2-溴吡啶-4-硼酸频哪酯 | 458532-82-6

• 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: 2-溴吡啶-4-硼酸频哪酯
• 中文别名: 2-溴吡啶-4-硼酸频那醇酯
• 英文名称: 2-bromo-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine
• 英文别名: 2-[4-(2-bromo)pyridine]-4,4,5,5-tetramethyl-1,3-dioxaborolane
• CAS: 458532-82-6
• 化学式: C₁₁H₁₅BBrNO₂
• 分子量: 283.961
• InChiKey: NQVRUHXWNFMWQB-UHFFFAOYSA-N

物化性质

• 熔点：
  80-83°C
• 沸点：
  354.7±27.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)
• 稳定性/保质期：

  按规定使用和贮存不会分解，也不会与氧化物反应。

计算性质

• 辛醇/水分配系数(LogP)：
  2.14
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  31.4
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2934999090
• 危险性防范说明：
  P261,P280,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H332,H335

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
2-Bromopyridine-4-boronic acid, pinacol ester
Product Name:
Synonyms:

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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.
2-Bromopyridine-4-boronic acid, pinacol ester
Ingredient name:
CAS number: 458532-82-6

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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: C11H15BBrNO2
Molecular weight: 284.0

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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

反应信息

• 作为反应物：
  描述：

  2-溴吡啶-4-硼酸频哪酯 在 正丁基锂 、 1,1'-双(二苯膦基)二茂铁二氯化钯(II)二氯甲烷复合物 、 caesium carbonate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.0h， 生成 (4-(p-tolyl)pyridin-2-yl)(3,4,5-trimethoxyphenyl)methanol
  参考文献：
  名称：

  新型6-芳基-2-苯甲酰基-吡啶类具有微弱抗增殖特性的微管蛋白聚合抑制剂的结构-活性关系研究。

  摘要：

  我们最近报道了微管蛋白的晶体结构与秋水仙碱结合位点抑制剂（CBSI），ABI-231，具有2-芳基-4-苯甲酰基-咪唑（ABI）的复合物。基于此和其他晶体结构，在此我们报道了一系列新颖的ABI-231吡啶类似物的结构-活性关系研究，其中化合物4v对一组癌细胞最有效（平均IC50〜1.8 nM）线。我们确定了另一种有效的CBSI ABI-274和4v与微管蛋白复合的晶体结构，并确认了它们在秋水仙碱位点的直接结合。4v抑制微管蛋白聚合，强烈抑制A375黑色素瘤肿瘤生长，诱导肿瘤坏死，破坏肿瘤血管生成，并导致体内肿瘤细胞凋亡。总的来说，

  DOI：

  10.1021/acs.jmedchem.9b01815
• 作为产物：
  描述：

  2,4-二溴吡啶 、 频哪醇 在 正丁基锂 、 四甲基乙二胺 、 硼酸三异丙酯 、 溶剂黄146 作用下， 以 乙醚 为溶剂， 反应 7.0h， 以66%的产率得到2-溴吡啶-4-硼酸频哪酯
  参考文献：
  名称：

  新型卤代吡啶基硼酸和酯的合成。第3部分：2或3-卤代吡啶-4-基硼酸和酯

  摘要：

  本文描述了用于合成和一般的方法的新的2-，或3-卤代吡啶-4-基硼酸和酯隔离12 - 14，18 - 20。考虑到使用n BuLi进行区域选择性的卤素金属交换或使用LDA进行定向原金属化并随后从适当的单或二卤代吡啶开始用三异丙基硼酸酯淬灭，制备这些化合物。迄今为止研究的所有底物均提供单一的区域异构硼酸或酯产物。另外，已经发现这些化合物与一系列的芳基卤化物进行了Pd催化的偶联，并授权了一种制备新吡啶库的策略。

  DOI：

  10.1016/s0040-4020(02)00416-7

文献信息

• <i>para</i> ‐Selective C−H Borylation of (Hetero)Arenes by Cooperative Iridium/Aluminum Catalysis
  作者：Lichen Yang、Kazuhiko Semba、Yoshiaki Nakao

  DOI：10.1002/anie.201701238

  日期：2017.4.18

  para‐Selective C−H borylation of benzamides and pyridines has been achieved by cooperative iridium/aluminum catalysis. A combination of iridium catalysts commonly employed for arene C−H borylation and bulky aluminum‐based Lewis acid catalysts provides an unprecedented strategy for controlling the regioselectivity of C−H borylation to give variously substituted (hetero)arylboronates, which are versatile

  苯甲酰胺和吡啶的对位C-H硼化已通过铱/铝协同催化实现。芳烃CH硼化中常用的铱催化剂和庞大的铝基路易斯酸催化剂的结合提供了一种空前的策略，可控制CH硼化的区域选择性，从而得到各种取代的（杂）芳基硼酸酯，它们是复杂的多用途合成中间体多取代的芳族化合物。
• Rh^III-Catalyzed Direct Heteroarylation of C(sp³)–H and C(sp²)–H Bonds in Heterocycles with <i>N</i>-Heteroaromatic Boronates
  作者：Huai-Wei Wang、Jia-Xue Wu、Yu-Han Qiao、Yong-Fei Li、Da-Cheng Li、Jian-Min Dou、Qing-Xia Yao、Yi Lu

