2,3,5,6-四氟苯硼酸 | 511295-01-5

• 物质功能分类: 有机原料 - 有机氟化合物 - 氟苯硼酸系列
• 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: 2,3,5,6-四氟苯硼酸
• 英文名称: (2,3,5,6-tetrafluorophenyl)boronic acid
• CAS: 511295-01-5
• 化学式: C₆H₃BF₄O₂
• 分子量: 193.893
• InChiKey: SORPNEUIIZJCBF-UHFFFAOYSA-N

物化性质

• 熔点：
  143-145°C
• 沸点：
  263℃
• 密度：
  1.53
• 闪点：
  113℃
• 稳定性/保质期：
  按规定使用和贮存的不会分解，避免接触氧化物。

计算性质

• 辛醇/水分配系数(LogP)：
  -0.08
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  6

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S26,S36
• 危险类别码：
  R36/37/38
• 海关编码：
  2931900090
• 危险性防范说明：
  P261,P264,P271,P280,P302+P352,P304+P340+P312,P305+P351+P338,P332+P313,P337+P313,P362,P403+P233,P405,P501
• 危险性描述：
  H315,H319,H335
• 储存条件：
  请将药品存放在密闭、阴凉、干燥的地方。

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
2,3,5,6-Tetrafluorophenylboronic acid
Product Name:
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
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: 2,3,5,6-Tetrafluorophenylboronic acid
CAS number: 511295-01-5

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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
This product should be handled only by, or under the close supervision of, those properly qualified
Handling:
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
Melting point: No data
Flash point: No data
Density: No data
Molecular formula: C6H3BF4O2
Molecular weight: 193.9

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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, hydrogen fluoride.

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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：

  2,3,5,6-四氟苯硼酸 在 三氟乙酸 、 potassium hydroxide 作用下， 以 1,4-二氧六环 、 水 为溶剂， 生成 1,2,4,5-四氟苯
  参考文献：
  名称：

  碱催化的芳基-B（OH）2的原去硼烷：从协调的质子转移到瞬态芳基阴离子的解放。

  摘要：

  Kuivila于50年前发表的开创性研究表明，硼酸酯的ipso质子化是芳基硼酸的碱催化原脱硼硼烷的机理。但是，该研究仅限于酸性条件下的紫外分光光度法分析，并且估计了水的缔合常数（K a）。借助于NMR，停止流IR和骤冷流技术，现在已经在70°C的二恶烷水溶液中，在pH> 13的条件下，测定了30种不同的芳基硼酸的碱催化原硼酸脱氢反应的动力学。研究中包括C 6 H n F （5- n） B（OH）2的所有20个异构体半衰期跨越9个数量级：<3毫秒至6.5个月。在具有pH率分布，对组合ķ一个和Δ小号⧧值，动力学同位素效应（2 H，10 B，13 C），线性自由能的关系，并密度泛函理论计算，我们已经确定，涉及一种机械制度硼酸酯的单分子杂化与协同的ipso质子化/ C–B裂解竞争。芳基硼酸的相对路易斯酸度与它们的原脱硼氢硼酸速度不相关，特别是当存在邻位取代基时。值得注意的是，3,5-二硝基苯基硼酸

  DOI：

  10.1021/jacs.7b07444
• 作为产物：
  描述：

  硼酸三甲酯 、 1,2,4,5-四氟苯 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 以48%的产率得到2,3,5,6-四氟苯硼酸
  参考文献：
  名称：

  摘要：

  A general preparative procedure for polyfluorinated aryl(dihydroxy)boranes C6H5-nFnB(OH)(2) (n = 3 - 5) is described. Polyfluorinated aryl(dihydroxy)boranes are easily dehydrated to the corresponding tri(aryl)boroxins (C6H5-nFnBO)(3) by thermal or chemical treatment. The property of the acids C6H5-nFnB(OH)(2) to condensate depends on the number and on the position of the fluorine atoms in the aryl group. Examples of both classes of boron compounds were isolated as pure individuals and characterized by multinuclear NMR spectroscopy.

