3,4,5-三氯苯硼酸频那醇酯 | 942069-95-6

• 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: 3,4,5-三氯苯硼酸频那醇酯
• 中文别名: 3,4,5-三氯苯基硼酸频哪醇酯
• 英文名称: 3,4,5-trichlorophenylboronic acid pinacol ester
• 英文别名: 5-Bpin-1,2,3-trichlorobenzene；4,4,5,5-tetramethyl-2-(3,4,5-trichlorophenyl)-1,3,2-dioxaborolane
• CAS: 942069-95-6
• 化学式: C₁₂H₁₄BCl₃O₂
• 分子量: 307.412
• InChiKey: OTPVENHYVDCFAO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.95
• 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：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

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
• 储存条件：
  2-8℃，干燥保存，并密封。

SDS

Material Safety Data Sheet

---

Section 1. Identification of the substance
Product Name: 3,4,5-Trichlorophenylboronic acid, pinacol ester
Synonyms: 4,4,5,5-Tetramethyl-2-(3,4,5-trichlorophenyl)-1,3,2-dioxaborolane

---

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

---

Section 3. Composition/information on ingredients.
Ingredient name: 3,4,5-Trichlorophenylboronic acid, pinacol ester
CAS number: 942069-95-6

---

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.

---

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.

---

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.

---

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, refrigerated.
Storage:

---

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.

---

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: C12H14BCl3O2
Molecular weight: 307.4

---

Section 10. Stability and reactivity
Conditions to avoid: Heat, flames and sparks.
Materials to avoid: Oxidizing agents.
Possible hazardous combustion products: Carbon monoxide, hydrogen chloride.

---

Section 11. Toxicological information
No data.

---

Section 12. Ecological information
No data.

---

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.

---

Section 14. Transportation information
Non-harzardous for air and ground transportation.

---

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.

---

SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  3,4,5-三氯苯硼酸频那醇酯 在 copper diacetate 、 三乙胺 、 sodium nitrite 作用下， 以 乙腈 为溶剂， 反应 12.0h， 以0.101 g的产率得到1,2,3-三氯-5-硝基苯
  参考文献：
  名称：

  带有芳基化的芳烃的邻位/对位导向基团的亚硝化

  摘要：

  在本文中，我们报道了荟萃芳烃的-nitration轴承邻/对位用铱催化的C-H硼化反应之后是新开发的铜（II）粗频哪醇的芳基硼酸酯入的催化的变换引导组（多个）以一锅的方式对应的硝基芳烃。该协议允许的合成元-nitrated芳烃是乏味来制备或使用现有的方法需要多步合成。该反应可耐受多种邻位/对位导向基团，例如-F，-Cl，-Br，-CH 3，-Et，-i Pr -OCH 3和-OCF 3。它还提供对π电子缺陷杂环的硝基衍生物（例如吡啶和喹啉衍生物）的区域选择性访问。该方法的应用在复杂分子的后期修饰中以及在以克级制备到FDA批准的药物Nilotinib途中的中间体中得到了证明。最后，我们证明了通过该策略获得的硝基产物也可以通过Baran的胺化方案直接转化为苯胺或受阻胺。

  DOI：

  10.1002/chem.201901633
• 作为产物：
  描述：

  频那醇硼烷 、 三氯苯 在 IrH₂(Bpin){κ³-P,O,P-[xant(PiPr₂)₂]} 、 环己烯 作用下， 反应 18.0h， 以98%的产率得到3,4,5-三氯苯硼酸频那醇酯
  参考文献：
  名称：

  饱和氢化物-硼烷基-铱-POP配合物催化的芳烃直接CH硼化反应：元素步骤的动力学分析。

  摘要：

  饱和三氢化IRH 3 {κ 3 -P，O，P- [xant（P我镨2）2 ]}（1 ; xant（P我镨2）2 = 9,9-二甲基-4,5-双（二二异丙基）呫吨）激活频哪醇（HBpin）的两个分子的B-H键到形成H 2，氢化物氧硼衍生物IRH 2（BPIN）{κ 3 -P，O，P- [xant（P我镨2）2 ]}（2）和IRH（BPIN）2 {κ 3 -P，O，P- [xant（P我镨2）2]}（3）顺序排列。配合物3激活两个苯分子的CH键形成PhBpin，并以顺序方式再生2和1。因此，复合物1，2，和3限定两个周期用于与HBpin芳烃，其具有二氢化的催化直接C-H硼化2作为共同中间体。芳烃的CH键活化是两个循环的决定速率的步骤，因为CH氧化加成3的速度快于2。对1和2的反应进行动力学研究的结果HBpin的化合物支持氢化物配体在BH键激活中的协同功能。加入硼烷的氢化物的硼原子的促进B-H键的通过的κ形成协调1

  DOI：

  10.1002/chem.202001838

文献信息

• Regioselective Conversion of Arenes to<i>N</i>-aryl-1,2,3-triazoles Using CH Borylation
  作者：Rajavel Srinivasan、Anthony G. Coyne、Chris Abell