  DOI：10.1021/acs.orglett.1c02546

  日期：2021.9.17

  Herein, we disclose a RhIII-catalyzed heteroarylation of C(sp3)–H and C(sp2)–H bonds in heterocycles with organoboron reagents. This protocol displays high efficiency and excellent functional group tolerance. A range of heterocyclic boronates with strong coordinating atoms, including pyridine, pyrimidine, pyrazole, thiophene, and furan derivatives, can be extensively served as the coupling reagents

  在此，我们公开了用有机硼试剂使杂环中的 C(sp 3 )-H 和 C(sp 2 )-H 键发生 Rh III催化的杂芳基化反应。该协议显示出高效率和出色的官能团耐受性。一系列具有强配位原子的杂环硼酸酯，包括吡啶、嘧啶、吡唑、噻吩和呋喃衍生物，可广泛用作偶联剂。直接杂芳基化方法可以在合成具有多个杂环的药物分子方面提供潜在的应用。
• The synthesis of aryl-heteroaryl derivatives <i>via</i> the Rh^III-catalyzed heteroarylation of arenes and heteroaromatic boronates
  作者：Huai-Wei Wang、Jia-Xue Wu、Da-Cheng Li、Yu-Han Qiao、Qing-Xia Yao、Wen-Can Sun、Jian-Min Dou

  DOI：10.1039/d1ob02201f

  日期：——

  An efficient RhIII-catalyzed strategy for constructing aryl-heteroaryl derivatives with removable ketoxime ether auxiliaries via direct C–H heteroarylation based on arenes and heteroaromatic boronates has been disclosed. This protocol could tolerate various pyridine, pyrimidine, pyrazole, thiophene, and furan heteroaromatic boronates well, providing the desired products with high reactivities and excellent

  已经公开了一种有效的 Rh III催化策略，用于通过基于芳烃和杂芳族硼酸盐的直接 C-H 杂芳基化构建具有可去除酮肟醚助剂的芳基-杂芳基衍生物。该方案可以很好地耐受各种吡啶、嘧啶、吡唑、噻吩和呋喃杂芳族硼酸盐，提供具有高反应性和优异区域选择性的所需产物。易于合成的可及性可能为合成含有芳基-杂芳基基序的杂环药物分子提供了应用潜力。
• Rh^III-Catalyzed C–H <i>N</i>-Heteroarylation and Esterification Cascade of Carboxylic Acid with Organoboron Reagents and 1,2-Dichloroethane in One-Pot Synthesis
  作者：Huai-Wei Wang、Jia-Xue Wu、Xian-Qiang Huang、Da-Cheng Li、Su-Na Wang、Yi Lu、Jian-Min Dou

  DOI：10.1021/acs.orglett.2c02075

  日期：2022.8.12

  1,2-dichloroethane in a one-pot synthesis has been disclosed. The strong coordinating ability of ortho- and meta-substituted pyridine boronates and pyrazoles as well as unsubstituted pyrimidine allows them to serve as the coupling partners. This protocol allows late-stage modification of the key precursor of roflumilast and compounds of pharmaceutical interest, which highlights the potential application

  已经公开了在一锅合成中芳基羧酸与N-杂芳族硼酸酯和 1,2-二氯乙烷的 Rh III催化的 C(sp 2 )-H N-杂芳基化和酯化级联反应。邻位和间位取代的吡啶硼酸盐和吡唑以及未取代的嘧啶具有很强的配位能力，可以作为偶联配偶体。该协议允许对罗氟司特的关键前体和药物感兴趣的化合物进行后期修改，这突出了这种合成方法的潜在应用。
• One-Pot Construction of Heteroarylation/Esterification Products of Acrylic Acids via Iridium(III)-Catalyzed C–H Activation
  作者：Jia-Xue Wu、Huai-Wei Wang、Wen-Zeng Duan、Hong-Han Ji、Jian-Min Dou、Xian-Qiang Huang、Yi Lu、Da-Cheng Li

  DOI：10.1021/acs.orglett.2c03245

  日期：2022.12.9

  carboxylate-assisted iridium(III)-catalyzed regioselective C(sp2)–H heteroarylation/esterification reaction of acrylic acid is disclosed herein for the first time. This catalytic protocol tolerates various α-substituted, β-substituted, and α, β-disubstituted acrylic acids as well as heteroaromatic boronates well. The resulting 3,4-dihydro-2H-pyran-6-carboxylic acid derivative 3r highlighted the AIE-active luminophore

  本文首次公开了羧酸盐辅助的铱 (III) 催化的区域选择性 C(sp 2 )–H 杂芳基化/酯化反应。该催化方案可以很好地耐受各种 α-取代、β-取代和 α, β-二取代丙烯酸以及杂芳族硼酸酯。由此产生的 3,4-dihydro-2 H -pyran-6-carboxylic acid 衍生物3r突出了具有多重发射信号特性和 28% 的高量子产率的 AIE 活性发光团，展示了该方法在合成含氮有机功能材料。