  DOI：

  10.1002/1521-3749(200213)628:13<2827::aid-zaac2827>3.0.co;2-n

文献信息

• An “On-Cycle” Precatalyst Enables Room-Temperature Polyfluoroarylation Using Sensitive Boronic Acids
  作者：Liye Chen、Haydn Francis、Brad P. Carrow

  DOI：10.1021/acscatal.8b00341

  日期：2018.4.6

  fluorinated arylboronic acid building blocks in cross-coupling has remained challenging, because of their acute base sensitivity. We report a general solution to this problem using a true catalytic intermediate, Pd(PAd3)(p-FC6H4)Br, as a uniquely effective “on-cycle” precatalyst that allows Suzuki–Miyaura coupling to occur much faster than even the most severe protodeboronation side reactions. Control of boron

  交叉偶联中使用氟化芳基硼酸结构单元仍然具有挑战性，因为它们具有敏锐的碱敏感性。我们报告了使用真正的催化中间体Pd（PAd 3）（p -FC 6 H 4）Br作为唯一有效的“循环”预催化剂，可以使Suzuki-Miyaura偶联发生的速度快得多的一般解决方案。即使是最严重的原去硼副反应。还发现控制活性酸形式和休眠酯形式之间的硼形态在平衡催化速率与试剂分解之间起着至关重要的作用。该方法与任何氟化模式，对碱不稳定的官能团以及一系列溴（杂）芳烃均兼容。
• Mechanistic Insights into C(sp ² )−C(sp)N Reductive Elimination from Gold(III) Cyanide Complexes
  作者：Alexandre Genoux、Jorge A. González、Estíbaliz Merino、Cristina Nevado

  DOI：10.1002/anie.202005731

  日期：2020.10.5

  elimination for the overall C(sp2)−C(sp)N bond forming reaction is characterized herein, for the first time, complementing previous studies reported for C(sp3)−C(sp3), C(sp2)−C(sp2), and C(sp3)−C(sp2) bond formation processes taking place on gold(III) species.

  已制备了新的膦连接的二氰基芳基金（III）配合物家族，并已详细研究了它们对还原消除的反应性。激活的高度正熵和主要的12/13 C KIE都表明后期的过渡过渡态，而Hammett分析和DFT计算表明该过程是异步的。结果，本文首次表征了涉及整个C（sp 2）-C（sp）N键形成反应的异步协同还原消除的独特机制，是对先前报道的C（sp 3）-研究的补充C（sp 3），C（sp 2）-C（sp 2）和C（sp 3）-C（sp 2）在金（III）物种上发生的键形成过程。
• “Cationic” Suzuki–Miyaura Coupling with Acutely Base-Sensitive Boronic Acids
  作者：Liye Chen、Daniel R. Sanchez、Bufan Zhang、Brad P. Carrow

  DOI：10.1021/jacs.7b07687

  日期：2017.9.13

  base-promoted protodeboronation of polyfluoroaryl and heteroaryl boronic acids complicates their use in Suzuki-Miyaura coupling (SMC) because a base is generally required for catalysis. We report a "cationic" SMC method using a PAd3-Pd catalyst that proceeds at rt in the absence of a base or metal mediator. A wide range of sensitive boronic acids, particularly polyfluoroaryl substrates that are poorly compatible

  多氟芳基和杂芳基硼酸的快速、碱促进的原脱硼使它们在 Suzuki-Miyaura 偶联 (SMC) 中的使用复杂化，因为催化通常需要碱。我们报告了一种使用 PAd3-Pd 催化剂的“阳离子”SMC 方法，该催化剂在没有碱或金属介体的情况下在室温下进行。各种敏感的硼酸，特别是与经典 SMC 条件相容差的多氟芳基底物，会发生干净的偶联。化学计量实验涉及有机钯阳离子的中介作用，它支持长期假定的 SMC 中金属转移的阳离子途径。
• Protodeboronation of (Hetero)Arylboronic Esters: Direct versus Prehydrolytic Pathways and Self-/Auto-Catalysis
  作者：Hannah L. D. Hayes、Ran Wei、Michele Assante、Katherine J. Geogheghan、Na Jin、Simone Tomasi、Gary Noonan、Andrew G. Leach、Guy C. Lloyd-Jones

