丁-1-烯-4-硼酸频哪醇酯 | 331958-92-0

• 物质功能分类: 化学试剂 - 有机试剂 - 酯类
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 中文名称: 丁-1-烯-4-硼酸频哪醇酯
• 英文名称: 2-(but-3-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: 2-(but-3-enyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；2-(3-buten-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；2-but-3-enyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 331958-92-0
• 化学式: C₁₀H₁₉BO₂
• mdl: MFCD11858602
• 分子量: 182.071
• InChiKey: RGCTUSLNTQXCHW-UHFFFAOYSA-N

物化性质

• 沸点：
  193.1±19.0 °C(Predicted)
• 密度：
  0.88±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.22
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2931900090
• 危险性防范说明：
  P501,P210,P280,P370+P378,P403+P235
• 危险性描述：
  H302,H227
• 储存条件：
  室温且干燥

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: But-1-ene-4-boronic acid pinacol ester
Synonyms:

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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: But-1-ene-4-boronic acid pinacol ester
CAS number: 331958-92-0

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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, 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
Appearance: Not specified
Boiling point: No data
No data
Melting point:
Flash point: No data
Density: No data
Molecular formula: C10H19BO2
Molecular weight: 182.1

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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.

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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：

  丁-1-烯-4-硼酸频哪醇酯 在 Ni(dppp)Br₂ 、 二苯基膦 、 zinc(II) iodide 、 锌 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以80%的产率得到顺式-2-丁烯-1-硼酸频那醇酯
  参考文献：
  名称：

  Double-Bond Isomerization: Highly Reactive Nickel Catalyst Applied in the Synthesis of the Pheromone (9Z,12Z)-Tetradeca-9,12-dienyl Acetate

  摘要：

  A highly reactive nickel catalyst comprising NiCl2(dppp) or NiCl2(dppe) with zinc powder, ZnI2 and Ph2PH, was applied in the isomerization of terminal alkenes to Z-2-alkenes. The double-bond geometry of the 2-alkene can be controlled via the reaction temperature to yield the 2-Z-alkenes in excellent yields and high Z-selectivities. The formation of other constitutional isomers, such as 3-alkenes, is suppressed on the basis of the proposed mechanism via a 1,2-hydride shift from the metal to the Ph2P ligand. The nickel-catalyzed isomerization reaction was then applied in the synthesis of (9Z,12Z)-tetradeca-9,12-dienyl acetate, a pheromone with a 2Z,5Z-diene subunit.

  DOI：

  10.1021/acs.orglett.5b01230
• 作为产物：
  描述：

  2-(cyclopropylmethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 hydrocynnamaldehyde 、 BCl₃ 、 C₆H₅BCl₂ 作用下， 以 氘代氯仿 为溶剂， 生成 丁-1-烯-4-硼酸频哪醇酯
  参考文献：
  名称：

  Homoallylboration and Homocrotylboration of Aldehydes

  摘要：

  A simple method for addition of homoallylic fragments to aldehydes is described. Cydopropanated allylboration reagents react with aldehydes in the presence of PhBCl2 to give high yields of bishomoallyl alcohols. Cyclopropanated cis- and trans-crotyl reagents afford the corresponding 1,3-anti- and 1,3-syn-methyl-substituted "homocrotylated" alcohols with high selectivity, consistent with a Zimmerman-Traxler transition state. Accordingly, the optically active alpha-substituted reactant affords the E-substituted product in 97:3 er.

  DOI：

  10.1021/ja2048682

文献信息

• Transition metal- and light-free radical borylation of alkyl bromides and iodides using silane
  作者：Beiqi Sun、Sihan Zheng、Fanyang Mo

  DOI：10.1039/d1cc02134f

  日期：——

  for borylation of alkyl bromides and iodides to alkyl boronic esters under transition metal- and light-free conditions. A series of substrates with a wide range of functional groups were effectively transformed into the borylation products in moderate to good yields. Mechanistic studies, including radical clock experiments and DFT calculations, gave detailed insight into the radical borylation process

  我们报告了在无过渡金属和无光条件下将烷基溴和碘化物硼化为烷基硼酸酯的操作简单和中性的条件。一系列具有广泛功能基团的底物以中等到良好的产率有效地转化为硼酸酯化产物。包括自由基时钟实验和DFT计算在内的机理研究，使人们对自由基硼化过程有了更深入的了解。
• Photoinduced decarboxylative borylation of carboxylic acids
  作者：Alexander Fawcett、Johan Pradeilles、Yahui Wang、Tatsuya Mutsuga、Eddie L. Myers、Varinder K. Aggarwal

  DOI：10.1126/science.aan3679

  日期：2017.7.21

  283 Light facilitates the replacement of carboxylic acids with boron esters in the absence of metal catalysts. The conversion of widely available carboxylic acids into versatile boronic esters would be highly enabling for synthesis. We found that this transformation can be effected by illuminating the N-hydroxyphthalimide ester derivative of the carboxylic acid under visible light at room temperature

