2-甲基硫代苯硼酸频那醇酯 | 1072945-09-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 中文名称: 2-甲基硫代苯硼酸频那醇酯
• 中文别名: 2-甲基硫代苯基硼酸,频哪醇酯
• 英文名称: 4,4,5,5-tetramethyl-2-(2-(methylthio)phenyl)-1,3,2-dioxaborolane
• 英文别名: 4,4,5,5-tetramethyl-2-(2-methylsulfanylphenyl)-1,3,2-dioxaborolane
• CAS: 1072945-09-5
• 化学式: C₁₃H₁₉BO₂S
• 分子量: 250.17
• InChiKey: SLJWZEVOGXSTOM-UHFFFAOYSA-N

物化性质

• 熔点：
  77.5-78.6 °C
• 沸点：
  340.9±25.0 °C(Predicted)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.71
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  43.8
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2934999090

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: 2-Methylthiophenylboronic 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: 2-Methylthiophenylboronic acid, pinacol ester
CAS number: 1072945-09-5

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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: C13H19BO2S
Molecular weight: 250.2

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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, sulfur 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

反应信息

• 作为反应物：
  描述：

  2-甲基硫代苯硼酸频那醇酯 在 copper(ll) bromide 作用下， 以 甲醇 、 水 为溶剂， 以57%的产率得到2-溴茴香硫醚
  参考文献：
  名称：

  路易斯酸碱相互作用控制的芳基硫醚的邻位碳氢硼化

  摘要：

  开发了铱/联吡啶催化的芳基硫醚的邻位选择性CH硼化反应。高配位选择性是通过配体的硼基与底物的硫原子之间的路易斯酸碱相互作用实现的。这是由配体与底物之间的路易斯酸碱相互作用控制的催化和区域选择性CH转化的第一个例子。CH硼化反应可以以克为单位进行，并以生物活性分子为底物，证明了其对后期区域选择性CH硼化的适用性。一种生物活性分子是由邻硼酸盐化的产物通过将产物的硼烷基和甲硫基基团转化而合成的。

  DOI：

  10.1002/anie.201610041
• 作为产物：
  描述：

  茴香硫醚 、 联硼酸频那醇酯 在 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 5-(2-(4-(trifluoromethyl)-1,3,2-dioxaborolan-2-yl)phenyl)-2,2'-bipyridine 作用下， 以 对二甲苯 为溶剂， 反应 24.0h， 以64%的产率得到2-甲基硫代苯硼酸频那醇酯
  参考文献：
  名称：

  路易斯酸碱相互作用控制的芳基硫醚的邻位碳氢硼化

  摘要：

  开发了铱/联吡啶催化的芳基硫醚的邻位选择性CH硼化反应。高配位选择性是通过配体的硼基与底物的硫原子之间的路易斯酸碱相互作用实现的。这是由配体与底物之间的路易斯酸碱相互作用控制的催化和区域选择性CH转化的第一个例子。CH硼化反应可以以克为单位进行，并以生物活性分子为底物，证明了其对后期区域选择性CH硼化的适用性。一种生物活性分子是由邻硼酸盐化的产物通过将产物的硼烷基和甲硫基基团转化而合成的。

  DOI：

  10.1002/anie.201610041

文献信息

• Remarkably Efficient Iridium Catalysts for Directed C(sp²)–H and C(sp³)–H Borylation of Diverse Classes of Substrates
  作者：Md Emdadul Hoque、Mirja Md Mahamudul Hassan、Buddhadeb Chattopadhyay

  DOI：10.1021/jacs.0c13415

  日期：2021.4.7

  aliphatic substrates for selective C(sp3)–H bond borylations. Heterocyclic molecules are selectively borylated using the inherently elevated reactivity of the C–H bonds. A number of late-stage C–H functionalization have been described using the same catalysts. Furthermore, we show that one of the catalysts could be used even in open air for the C(sp2)–H and C(sp3)–H borylations enabling the method more general

  在这里，我们描述了一类新的 C-H 硼化催化剂的发现及其在芳族、杂芳族和脂肪族系统的区域选择性 C-H 硼化中的应用。新催化剂具有 Ir-C(噻吩基) 或 Ir-C(呋喃基) 阴离子配体，而不是标准 C-H 硼化条件中使用的二胺型中性螯合配体。据报道，这些新发现的催化剂的使用对不同种类的芳烃底物显示出优异的反应性和邻位选择性，并具有高分离产率。此外，该催化剂被证明对大量脂肪族底物的选择性 C(sp 3)–H 键硼化。杂环分子利用 C-H 键固有的高反应性选择性地硼化。已经使用相同的催化剂描述了许多后期 C-H 功能化。此外，我们表明其中一种催化剂甚至可以在露天用于 C(sp 2 )-H 和 C(sp 3 )-H 硼酸化，从而使该方法更加通用。初步的机理研究表明，活性催化中间体是 Ir(bis)boryl 络合物，连接的配体作为双齿配体。总的来说，这项研究强调了新型 C-H 硼酸化催化剂的发现，这些催化剂应该在
• Palladium‐Catalyzed Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction Selectivity by Computation
  作者：Chengwei Liu、Chong‐Lei Ji、Xin Hong、Michal Szostak