  DOI：10.1002/chem.201403021

  日期：2014.9.8

  A one‐pot protocol for the synthesis of N‐aryl 1,2,3‐triazoles from arenes by an iridium‐catalyzed CH borylation/copper catalyzed azidation/click sequence is described. 1 mol % of Cu(OTf)2 was found to efficiently catalyze both the azidation and the click reaction. The applicability of this method is demonstrated by the late‐stage chemoselective installation of 1,2,3‐triazole moiety into unactivated

  的单釜协议用于合成Ñ -芳基的1,2,3-三唑从芳烃通过铱催化的Ç  ħ硼化/铜催化的叠氮化/击序列进行说明。发现1mol％的Cu（OTf）2有效地催化了叠氮化和点击反应。1,2,3-三唑部分在化学上重要的未活化分子的后期化学选择性安装证明了该方法的适用性。
• Process for the synthesis of phenols from arenes
  申请人：Board of Trustees of Michigan State University

  公开号：US20040030197A1

  公开（公告）日：2004-02-12

  A process to synthesize substituted phenols such as those of the general formula RR′R″Ar(OH) wherein R, R′, and R″ are each independently hydrogen or any group which does not interfere in the process for synthesizing the substituted phenol including, but not limited to, halo, alkyl, alkoxy, carboxylic ester, amine, amide; and Ar is any variety of aryl or hetroaryl by means of oxidation of substituted arylboronic esters is described. In particular, a metal-catalyzed C—H activation/borylation reaction is described, which when followed by direct oxidation in a single or separate reaction vessel affords phenols without the need for any intermediate manipulations. More particularly, a process wherein Ir-catalyzed borylation of arenes using pinacolborane (HBPin) followed by oxidation of the intermediate arylboronic ester by OXONE is described.

  描述了一种合成取代酚的过程，如通式RR′R″Ar(OH)中的那些，其中R、R′和R″分别独立地是氢或不干扰合成取代酚过程的任何基团，包括但不限于卤素、烷基、烷氧基、羧酸酯、胺、酰胺；Ar是芳基或杂芳基的任何种类，通过氧化取代芳基硼酸酯来实现。具体地，描述了一种金属催化的C—H活化/硼化反应，随后在单个或分离的反应容器中直接氧化，从而获得酚，无需任何中间操作。更具体地，描述了一种通过Ir催化的芳烃硼化反应，使用二醇硼烷（HBPin）后，通过OXONE氧化中间芳基硼酸酯的过程。
• 4-Azolylphenyl isoxazoline insecticides acting at the GABA gated chloride channel
  作者：George P. Lahm、Daniel Cordova、James D. Barry、Thomas F. Pahutski、Ben K. Smith、Jeffrey K. Long、Eric A. Benner、Caleb W. Holyoke、Kathleen Joraski、Ming Xu、Mark E. Schroeder、Ty Wagerle、Michael J. Mahaffey、Rejane M. Smith、My-Hahn Tong

  DOI：10.1016/j.bmcl.2013.03.031

  日期：2013.5

  Isoxazoline insecticides have been shown to be potent blockers of insect GABA receptors with excellent activity on a broad pest range, including Lepidoptera and Hemiptera. Herein we report on the synthesis, biological activity and mode-of-action for a class of 4-heterocyclic aryl isoxazoline insecticides. (C) 2013 Elsevier Ltd. All rights reserved.
• Harnessing C–H Borylation/Deborylation for Selective Deuteration, Synthesis of Boronate Esters, and Late Stage Functionalization
  作者：Venkata A Kallepalli、Kristin A. Gore、Feng Shi、Luis Sanchez、Ghayoor A. Chotana、Susanne L. Miller、Robert E. Maleczka、Milton R. Smith

  DOI：10.1021/acs.joc.5b01588

  日期：2015.8.21

  Ir-catalyzed deborylation can be used to selectively deuterate aromatic and heteroaromatic substrates. Combined with the selectivities of Ir-catalyzed C-H borylations, uniquely labeled compounds can be prepared. In addition, diborylation/deborylation reactions provide monoborylated regioisomers that complement those prepared by C-H borylation. Comparisons between Ir-catalyzed deborylations and Pd-catalyzed deborylations of diborylated indoles described by Movassaghi are made. The Ir-catalyzed process is more effective for deborylating aromatics and is generally more effective in the monodeborylation of diborylated thiophenes. These processes can be applied to complex molecules such as dopidogrel.
• C−H Activation/Borylation/Oxidation:  A One-Pot Unified Route To Meta-Substituted Phenols Bearing Ortho-/Para-Directing Groups
  作者：Robert E. Maleczka,、Feng Shi、Daniel Holmes、Milton R. Smith

  DOI：10.1021/ja0349857

  日期：2003.7.1

  An efficient one-pot C-H activation/borylation/oxidation protocol for the preparation of phenols is described. This method is particularly attractive for the generation of meta-substituted phenols bearing ortho-/para-directing groups, as such substrates are difficult to access by other phenol syntheses.