4-羟甲基苯硼酸 | 59016-93-2

• 物质功能分类: 化学试剂 - 有机试剂 - 硼酸
• 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-羟甲基苯硼酸
• 中文别名: 4-(羟基甲基)苯硼酸；对羟甲基苯硼酸；4-羟甲基苯基硼酸；4-（羟甲基）苯硼酸；4-(羟甲基)苯硼酸
• 英文名称: p-hydroxymethylphenylboronic acid
• 英文别名: 4-(hydroxymethyl)phenylboronic acid；4-(hydroxymethyl)benzeneboronic acid；[4-(hydroxymethyl)phenyl]boronic acid
• CAS: 59016-93-2
• 化学式: C₇H₉BO₃
• mdl: MFCD00792672
• 分子量: 151.958
• InChiKey: PZRPBPMLSSNFOM-UHFFFAOYSA-N

物化性质

• 熔点：
  251-256 °C (lit.)
• 沸点：
  362.0±44.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)
• 稳定性/保质期：
  避免接触氧化物

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.142
• 拓扑面积：
  60.7
• 氢给体数：
  3
• 氢受体数：
  3

安全信息

• 危险等级：
  IRRITANT
• 危险品标志：
  Xi
• 安全说明：
  S26,S37/39
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 海关编码：
  2931900090
• 危险品运输编号：
  NONH for all modes of transport
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H315,H319,H335
• 储存条件：
  冰冻保存

SDS

Name:	4-(Hydroxymethyl)phenylboronic acid Material Safety Data Sheet
Synonym:	None Known
CAS:	59016-93-2

Section 1 - Chemical Product MSDS Name:4-(Hydroxymethyl)phenylboronic acid Material Safety Data Sheet
Synonym:None Known

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
59016-93-2	4-(Hydroxymethyl)phenylboronic acid	ca. 100	unlisted

Hazard Symbols: XI
Risk Phrases: 36/37/38

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Irritating to eyes, respiratory system and skin.
Potential Health Effects
Eye:
Causes eye irritation. May cause chemical conjunctivitis.
Skin:
Causes skin irritation. May be harmful if absorbed through the skin.
Ingestion:
May cause irritation of the digestive tract. May be harmful if swallowed.
Inhalation:
Causes respiratory tract irritation. May be harmful if inhaled. Can produce delayed pulmonary edema.
Chronic:
No information found.

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Section 4 - FIRST AID MEASURES
Eyes: Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse.
Ingestion:
Never give anything by mouth to an unconscious person. Get medical aid. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water. Wash mouth out with water.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid. Do NOT use mouth-to-mouth resuscitation.
Notes to Physician:
Treat symptomatically and supportively.

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Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Vacuum or sweep up material and place into a suitable disposal container. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Minimize dust generation and accumulation. Avoid breathing dust, vapor, mist, or gas. Avoid contact with eyes, skin, and clothing.
Keep container tightly closed. Avoid ingestion and inhalation. Use with adequate ventilation. Wash clothing before reuse.
Storage:
Store in a tightly closed container. Store in a dry area. Keep refrigerated. (Store below 4C/39F.)

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 59016-93-2: Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure limits are exceeded or if irritation or other symptoms are experienced.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Powder
Color: white to off-white
Odor: odorless
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 287 - 289 deg C
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: 25 g/l
Specific Gravity/Density:
Molecular Formula: C7H9BO3
Molecular Weight: 151.96

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable at room temperature in closed containers under normal storage and handling conditions.
Conditions to Avoid:
Incompatible materials, dust generation.
Incompatibilities with Other Materials:
Oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, carbon dioxide, boron oxides.
Hazardous Polymerization: Will not occur.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 59016-93-2 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
4-(Hydroxymethyl)phenylboronic acid - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION

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Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

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Section 14 - TRANSPORT INFORMATION

IATA
No information available.
IMO
No information available.
RID/ADR
No information available.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: XI
Risk Phrases:
R 36/37/38 Irritating to eyes, respiratory system
and skin.
Safety Phrases:
S 26 In case of contact with eyes, rinse immediately
with plenty of water and seek medical advice.
S 37/39 Wear suitable gloves and eye/face
protection.
WGK (Water Danger/Protection)
CAS# 59016-93-2: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 59016-93-2 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 59016-93-2 is not listed on the TSCA inventory.
It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

