3-硝基苯硼酸频哪醇酯 | 68716-48-3

• 物质功能分类: 化学试剂 - 有机试剂 - 硼酸酯
• 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-硝基苯硼酸频哪醇酯
• 中文别名: 3-硝基苯硼酸酸频哪醇酯；3-(4,4,5,5-四甲基-1,3,2-二氧硼烷)硝基苯
• 英文名称: 4,4,5,5-tetramethyl-2-(3-nitrophenyl)-1,3,2-dioxaborolane
• 英文别名: 3-nitrophenylboronic acid pinacol ester；4,4,5,5-tetramethyl-2-(3-nitrophenyl)-1,3,2‑dioxaborolane
• CAS: 68716-48-3
• 化学式: C₁₂H₁₆BNO₄
• mdl: MFCD05663879
• 分子量: 249.074
• InChiKey: JWEAFTZTLIGAQU-UHFFFAOYSA-N

物化性质

• 熔点：
  76-80 °C (lit.)
• 沸点：
  351.7±25.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)
• 稳定性/保质期：
  常温常压下稳定，应远离氧化剂。

计算性质

• 辛醇/水分配系数(LogP)：
  3.85
• 重原子数：
  18
• 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：
  64.3
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• TSCA：
  No
• 危险品标志：
  Xi
• 安全说明：
  S26,S36/37
• 危险类别码：
  R36/37/38
• WGK Germany：
  2
• 海关编码：
  2934999090
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H315,H319,H335
• 储存条件：
  存放在密封容器内，并置于阴凉、干燥处。储存位置须远离氧化剂，避免阳光直射，最好在室温下保存。

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: 3-Nitrophenylboronic acid, pinacol ester
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
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: 3-Nitrophenylboronic acid, pinacol ester
CAS number: 68716-48-3

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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.
Immediately wash skin with copious amounts of water for at least 15 minutes. Assure adequate
Eye contact:
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
No data
Boiling point:
Melting point: No data
Flash point: No data
Density: No data
Molecular formula: C12H16BNO4
Molecular weight: 249.1

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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, nitrogen oxides.

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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

用途

3-硝基苯硼酸频哪醇酯可用作医药合成中间体。

制备

3-硝基苯硼酸频哪醇酯的制备如下：在氩气保护下的干燥管式反应器中，将1毫摩尔3-硝基苯重氮四氟硼酸盐和10微摩尔（1.8毫克）二茂铁溶解于2毫升无水乙腈中。然后向该溶液中加入2毫摩尔（226毫克）二异丙基氨基硼烷，并在室温下搅拌2小时30分钟。通过在0℃下缓慢滴加2毫升无水甲醇淬灭反应混合物并在室温下再搅拌1小时。除去所有挥发性物质后，在2毫升乙醚中加入1.3当量的频哪醇，将混合物在室温下搅拌4小时。随后用50克/升氯化铜溶液（2×5毫升）洗涤粗产物，并分出有机层、用无水硫酸钠干燥，过滤并浓缩至干。所得油状物溶解于二氯甲烷中并通过硅胶垫过滤，以二氯甲烷洗脱，最终得到相应的硼酸酯3-硝基苯硼酸频哪醇酯。

反应信息

• 作为反应物：
  描述：

  3-硝基苯硼酸频哪醇酯 在 copper(I) oxide 、 1,10-菲罗啉 、 potassium iodide 作用下， 以 甲醇 、 水 为溶剂， 反应 1.0h， 以87%的产率得到1-碘-3-硝基苯
  参考文献：
  名称：

  通过铱催化的C–H硼化作用对芳烃进行立体控制的碘化

  摘要：

  报道了一种通过连续的C–H硼化和碘化制备芳基和杂芳基碘化物的温和方法。该过程的区域选择性由C–H硼化步骤中的空间效应控制，是对现有形成芳基碘化物的方法的补充。硼酸酯的碘化具有放射性标记的芳基碘化物的合成潜力，正如SPECT成像的潜在示踪剂的简明合成所证明的那样。

  DOI：

  10.1021/ol303164h
• 作为产物：
  描述：

  间硝基苯酚 在 硫酰氟 、 sodium acetate 、 二异丙胺 、 palladium dichloride 、 2-二环己基磷-2,4,6-三异丙基联苯 作用下， 以 二氯甲烷 、 异丙醇 为溶剂， 反应 16.0h， 生成 3-硝基苯硼酸频哪醇酯
  参考文献：
  名称：

