845-46-2
• 化学式: C₇H₉BBrNO₃
• 分子量: 245.868
• InChiKey: RLPXRCAGOQMYBN-UHFFFAOYSA-N

物化性质

• 熔点：
  103-105 °C
• 沸点：
  374.8±52.0 °C(Predicted)
• 密度：
  1.61±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.08
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  62.6
• 氢给体数：
  2
• 氢受体数：
  4

安全信息

• 海关编码：
  2933399090
• 危险性防范说明：
  P261,P264,P271,P280,P302+P352,P304+P340+P312,P305+P351+P338,P332+P313,P337+P313,P362,P403+P233,P405,P501
• 危险性描述：
  H315,H319,H335

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
5-Bromo-2-ethoxypyridine-4-boronic acid
Product Name:
Synonyms: 5-Bromo-2-ethoxypyridin-4-ylboronic acid; 5-Bromo-2-ethoxy-4-pyridineboronic acid

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Section 2. Hazards identification
Harmful by inhalation, in contact with skin, and if swallowed.
H315: Causes skin irritation
H319: Causes serious eye irritation
H335: May cause respiratory irritation
P261: Avoid breathing dust/fume/gas/mist/vapours/spray
Wear protective gloves/protective clothing/eye protection/face protection
P280:
P305+P351+P338: IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses if present
and easy to do – continue rinsing
P304+P340: IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing
P405: Store locked up

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Section 3. Composition/information on ingredients.
5-Bromo-2-ethoxypyridine-4-boronic acid
Ingredient name:
CAS number: 612845-46-2

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Section 4. First aid measures
Immediately wash skin with copious amounts of water for at least 15 minutes while removing
Skin contact:
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.
Wash out mouth with copious amounts of water for at least 15 minutes. Seek medical attention.
Ingestion:

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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.
Store in closed vessels, under −20◦C.
Storage:

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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
Not specified
Appearance:
Boiling point: No data
Melting point: No data
Flash point: No data
Density: No data
Molecular formula: C7H9BBrNO3
Molecular weight: 245.9

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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

5-溴-2-乙氧基砒啶-4-硼酸是一种有机中间体，主要用于Suzuki等偶联反应，在实验室研发和化工医药合成过程中发挥重要作用。

制备方法如下： 在-78℃下，将5-溴-2-甲氧基吡啶（9）（727mg，3.9mmol）溶解于无水THF（10mL）中，并滴加入LDA（2.0M的庚烷-THF-乙苯溶液，2.0mL，4.0mmol）。将反应混合物在-78℃下搅拌1小时后，再滴加TIPB（1.5g，7.8mmol），继续搅拌1小时。随后用10mL的H2O淬灭，并使其温热至20℃过夜。对反应液进行处理：水层使用48％HBr水溶液酸化至pH 4以沉淀，最终得到产物3-溴-6-甲氧基-4-吡啶基硼酸。

5-溴-2-乙氧基砒啶-4-硼酸的合成参照上述方法。原料包括： 5-溴-2-乙氧基吡啶（10）（261mg，1.3mmol），THF（10mL）和LDA（2.0M庚烷-THF-乙苯溶液，0.8mL，1.5mmol）。产物为白色固体，产率为74mg，约23％。

反应信息

• 作为反应物：
  描述：

  2-溴-5-硝基噻吩 、 5-溴-2-乙氧基砒啶-4-硼酸 在 bis-triphenylphosphine-palladium(II) chloride caesium carbonate 作用下， 以 1,4-二氧六环 为溶剂， 反应 59.0h， 以44%的产率得到3-bromo-4-(5-nitro-2-thienyl)-6-ethoxypyridine
  参考文献：
  名称：

  New Shelf-Stable Halo- and Alkoxy-SubstitutedPyridylboronic Acids and their Suzuki Cross-Coupling Reactions toYield Heteroarylpyridines

  摘要：

  新合成的稳定的吡啶硼酸具有以下特点：溴锂交换反应随后与三异丙基硼酸酯（TIPB）反应，生成了2-氟-5-吡啶硼酸（4）、3-溴-5-吡啶硼酸（5）和2-乙氧基-5-吡啶硼酸（6）；导向锂化反应后与三甲基硼酸酯（TMB）或TIPB反应，得到了2-甲氧基-3-吡啶硼酸（8）、3-溴-6-甲氧基-4-吡啶硼酸（11）和3-溴-6-乙氧基-4-吡啶硼酸（12）。将吡啶硼酸4、6、8和11与3-溴喹啉进行交叉偶联反应（[Cs2CO3, Pd(PPh3)2Cl2, 1,4-二氧烷, 95 °C]），得到吡啶基喹啉衍生物13和15-17，产率为50-77%；5的类似反应由于产物14的进一步原位反应，产率较低。将12与2-溴-5-硝基噻吩进行交叉偶联，得到3-溴-4-(5-硝基-2-噻吩基)-6-乙氧基吡啶（18）。