  照亮碳硼化的道路 硼取代基提供了多种反应性，并且它们的效用已经出现在制药领域。福西特等人。表明可见光可以诱导硼酸酯取代羧酸基团，这将有助于将它们引入各种化合物中。一旦酸被邻苯二甲酰亚胺取代基活化，它们就可以在酰胺溶剂中在光照下与儿茶酚硼烷二聚体反应，无需催化剂或其他添加剂。该反应似乎通过光引发后的自由基链增长进行。科学，这个问题 p。283 Light 有助于在没有金属催化剂的情况下用硼酯替代羧酸。将广泛可用的羧酸转化为多功能硼酸酯将非常有助于合成。我们发现，在二硼试剂双（儿茶酚）二硼存在下，在室温下，在可见光下照射羧酸的 N-羟基邻苯二甲酰亚胺酯衍生物，可以实现这种转化。简单的后处理可以分离频哪醇硼酸酯。实验证据表明，硼基自由基中间体参与了该过程。该方法通过伯、仲和叔烷基羧酸以及各种天然产物羧酸的转化来说明，从而证明其广泛的实用性和官能团耐受性。
• Manganese-Catalyzed Borylation of Unactivated Alkyl Chlorides
  作者：Thomas C. Atack、Silas P. Cook

  DOI：10.1021/jacs.6b03157

  日期：2016.5.18

  of (bis)pinacolatodiboron with a wide range of alkyl halides, demonstrating the first manganese-catalyzed coupling with alkyl electrophiles. This method allows access to primary, secondary, and tertiary boronic esters from the parent chlorides, which were previously inaccessible as coupling partners. The reaction proceeds in high yield with as little as 1000 ppm catalyst loading, while 5 mol % can

  使用低成本的溴化锰 (MnBr2) 和四甲基乙二胺 (TMEDA) 催化（双）频哪醇二硼与多种烷基卤化物的交叉偶联，证​​明了锰催化与烷基亲电试剂的首次偶联。该方法允许从母体氯化物中获得伯、仲和叔硼酸酯，这些以前作为偶联伙伴是无法获得的。该反应以低至 1000 ppm 的催化剂负载量以高产率进行，而 5 mol% 可在短短 30 分钟内提供高产率。最后，自由基时钟实验表明，在 0 °C 时，直接硼酸化作用胜过其他自由基过程，从而提供合成有用的、温度控制的反应结果。
• Efficient synthesis of alkylboronic esters <i>via</i> magnetically recoverable copper nanoparticle-catalyzed borylation of alkyl chlorides and bromides
  作者：Mahadev L. Shegavi、Abhishek Agarwal、Shubhankar Kumar Bose

  DOI：10.1039/d0gc00677g

  日期：——

  report a magnetically separable Cu nanocatalyst (Fe-DOPA-Cu) for the borylation of alkyl halides with alkoxy diboron reagents, providing alkylboronic esters in high yields, with broad functional group tolerance under mild reaction conditions. The procedure is also applicable to the borylation of benzyl chlorides and bromides. Radical clock experiments support a radical-mediated process. Easy recycling of

  我们报告了一种可磁分离的铜纳米催化剂（Fe-DOPA-Cu），用于烷基卤化物与烷氧基二硼试剂的硼酸酯化，可提供高产率的烷基硼酸酯，在温和的反应条件下具有宽泛的官能团耐受性。该方法也适用于苄基氯和溴化物的硼化。激进的时钟实验支持激进介导的过程。催化剂易于循环使用，最多十次运行不会造成活性显着下降。
• Highly Efficient Synthesis of Alkylboronate Esters via Cu(II)-Catalyzed Borylation of Unactivated Alkyl Bromides and Chlorides in Air
  作者：Shubhankar Kumar Bose、Simon Brand、Helen Oluwatola Omoregie、Martin Haehnel、Jonathan Maier、Gerhard Bringmann、Todd B. Marder

  DOI：10.1021/acscatal.6b02918

  日期：2016.12.2

  A copper(II)-catalyzed borylation of alkyl halides with bis(pinacolato)diboron (B2pin2) has been developed, which can be carried out in air, providing a wide range of primary, secondary, and some tertiary alkylboronates in high yields. A variety of functional groups are tolerated and the protocol is also applicable to unactivated alkyl chlorides (including 1,1- and 1,2-dichlorides). Preliminary mechanistic

  已经开发出了铜（II）催化的卤化烷基卤与双（频哪醇）二硼化硼（B 2 pin 2），该反应可以在空气中进行，从而提供高范围的伯，仲和某些叔烷基硼酸酯。产量。可以耐受多种官能团，该方案也适用于未活化的烷基氯化物（包括1,1-和1,2-二氯化物）。初步的机理研究表明，这种硼化反应涉及单电子过程。