  使用硫酰氟活化对苯酚进行硼基化

  摘要：

  硼酸酯作为有机合成中的关键原材料和中心中间体的应用越来越广泛。从高度丰富且可再生的原料中合成它们仍然很有趣。在这里，我们报告了一种从苯酚合成芳基/杂芳基硼酸酯的有效且一锅法。在该方法中，苯酚首先被硫酰氟活化形成芳基氟磺酸盐，然后与双(频哪醇)二硼发生钯催化的脱氧硼化反应，得到一系列硼酸酯。该方法表现出优异的官能团耐受性，适用于天然产物和现有药物分子的合成。此外，该方案还适用于生物质衍生的酚类的硼化，包括天然存在的和生物活性的化合物。尤其，小鼠乳腺癌细胞中的2 O 2 。

  DOI：

  10.1039/d3gc01923c

文献信息

• Additive- and Photocatalyst-Free Borylation of Arylazo Sulfones under Visible Light
  作者：Yuliang Xu、Xinying Yang、Hao Fang

  DOI：10.1021/acs.joc.8b01662

  日期：2018.10.19

  developed a photocatalyst-free and additive-free, visible light induced borylation reaction using arylazo sulfones as starting material. This protocol shows some advantages such as mild conditions, simple equipment, and wide substrate scope, which gives a complementary protocol for the preparation of arylboronates.

  我们开发了一种以芳基偶氮砜为起始原料的无光催化剂和无添加剂的可见光诱导的硼酸酯化反应。该方案显示出一些优点，例如温和的条件，简单的设备和广泛的底物范围，为制备芳基硼酸酯提供了补充方案。
• 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。
• Efficient phosphine ligands for the one-pot palladium-catalyzed borylation/Suzuki–Miyaura cross-coupling reaction
  作者：You Chen、Hui Peng、Yun-Xiao Pi、Tong Meng、Ze-Yu Lian、Meng-Qi Yan、Yan Liu、Sheng-Hua Liu、Guang-Ao Yu

  DOI：10.1039/c4ob02436b

  日期：——

  We report the synthesis of 2-(anthracen-9-yl)-1H-inden-3-yl dicyclohexylphosphine and its use in palladium-catalyzed borylation/Suzuki-Miyaura cross-coupling reaction to prepare a variety of symmetrical and unsymmetrical biaryl compounds in excellent yield.

  我们报告了2-（蒽-9-基）-1H-茚满-3-基二环己基膦的合成及其在钯催化的硼化/铃木-宫浦交叉偶联反应中的制备，以制备各种对称和不对称的联芳基化合物。优良的产量。
• Direct Conversion of Arylamines to Pinacol Boronates: A Metal-Free Borylation Process
  作者：Fanyang Mo、Yubo Jiang、Di Qiu、Yan Zhang、Jianbo Wang

  DOI：10.1002/anie.200905824

  日期：2010.3.1

  Leave the metal out: Arylboronates are produced in moderate to good yields by direct borylation of readily available aryl amines (see scheme). The reaction can be carried out under air at room temperature and transition‐metal catalysis is not required. The boronate products can be used without purification in Suzuki–Miyaura cross‐coupling reactions.

  排除金属：芳基硼酸酯是通过将容易获得的芳基胺直接硼化而以中等至良好的产率生产的（参见方案）。该反应可在室温下于空气中进行，不需要过渡金属催化。硼酸酯产物无需纯化即可用于Suzuki-Miyaura交叉偶联反应。
• Cu₂O-Mediated Room Temperature Cyanation of Aryl Boronic Acids/Esters and TMSCN
  作者：Yong Ye、Yanhua Wang、Pengtang Liu、Fushe Han

  DOI：10.1002/cjoc.201200711

  日期：2013.1

  A method for the efficient and reliable synthesis of aryl nitriles via the Cu2O‐catalyed cross‐coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron‐rich and deficient, sterically very congested, and labile functionalities were tolerated. Moreover, the reaction can proceed under mild conditions at room temperature. These advantages paired

  提出了一种通过Cu 2 O催化的芳基硼酸或酯与TMSCN的交叉偶联有效而可靠地合成芳基腈的方法。可以容忍各种各样的基板，这些基板被富电子和不足的电子装饰，空间上非常拥挤，并且功能不稳定。此外，该反应可以在室温下在温和条件下进行。这些优点与廉价，易得且不含卤素的Cu 2 O用作催化剂相结合，使该方案成为芳基氰化反应的诱人选择。