  DOI：

  10.1055/s-2003-39158
• 作为产物：
  描述：

  5-溴-2-乙氧基吡啶 在 lithium diisopropyl amide 、 硼酸三异丙酯 作用下， 以 四氢呋喃 、 正庚烷 、 乙基苯 为溶剂， 反应 2.0h， 以23%的产率得到5-溴-2-乙氧基砒啶-4-硼酸
  参考文献：
  名称：

  New Shelf-Stable Halo- and Alkoxy-SubstitutedPyridylboronic Acids and their Suzuki Cross-Coupling Reactions toYield Heteroarylpyridines

  摘要：

  新合成的稳定的吡啶硼酸具有以下特点：溴锂交换反应随后与三异丙基硼酸酯（TIPB）反应，生成了2-氟-5-吡啶硼酸（4）、3-溴-5-吡啶硼酸（5）和2-乙氧基-5-吡啶硼酸（6）；导向锂化反应后与三甲基硼酸酯（TMB）或TIPB反应，得到了2-甲氧基-3-吡啶硼酸（8）、3-溴-6-甲氧基-4-吡啶硼酸（11）和3-溴-6-乙氧基-4-吡啶硼酸（12）。将吡啶硼酸4、6、8和11与3-溴喹啉进行交叉偶联反应（[Cs2CO3, Pd(PPh3)2Cl2, 1,4-二氧烷, 95 °C]），得到吡啶基喹啉衍生物13和15-17，产率为50-77%；5的类似反应由于产物14的进一步原位反应，产率较低。将12与2-溴-5-硝基噻吩进行交叉偶联，得到3-溴-4-(5-硝基-2-噻吩基)-6-乙氧基吡啶（18）。

  DOI：

  10.1055/s-2003-39158

文献信息

• New Shelf-Stable Halo- and Alkoxy-SubstitutedPyridylboronic Acids and their Suzuki Cross-Coupling Reactions toYield Heteroarylpyridines
  作者：Martin R. Bryce、Paul R. Parry、Brian Tarbit

  DOI：10.1055/s-2003-39158

  日期：——

  New shelf-stable pyridylboronic acids have been synthesized: bromine-lithium exchange followed by reaction with triisopropylborate (TIPB) yielded 2-fluoro-5-pyridylboronic acid (4), 3-bromo-5-pyridylboronic acid (5) and 2-ethoxy-5-pyridylboronic acid (6); directed lithiation followed by reaction with trimethylborate (TMB) or TIPB afforded 2-methoxy-3-pyridylboronic acid (8), 3-bromo-6-methoxy-4-pyridylboronic acid (11) and 3-bromo-6-ethoxy-4-pyridylboronic acid (12). Cross-coupling of pyridylboronic acids 4, 6, 8, and 11 with 3-bromoquinoline [Cs2CO3, Pd(PPh3)2Cl2, 1,4-dioxane, 95 °C] gave pyridinylquinoline derivatives 13, 15-17 in 50-77% yields: the analogous reaction of 5 was low yielding due to further in situ reactions of the product 14. Cross-coupling of 12 with 2-bromo-5-nitrothiophene gave 3-bromo-4-(5-nitro-2-thienyl)-6-ethoxypyridine (18).

  新合成的稳定的吡啶硼酸具有以下特点：溴锂交换反应随后与三异丙基硼酸酯（TIPB）反应，生成了2-氟-5-吡啶硼酸（4）、3-溴-5-吡啶硼酸（5）和2-乙氧基-5-吡啶硼酸（6）；导向锂化反应后与三甲基硼酸酯（TMB）或TIPB反应，得到了2-甲氧基-3-吡啶硼酸（8）、3-溴-6-甲氧基-4-吡啶硼酸（11）和3-溴-6-乙氧基-4-吡啶硼酸（12）。将吡啶硼酸4、6、8和11与3-溴喹啉进行交叉偶联反应（[Cs2CO3, Pd(PPh3)2Cl2, 1,4-二氧烷, 95 °C]），得到吡啶基喹啉衍生物13和15-17，产率为50-77%；5的类似反应由于产物14的进一步原位反应，产率较低。将12与2-溴-5-硝基噻吩进行交叉偶联，得到3-溴-4-(5-硝基-2-噻吩基)-6-乙氧基吡啶（18）。