3,5-二氟苯硼酸频那醇酯 | 863868-36-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 3,5-二氟苯硼酸频那醇酯
• 中文别名: 3,5-二氟苯硼酸频呐醇酯
• 英文名称: 2-(3,5-difluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: 3,5-difluorophenylboronic acid pinacol ester
• CAS: 863868-36-4
• 化学式: C₁₂H₁₅BF₂O₂
• 分子量: 240.058
• InChiKey: NBMGRDOMOTUSOT-UHFFFAOYSA-N

物化性质

• 熔点：
  49.0 to 53.0 °C
• 沸点：
  285.6±30.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)
• 溶解度：
  溶于甲醇

计算性质

• 辛醇/水分配系数(LogP)：
  2.26
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

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

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: 3,5-Difluorophenylboronic acid, pinacol ester
Synonyms: 2-(3,5-Difluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

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Section 2. Hazards identification
Harmful by inhalation, in contact with skin, and if swallowed.

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Section 3. Composition/information on ingredients.
Ingredient name: 3,5-Difluorophenylboronic acid, pinacol ester
CAS number: 863868-36-4

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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.
Store in closed vessels.
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
Appearance: Not specified
Boiling point: No data
No data
Melting point:
Flash point: No data
Density: No data
Molecular formula: C12H15BF2O2
Molecular weight: 240.1

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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, hydrogen fluoride.

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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：

  3,5-二氟苯硼酸频那醇酯 在 gold(III) chloride 、 N-溴代丁二酰亚胺(NBS) 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 24.0h， 以84%的产率得到2-(2-溴-3,5-二氟苯基)-4,4,5,5-四甲基-1,3,2-二噁硼烷
  参考文献：
  名称：

  金（III）芳香族硼酸酯的催化的卤化与Ñ -Halosuccinimides

  摘要：

  芳环上带有卤素取代基的芳族硼酸酯可通过AuCl 3催化的N-卤代琥珀酰亚胺的卤化反应合成。

  DOI：

  10.1021/ol102350v
• 作为产物：
  描述：

  3,5-二氟苯甲酸 在 4-二甲氨基吡啶 、 4-(叔丁氧羰基)吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran 为溶剂， 反应 17.0h， 生成 3,5-二氟苯硼酸频那醇酯
  参考文献：
  名称：

  N-羟基邻苯二甲酰亚胺酯对异烟酸酯的催化（杂）芳基和烯基羧酸的脱羧硼化反应

  摘要：

  芳基和链烯基羧酸与双（频哪醇合）二硼的脱羧硼化通过实现Ñ使用-hydroxyphthalimide酯叔异烟酸丁酯在无碱条件下作为催化剂。可以将具有不同官能团和电子特性的各种芳基羧酸平稳地转化为芳基硼酸酯，包括在过渡金属催化下难以脱羧的芳基硼酸酯，从而提供了一种新方法，使羧酸可以用作有机合成中的基础。机理分析表明，该反应通过自由基脱羧产生的瞬态芳基与吡啶稳定的持久性硼基的偶联而进行。氧化还原活性酯的活化可以通过分子内单电子转移（SET）过程，通过吡啶-二硼-邻苯二甲酰亚胺加合物进行，并说明了无碱反应条件。

  DOI：

  10.1021/acs.orglett.7b01950

文献信息

• Synthesis of Pinacol Arylboronates from Aromatic Amines: A Metal-Free Transformation
  作者：Di Qiu、Liang Jin、Zhitong Zheng、He Meng、Fanyang Mo、Xi Wang、Yan Zhang、Jianbo Wang

  DOI：10.1021/jo3018878

  日期：2013.3.1

  A metal-free borylation process based on Sandmeyer-type transformation using arylamines derivatives as the substrates has been developed. Through optimization of the reaction conditions, this novel conversion can be successfully applied to a wide range of aromatic amines, affording borylation products in moderate to good yields. Various functionalized arylboronates, which are difficult to access by

  基于芳基胺衍生物作为底物的基于Sandmeyer型转化的无金属硼化工艺已得到开发。通过优化反应条件，这种新颖的转化方法可以成功地应用于各种芳族胺，从而以中等至良好的收率获得硼酸酯化产物。通过这种无金属的转化，可以容易地获得各种难以通过其他方法获得的官能化的芳基硼酸酯。此外，在不纯化硼酸酯化产物的情况下，Suzuki-Miyaura交叉偶联后即可进行这种转化，从而增强了该方法的实用性。已经提出了可能的涉及自由基物质的反应机理。
• Palladium(<scp>ii</scp>)-catalysed ortho-arylation of N-benzylpiperidines
  作者：Peng Wen Tan、Maxwell Haughey、Darren J. Dixon

  DOI：10.1039/c5cc00410a

  日期：——

  Pd(II)-catalysed ortho-arylation of benzylic heterocycles with arylboronic acid pinacol esters (Ar-BPin) via directed C-H bond activation to generate the desired biaryl products is reported. This methodology is efficient and applicable to a wide range of functionalised Ar-BPin and benzylic heterocycles, allowing the direct synthesis of important biaryl motifs in modest to good yield.