  DOI：10.1002/anie.201810145

  日期：2018.12.17

  demonstrated in the selective borylation of a variety of aromatics (>50 examples). This strategy was used in the late‐stage derivatization of pharmaceuticals and natural products. Computations reveal the mechanistic details of the unprecedented C−O bond activation of carboxylic acids. By circumventing the challenging decarboxylation, this strategy provides a general synthetic platform to access arylpalladium

  据报道羧酸的脱羰基硼酸酯化。在催化剂控制的条件下，对羧酸进行原位可及的空间受阻的酰基衍生物进行试剂脱羰后，会立即生成亲电子碳。该方法的范围和潜在影响在各种芳烃的选择性硼化中得到证明（> 50个实例）。该策略用于药物和天然产品的后期衍生化。计算揭示了前所未有的羧酸氧键活化机理。通过规避具有挑战性的脱羧反应，该策略提供了一个通用的合成平台，可用于从芳基钯物质中获得由丰富的羧酸形成的各种键。
• METHOD OF MAKING SULFIDE COMPOUNDS
  申请人：Universal Display Corporation

  公开号：US20150246928A1

  公开（公告）日：2015-09-03

  According to one embodiment of the present disclosure, a method of making sulfide compounds using Scheme 1 is disclosed. In Scheme 1, X 1 , X 2 , and X 3 are independently selected from the group consisting of F, Cl, Br, and I; Y is selected from the group consisting of Cl, Br, and I; and R 1 and R 2 are independently selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkyl, aryl, and heteroaryl, wherein R 1 and R 2 may be further substituted, and wherein R 1 is optionally covalently linked to R 2 and the reaction is intramolecular. In some embodiments, no catalyst is used in Scheme 1.

  根据本公开的一种实施例，揭示了一种利用方案1制备硫化物化合物的方法。在方案1中，X1、X2和X3分别从F、Cl、Br和I组成的组中独立选择；Y从Cl、Br和I组成的组中选择；R1和R2从烷基、环烷基、烯基、环烯基、炔基、环炔基、烷基、芳基和杂环芳基组成的组中独立选择，其中R1和R2可能进一步被取代，且R1可选择性地共价连接到R2，并且反应是分子内的。在某些实施例中，方案1中不使用催化剂。
• Selective Sulfoxidation of Thioethers and Thioaryl Boranes with Nitrate, Promoted by a Molybdenum–Copper Catalytic System
  作者：Hanit Marom、Svetlana Antonov、Yanay Popowski、Michael Gozin

  DOI：10.1021/jo2001808

  日期：2011.7.1

  boronic ester functional groups, using nitrate salts as oxidants. This homogeneous catalytic reaction was carried out in acetonitrile, where the MoO2Cl2(OPPh3)2 complex 1 or a mixture of complex 1 with Cu(NO3)2 were used as catalysts. We examined the reaction mechanism using 1H, 15N, and 31P NMR techniques and 18O-labeled sodium nitrate (NaN18O3) and show that the thioethers are oxidized by nitrate, generating

  钼酶催化还原硝酸盐在氮的全球生物循环中起着核心作用。然而，在合成有机化学中使用硝酸盐作为氧化剂非常有限，并且通常需要非常强的酸性和其他极端反应条件。我们已经开发出一种高度化学选择性和高效的催化方法，用于使用硝酸盐作为氧化剂对含硼酸或硼酸酯官能团的硫醚和芳基硫醚进行硫氧化。该均相催化反应在乙腈中进行，其中MoO 2 Cl 2（OPPh 3）2配合物1或配合物1与Cu（NO 3）的混合物2用作催化剂。我们使用1 H，15 N和31 P NMR技术以及18 O标记的硝酸钠（NaN 18 O 3）检查了反应机理，结果表明硫醚被硝酸盐氧化，生成亚硝酸盐。我们的工作增加了有机硼化合物现有的化学转化方法，使人们可以直接接触各种可能适用于铃木交叉偶联化学的新底物。
• Palladium-Catalyzed Methylation of Aryl, Heteroaryl, and Vinyl Boronate Esters
  作者：Alexander M. Haydl、John F. Hartwig

  DOI：10.1021/acs.orglett.9b00025

  日期：2019.3.1

  method for the direct methylation of aryl, heteroaryl, and vinyl boronate esters is reported, involving the reaction of iodomethane with aryl-, heteroaryl-, and vinylboronate esters catalyzed by palladium and PtBu2Me. This transformation occurs with a remarkably broad scope and is suitable for late-stage derivatization of biologically active compounds via the boronate esters. The unique capabilities

  报道了一种使芳基，杂芳基和乙烯基硼酸酯直接甲基化的方法，该方法涉及碘甲烷与由钯和​​PtBu 2 Me催化的芳基，杂芳基和乙烯基硼酸酯的反应。这种转化发生的范围非常广，并且适合于通过硼酸酯进行生物活性化合物的后期衍生化。通过串联形成碳-硼键形成反应和钯催化的甲基化反应，证明了该方法的独特功能。