简介

4-羟甲基苯硼酸是一种性能更加优越的取代苯硼酸，尤其在中性水溶液中对糖类物质有更强的结合能力。这种配基具有低酸解离常数（pKa）和强烈的顺式二羟基化合物结合力，在中性和酸性条件下能专一性富集如核苷、糖蛋白等顺式二羟基化合物。此外，4-羟甲基苯硼酸还具有很高的保留容量，适合高通量分析复杂的生物样品，有效解决了目前硼亲和材料所面临的问题。

用途

作为一种硼酸衍生物，4-羟甲基苯硼酸广泛应用于有机合成中用于碳-碳键的形成。在Suzuki偶联反应中，芳基卤化物与硼酸芳基或乙烯基酯使用Pd(PPb)4进行偶联。

应用

由于其强结合能力和优良的水溶性，4-羟甲基苯硼酸具有比其他类别取代硼酸更优越的糖类物质识别能力，在中性条件下尤其表现出色。这类取代苯硼酸被广泛用作亲和配基来识别糖蛋白，如TF抗体和HI病毒中的gp-120，并且也被用于酶抑制剂如抗椎体虫剂的研究。4-羟甲基苯硼酸的这些特性可能有助于解决现有硼亲和材料所存在的问题。

应用示例

4-羟甲基苯硼酸可用于制备具有特定结构的4-氨基嘧啶氮杂环衍生物，这类化合物是一种BTK抑制剂。BTK在骨髓细胞功能中通过免疫复合体激活FcγR信号，在巨噬细胞中能阻断FcγRIII诱导的INF-α、IL-1β和IL-6产物产生，并通过NF-kB活化阻止BCR依赖的B细胞增殖，这为BTK在治疗自身免疫疾病提供了有力证据。此外，BTK已被证实是治疗淋巴瘤相关疾病的潜在靶点。

制备 第一步：4-羟甲基苯硼酸频哪醇酯的合成

将4-溴甲基苯甲酸甲酯（10.02克）、频哪醇二硼（13.00克）、醋酸钾（1.28克）和[1,1’-双(二苯基膦)二茂铁]二氯化钯（0.095克），加入到装有磁力搅拌器的三口瓶中，抽真空、充氮气。在氮气氛下，加入30毫升二氧六环，在100℃反应12小时后冷却至室温。然后依次用水洗两次、盐水洗一次，并用无水硫酸镁干燥。过滤后浓缩除去溶剂，残留物经柱层析分离（淋洗剂：乙酸乙酯∶己烷=1∶50），得到白色固体4-羟甲基苯硼酸频哪醇酯，收率92%。

第二步：4-羟甲基苯硼酸的合成

将第一步所得产物（1.12克）溶解在30毫升四氯化碳中，并加入N-溴代丁二酰亚胺（0.81克）、偶氮二异丁腈（0.036克），加热回流4小时后冷却至室温。反应液依次用水洗两次、盐水洗一次，再用无水硫酸镁干燥。过滤后减压除去溶剂，所得粗品溶解在50毫升乙醚中，并用15%氢氧化钾萃取三次。合并得到的水相，在冰浴中磁力搅拌下用盐酸调节pH至1，析出白色沉淀，收集并真空干燥获得白色固体4-羟甲基苯硼酸（0.45克），收率62%。

反应信息

• 作为反应物：
  描述：

  4-羟甲基苯硼酸 在 二氢吡啶 、 氧气 、 1,2,3,10a-tetrahydro-dipyrrolo[1,2-a;1',2'-d]pyrazine-5,10-dione 作用下， 反应 12.0h， 以70%的产率得到对羟基苯甲醇
  参考文献：
  名称：

  金属相容有机催化硼酸好氧氧化法合成双酚和二芳基醚

  摘要：

  单加氧酶激活分子氧能够氧化多种底物，主要是由于该过程与氧化还原活性金属的相容性。目前的研究表明，与单加氧酶类似，吡咯-脯氨酸 2,5-二酮哌嗪 (DKP) 有机催化剂在 Hantzsch 酯和 HFIP 存在下与铜 (II) 盐相容以活化分子氧。这些发现允许通过 DKP 促进的有氧氧化和随后形成的酚的金属氧化偶联或 Chan-Lam-Evans 型反应选择性地分散硼酸的氧化曲线，以合成酚、双酚和二芳基醚。

  DOI：

  10.1002/adsc.202200575
• 作为产物：
  描述：

  4-(hydroxymethyl)phenylboronic acid MIDA ester 在 sodium hydroxide 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以85%的产率得到4-羟甲基苯硼酸
  参考文献：
  名称：