  据报道，Pd（II）通过直接的CH键活化反应生成芳基硼酸频哪醇酯（Ar-BPin）来催化苄基杂环的邻芳基化反应，从而生成所需的联芳基产物。这种方法学是有效的，并且适用于各种功能化的Ar-BPin和苄基杂环，从而允许以适度到良好的产率直接合成重要的联芳基。
• Transformations of Aryl Ketones via Ligand‐Promoted C−C Bond Activation
  作者：Hanyuan Li、Biao Ma、Qi‐Sheng Liu、Mei‐Ling Wang、Zhen‐Yu Wang、Hui Xu、Ling‐Jun Li、Xing Wang、Hui‐Xiong Dai

  DOI：10.1002/anie.202006740

  日期：2020.8.17

  The coupling of aromatic electrophiles (aryl halides, aryl ethers, aryl acids, aryl nitriles etc.) with nucleophiles is a core methodology for the synthesis of aryl compounds. Transformations of aryl ketones in an analogous manner via carbon–carbon bond activation could greatly expand the toolbox for the synthesis of aryl compounds due to the abundance of aryl ketones. An exploratory study of this

  芳族亲电试剂（芳基卤化物，芳基醚，芳基酸，芳基腈等）与亲核试剂的偶联是合成芳基化合物的核心方法。由于芳基酮的丰度，通过碳-碳键活化以类似方式进行芳基酮的转化可大大扩展合成芳基化合物的工具箱。这种方法的探索性研究通常基于环应变释放和螯合辅助引发的碳-碳裂解，并且产物也仅限于特定的结构基序。在这里，我们报告了一种配体促进β-碳消除的策略，以激活碳-碳键，这导致芳基酮发生一系列转化，从而生成有用的芳基硼酸酯，以及联芳基，芳基腈和芳基烯烃。吡啶-恶唑啉配体的使用对于这种催化转化至关重要。据报道，通过简单的一锅操作，芳基酮的克级硼酸酯化反应。该策略的潜在效用还通过丙磺舒，阿达帕林和脱氧雌酮，芬芳类香囊素和载脂蛋白的天然产物的晚期药物分子多样化而得到证明。
• Radical Metal-Free Borylation of Aryl Iodides
  作者：Sandra Pinet、Mathieu Pucheault、Virginie Liautard、Mégane Debiais

  DOI：10.1055/s-0036-1588431

  日期：2017.11

  radicals, generated in situ. A simple metal-free borylation of aryl iodides mediated by a fluoride sp2–sp3 diboron adduct is described. The reaction conditions are compatible with various functional groups. Electronic effects of substituents do not affect the borylation while steric hindrance does. The reaction proceeds via a radical mechanism in which pyridine serves to stabilize the boryl radicals, generated

  作为合成中硼化的现代策略特别主题的一部分发布 抽象的 描述了由氟化物sp 2 –sp 3二硼加合物介导的简单的无金属碘化芳基碘化物。反应条件与各种官能团相容。取代基的电子效应不会影响硼酸酯化，而空间位阻会影响硼化。该反应通过自由基机理进行，其中吡啶用于稳定原位产生的硼烷基。 描述了由氟化物sp 2 –sp 3二硼加合物介导的简单的无金属碘化芳基碘化物。反应条件与各种官能团相容。取代基的电子效应不会影响硼酸酯化，而空间位阻会影响硼化。该反应通过自由基机理进行，其中吡啶用于稳定原位产生的硼烷基。
• Cobalt-Catalyzed Regioselective Borylation of Arenes: N-Heterocyclic Silylene as an Electron Donor in the Metal-Mediated Activation of C−H Bonds
  作者：Hailong Ren、Yu-Peng Zhou、Yunping Bai、Chunming Cui、Matthias Driess

  DOI：10.1002/chem.201605937

  日期：2017.4.27

  C−H Borylation of arenes has been a subject of great interest recently because of its atom‐economy and the wide applicability of borylated products in value‐added synthesis. A new bis(silylene)cobalt(II) complex bearing a bis(N‐heterocyclic silylene)‐pyridine pincer ligand (SiNSi) has been synthesized and structurally characterized. It enabled the regioselective catalytic C−H borylation of pyridines

  由于芳烃的原子经济性和硼酸盐化产物在增值合成中的广泛应用，近年来，芳烃的CH硼化已引起人们极大的兴趣。合成了一种新的带有双（N-杂环甲硅烷基）-吡啶钳式配体（SiNSi）的双（甲硅烷基）钴（II）配合物，并对其结构进行了表征。它使吡啶，呋喃和氟化芳烃的区域选择性催化CH硼化成为可能。值得注意的是，与以前已知的催化体系相比，它对氟化芳烃的硼化具有互补的区域选择性，这表明N杂环亚甲硅烷基供体在金属催化的催化应用中具有巨大的潜力。