4-甲基苯硼酸新戊基二醇酯 | 380481-66-3

• 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: 4-甲基苯硼酸新戊基二醇酯
• 中文别名: 4-甲苯硼酸新戊酸酯；4-甲基苯硼酸新戊二醇酯
• 英文名称: 5,5-dimethyl-2-(4-methylphenyl)-1,3,2-dioxaborinane
• 英文别名: 5,5-dimethyl-2-(p-tolyl)-1,3,2-dioxaborinane；4-methylphenylboronic acid neopentyl glycol ester；2-(4-methyl-phenyl)-5,5-dimethyl-[1,3,2]dioxaborinane；p-tolylboronic acid neopentylglycol ester；4-tolylboronic acid neopentyl glycol ester
• CAS: 380481-66-3
• 化学式: C₁₂H₁₇BO₂
• 分子量: 204.077
• InChiKey: ZSPBWRPQSPRISS-UHFFFAOYSA-N

物化性质

• 熔点：
  93-95°C
• 沸点：
  303.0±21.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)
• 稳定性/保质期：
  避氧化物

计算性质

• 辛醇/水分配系数(LogP)：
  1.76
• 重原子数：
  15
• 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：
  2

安全信息

• 海关编码：
  2934999090
• 安全说明：
  S24/25
• 危险性防范说明：
  P261,P264,P270,P271,P280,P301+P312+P330,P302+P352,P304+P340+P312,P305+P351+P338,P332+P313,P337+P313,P362,P403+P233,P405,P501
• 危险性描述：
  H302,H315,H319,H332,H335
• 储存条件：
  保存方法：存放在密闭、阴凉、干燥的地方。

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: 4-Methylphenylboronic acid neopentyl 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: 4-Methylphenylboronic acid neopentyl ester
CAS number: 380481-66-3

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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.
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: C12H17BO2
Molecular weight: 204.1

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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：

  4-甲基苯硼酸新戊基二醇酯 在 sodium tetrachloroaurate(III) dihyrate 、 potassium carbonate 作用下， 以 乙醇 为溶剂， 反应 24.0h， 以70%的产率得到4,4'-二甲基联苯
  参考文献：
  名称：

  简单金盐催化的芳基硼酸的均相偶联

  摘要：

  在催化量的金盐存在下，一定范围的芳基硼酸会发生均偶联反应，从而生成对称的联芳基。烯基硼酸，芳基硼酸酯和芳基硼酸酯也参与金催化的均偶联反应。

  DOI：

  10.1016/j.tetlet.2011.07.030
• 作为产物：
  描述：

  对甲基苯甲酸 在 4-二甲氨基吡啶 、 potassium phosphate 、 nickel(II) acetate tetrahydrate 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 三乙胺 、 1,3-二环己基氯化咪唑 、 sodium t-butanolate 作用下， 以 二氯甲烷 、 环己烷 、 甲苯 为溶剂， 反应 29.0h， 生成 4-甲基苯硼酸新戊基二醇酯
  参考文献：
  名称：

  镍催化酰胺的脱羰基硼化反应：酰基CN键活化的证据

  摘要：

  镍/ N-杂环卡宾催化体系已经建立用于与乙酰胺的decarbonylative硼化2 NEP 2由C-N键的激活。这种转变显示出良好的官能团相容性，可作为复杂化合物中酰胺基团后期硼化的强大合成工具。更重要的是，作为关键中间体，酰基镍配合物的结构首先通过X射线分析得以确认。此外，还观察到脱羰过程。这些发现证实了酰基CN键活化过程的关键机理。

  DOI：

  10.1002/anie.201603068
• 作为试剂：
  描述：

  1-(1Z)-1-hexen-1-yl-4-methylbenzene 在 bis(acetylacetonate)nickel(II) 、 二异丁基氢化铝 、 4-甲基苯硼酸新戊基二醇酯 、 三环己基膦 作用下， 以 正己烷 、 甲苯 为溶剂， 反应 16.0h， 以66%的产率得到1-(1E)-1-hexen-1-yl-4-methylbenzene
  参考文献：
  名称：

  Highly E-Selective, Stereoconvergent Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling of Alkenyl Ethers

  摘要：

  An improved method for the nickel-catalyzed Suzuki-Miyaura cross-coupling of alkenyl ethers is reported. This stereoconvergent protocol allows for the utilization of a wide range of alkenyl ethers and aryl boronic esters for the synthesis of variously substituted styrene derivatives. An olefinic mixture with respect to the alkenyl ethers can be employed, thereby circumventing the stereodefined synthesis of starting materials. Preliminary mechanistic investigations indicate a nickel-catalyzed olefin isomerization following initial stereoretentive cross-coupling.