  由简单 MIDA 硼酸酯多步合成复杂硼酸

  摘要：

  由于其对大多数合成试剂的敏感性，通常需要在使用之前引入硼酸官能团。克服了这一重要限制，我们在此报道空气和色谱稳定的 MIDA 硼酸盐与多种常用试剂兼容，这使得能够从简单的含 B 起始材料多步合成复杂的硼酸结构单元。X 射线和变温 NMR 研究将 MIDA 硼酸盐的独特稳定性与潜在反应性硼 p 轨道和/或氮孤对电子的动力学不可接近性联系起来。这些发现被共同利用，通过结构复杂的 MIDA 保护的卤代硼酸构件的迭代交叉偶联，实现了 (+)-crocacin C 的短程模块化全合成。

  DOI：

  10.1021/ja8063759
• 作为试剂：
  描述：

  GLPG-0634 中间体 、 4-羟甲基苯硼酸 在 4-羟甲基苯硼酸 作用下， 生成 cyclopropanecarboxylic acid [5-(4-hydroxymethyl-phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl]-amide
  参考文献：
  名称：

  NOVEL COMPOUND USEFUL FOR THE TREATMENT OF DEGENERATIVE AND INFLAMMATORY DISEASES

  摘要：

  本发明揭示了一种能够抑制JAK的新化合物，该化合物可以制备为药物组合物，并可用于哺乳动物包括人类的多种疾病的预防和治疗，例如，炎症性疾病、自身免疫疾病、增殖性疾病、移植排斥、涉及软骨周转障碍的疾病、先天性软骨畸形以及与IL6过度分泌相关的疾病，仅为举例。

  公开号：

  US20120142678A1

文献信息

• PYRAZOLO[1,5a]PYRIMIDINE DERIVATIVES AS IRAK4 MODULATORS
  申请人：Arora Nidhi

  公开号：US20120015962A1

  公开（公告）日：2012-01-19

  Compounds of the formula I or II: wherein X, m, Ar, R 1 and R 2 are as defined herein. The subject compounds are useful for treatment of IRAK-mediated conditions.

  式I或II的化合物： 其中X，m，Ar，R1和R2如本文所定义。所述化合物对于治疗IRAK介导的疾病是有用的。
• Compositions for Treatment of Cystic Fibrosis and Other Chronic Diseases
  申请人：Vertex Pharmaceuticals Incorporated

  公开号：US20150231142A1

  公开（公告）日：2015-08-20

  The present invention relates to pharmaceutical compositions comprising an inhibitor of epithelial sodium channel activity in combination with at least one ABC Transporter modulator compound of Formula A, Formula B, Formula C, or Formula D. The invention also relates to pharmaceutical formulations thereof, and to methods of using such compositions in the treatment of CFTR mediated diseases, particularly cystic fibrosis using the pharmaceutical combination compositions.

  本发明涉及含有上皮钠通道活性抑制剂与至少一种ABC转运蛋白调节剂化合物（A式、B式、C式或D式）的药物组合物。该发明还涉及这些药物配方，以及使用这些组合物治疗CFTR介导的疾病，特别是囊性纤维化的方法。
• IRAK DEGRADERS AND USES THEREOF
  申请人：Kymera Therapeutics, Inc.

  公开号：US20190192668A1

  公开（公告）日：2019-06-27

  The present invention provides compounds, compositions thereof, and methods of using the same.

  本发明提供了化合物、其组合物以及使用这些化合物的方法。
• Isotruxene-based porous polymers as efficient and recyclable photocatalysts for visible-light induced metal-free oxidative organic transformations
  作者：Haowen Zhang、Cen Zhou、Ying Zheng、Xiao Zhang

  DOI：10.1039/d1gc03165a

  日期：——

  The first implementation of isotruxene-based porous polymers (IsoPOPs) in catalysis is described, which allows oxidative chemical transformations to be conducted with air as the benign oxidant under visible-light irradiation in a metal-free fashion.

  描述了以异三萜基多孔聚合物（IsoPOPs）为基础的催化剂的首次实现，该催化剂允许在无金属的情况下，在可见光照射下使用空气作为温和氧化剂进行化学转化。
• METALLO-BETA-LACTAMASE INHIBITORS
  申请人：Merck Sharp & Dohme Corp.

  公开号：US20160333021A1

  公开（公告）日：2016-11-17

  The present invention relates to compounds of formula (I) that are metallo-β-lactamase inhibitors, the synthesis of such compounds, and the use of such compounds for use with β-lactam antibiotics for overcoming resistance.

  本发明涉及式(I)的化合物，这些化合物是金属β-内酰胺酶抑制剂，以及这些化合物的合成和与β-内酰胺类抗生素一起用于克服耐药性的用途。

表征谱图