  DOI：10.1021/jacs.1c06863

  日期：2021.9.15

  boronic esters under basic aqueous–organic conditions to be highly nuanced. In contrast to common assumption, esterification does not necessarily impart greater stability compared to the corresponding boronic acid. Moreover, hydrolysis of the ester to the boronic acid can be a dominant component of the overall protodeboronation process, augmented by self-, auto-, and oxidative (phenolic) catalysis when

  一系列硼酸酯的碱催化水解（ArB(OR) 2 → ArB(OH) 2）和原脱硼化（ArB(OR) 2 → ArH）的动力学和机理，包括八种不同的多元醇和 10 种多氟芳基和杂芳基部分，已通过原位和停流 NMR 光谱（19 F、1 H 和11 B）、pH 速率依赖性、同位素夹带进行了研究，2H KIE 和 KS-DFT 计算。该研究揭示了硼酸酯在碱性水-有机条件下的现象稳定性非常微妙。与通常的假设相反，与相应的硼酸相比，酯化不一定赋予更高的稳定性。此外，酯水解为硼酸可以是整个原脱硼过程的主要成分，当 pH 值接近硼酸的 p K a时，自催化、自催化和氧化（酚类）催化作用增强酯。
• Polyfluoroorganoboron-Oxygen Compounds. 7. Studies of Conversion of [(C6HnF5-n)B(OMe)3]- Into [(C6HnF5-n)2B(OMe)2]- (n = 0, 1)
  作者：Nicolai Yu. Adonin、Vadim V. Bardin、Hermann-Josef Frohn

  DOI：10.1135/cccc20081681

  日期：——

  Conversion of salts Li[(C₆H_nF_5-n)B(OMe)₃] (n = 0, 1) into (Li·DME)[(C₆H_nF_5-n)₂B(OMe)₂] was studied in dichloromethane-DME solution. The observed rate constants k decrease from (21.4 ± 0.9) × 10^-3 l mol^-1 s^-1 (Li[C₆F₅B(OMe)₃]) over (6.99 ± 0.11) × 10^-3 l mol^-1 s^-1 (Li[(2,3,5,6-C₆HF₄)B(OMe)₃]) to (2.94 ± 0.05) × 10^-3 l mol^-1 s^-1 (Li[(2,3,4,6-C₆HF₄)B(OMe)₃]), while Li[(2,3,4,5-C₆HF₄)B(OMe)₃] does not undergo any transformation. Hydrolysis of (Li·DME)[(C₆H_nF_5-n)₂B(OMe)₂] leads to corresponding borinic acids, whereas treatment of them with aqueous solution of M[HF₂] (M = Bu₄N, K) acidified with HF results in M[(C₆H_nF_5-n)₂BF₂] in high yields.

  在二氯甲烷-DME溶液中研究了盐Li[(C6HnF5-n)B(OMe)3] (n = 0, 1) 转化为(Li·DME)[(C6HnF5-n)2B(OMe)2]。观察到的速率常数k从(21.4 ± 0.9) × 10-3升摩尔-1秒-1 (Li[C6F5B(OMe)3]) 下降到(6.99 ± 0.11) × 10-3升摩尔-1秒-1 (Li[(2,3,5,6-C6HF4)B(OMe)3])，最终到(2.94 ± 0.05) × 10-3升摩尔-1秒-1 (Li[(2,3,4,6-C6HF4)B(OMe)3])，而Li[(2,3,4,5-C6HF4)B(OMe)3] 不发生任何转化。对(Li·DME)[(C6HnF5-n)2B(OMe)2]的水解导致相应的硼酸，而用含HF的水溶液处理它们，结果是高产率的M[(C6HnF5-n)2BF2] (M = Bu4N, K)。