  DOI：

  10.1021/acs.orglett.9b00946

文献信息

• RuH2(CO)(PPh3)3-catalyzed arylation of aromatic esters using arylboronates via C–H bond cleavages
  作者：Kentaroh Kitazawa、Masashi Kotani、Takuya Kochi、Michael Langeloth、Fumitoshi Kakiuchi

  DOI：10.1016/j.jorganchem.2010.01.022

  日期：2010.4

  The RuH2(CO)(PPh3)3-catalyzed C–H functionalization of aromatic esters with 5,5-dimethyl-2-aryl-[1,3,2]dioxaborinanes (arylboronates) gave the ortho arylation products. This coupling reaction can be performed with various combinations of isopropyl benzoate derivatives and arylboronates. Introduction of CF3 group in the aromatic ring increased the reactivity of the esters. Pinacolone effectively served

  RuH 2（CO）（PPh 3）3催化的芳香族酯与5,5-二甲基-2-芳基-[1,3,2]二氧杂硼烷酮（芳基硼酸酯）的C–H官能化反应得到邻芳基化产物。该偶联反应可以用异丙基苯甲酸酯衍生物和芳基硼​​酸酯的各种组合进行。在芳环中引入CF 3基团增加了酯的反应性。Pinacolone有效地充当了由C–H键断裂产生的氢化物的接受体，并且使用的pinacolone的量也影响了芳基化产物的收率。
• Efficient Synthesis of Aryl Boronates via Zinc-Catalyzed Cross-Coupling of Alkoxy Diboron Reagents with Aryl Halides at Room Temperature
  作者：Shubhankar Kumar Bose、Todd B. Marder

  DOI：10.1021/ol502120q

  日期：2014.9.5

  A zinc(II)/NHC system catalyzes the borylation of aryl halides with diboron (4) reagents in the presence of KOMe at rt. This transformation can be applied to a broad range of substrates with high functional group compatibility. Radical scavenger experiments do not support a radical-mediated process.

  锌（II）/ NHC系统在室温下在KOMe存在下催化芳基卤化物与二硼（4）试剂的硼酸酯化反应。这种转变可应用于具有高官能团相容性的各种基材。自由基清除剂实验不支持自由基介导的过程。
• Synthesis of Quaternary Carbon Stereocenters by Copper-Catalyzed Asymmetric Allylic Substitution of Allyl Phosphates with Arylboronates
  作者：Momotaro Takeda、Keishi Takatsu、Ryo Shintani、Tamio Hayashi

  DOI：10.1021/jo500068p

  日期：2014.3.21

  A copper-catalyzed asymmetric allylic substitution of γ,γ-disubstituted allyl phosphates with arylboronates has been developed for the construction of quaternary stereocenters. High regio- and enantioselectivities have been achieved by employing a hydroxy-bearing chiral N-heterocyclic carbene ligand, and both E and Z substrates provide the same enantiomer as the major product. The mechanistic aspect

  已经开发了用芳基硼酸酯的铜催化的γ，γ-二取代的烯丙基磷酸的不对称烯丙基取代基，用于构建季立体中心。通过使用带有羟基的手性N-杂环卡宾配体已经实现了高区域选择性和对映体选择性，并且E和Z底物均提供与主要产物相同的对映异构体。还已经研究了这种催化作用的机理，以发现1：1的铜/配体络合物最有可能导致当前的不对称催化作用，并且相对于烯丙基亲电试剂，反应以几乎完美的1,3-抗立体化学进行。
• Suzuki–Miyaura Coupling of Simple Ketones via Activation of Unstrained Carbon–Carbon Bonds
  作者：Ying Xia、Jianchun Wang、Guangbin Dong

  DOI：10.1021/jacs.8b02462

  日期：2018.4.25

  Here, we describe that simple ketones can be efficiently employed as electrophiles in Suzuki-Miyaura coupling reactions via catalytic activation of unstrained C-C bonds. A range of common ketones, such as cyclopentanones, acetophenones, acetone and 1-indanones, could be directly coupled with various arylboronates in high site-selectivity, which offers a distinct entry to more functionalized aromatic

  在这里，我们描述了通过催化激活无张力的 CC 键，简单的酮可以在 Suzuki-Miyaura 偶联反应中有效地用作亲电子试剂。一系列常见的酮，如环戊酮、苯乙酮、丙酮和1-茚满酮，可以直接与各种芳基硼酸酯以高位点选择性偶联，这为获得更多功能化的芳香酮提供了独特的途径。初步机理研究表明酮 α-CC 键通过氧化加成断裂。
• Borylation of organo halides and triflates using tetrakis(dimethylamino)diboron
  作者：Charles S. Bello、Joachim Schmidt-Leithoff

  DOI：10.1016/j.tetlet.2012.09.009

  日期：2012.11

  We report a new in situ borylation method using tetrakis(dimethylamino)diboron, DMA4B2, in the presence of a diol. Our method uses standard borylation conditions and readily available Pd-catalysts. The scope of this method includes aryl halides and triflates as well as vinyl halides and triflates. The method successfully works with a broad range of diols, enabling the selection of the best boronic

  我们报告了一种新的原位硼化方法，使用四（二甲基氨基）二硼，DMA 4 B 2，在二醇的存在下。我们的方法使用标准的硼化条件和现成的Pd催化剂。该方法的范围包括芳基卤化物和三氟甲磺酸酯以及乙烯基卤化物和三氟甲磺酸酯。该方法成功地与多种二醇一起使用，从而能够为随后的Suzuki偶联选择最佳的硼酸酯。