4-溴靛红 | 20780-72-7

• 物质功能分类: 生物化工 - 生化试剂 - 生物染料
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 中文名称: 4-溴靛红
• 中文别名: 4-溴吲哚满二酮；4-溴吲哚满-2,3-二酮；4-溴-1H-吲哚-2,3-二酮
• 英文名称: 4-bromoisatin
• 英文别名: 4-bromoindoline-2,3-dione；4-bromoindole-2,3-dione；4-bromo-1H-indole-2,3-dione；1H-4-bromoindole-2,3-dione；4-Brom-isatin
• CAS: 20780-72-7
• 化学式: C₈H₄BrNO₂
• mdl: MFCD03618555
• 分子量: 226.029
• InChiKey: ITRAKBJPMLKWIW-UHFFFAOYSA-N

物化性质

• 熔点：
  253-256
• 密度：
  1.826±0.06 g/cm3(Predicted)
• 溶解度：
  溶于二甲基甲酰胺

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  46.2
• 氢给体数：
  1
• 氢受体数：
  2

安全信息

• 危险等级：
  IRRITANT
• 危险品标志：
  Xi
• 海关编码：
  2933990090
• 危险性防范说明：
  P261,P280,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H332,H335
• 储存条件：
  存储条件：室温且密封保存。

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: 4-Bromoisatin
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-Bromoisatin
CAS number: 20780-72-7

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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: C8H4BrNO2
Molecular weight: 226

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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, nitrogen oxides, hydrogen bromide.

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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

制备方法与用途

应用 4-溴靛红是一种有机溴化物，可用作医药合成中间体。

制备方法 4-溴靛红的制备步骤如下：

1. 将3-溴苯胺（0.05 mol）、盐酸羟胺（0.15 mol）、硫酸钠（0.35 mol）、2N 盐酸和水合氯醛（0.06 mol）溶解于 250 mL 水中，在 90℃ 下反应 2 小时。通过 TLC 检测确认反应完全后，进行过滤并减压浓缩，直接进入下一步反应。
2. 向搅拌的浓硫酸溶液（20 mL）中分批加入步骤1得到的化合物，并将混合物加热至65℃。使用TLC分析确认反应完成后，冷却至室温并将反应混合物倒入冰水中（250 mL）。用水洗涤沉淀并干燥，然后用 5% NaOH 水溶液溶解粗产物，并用4NHCl（20 mL）酸化后过滤、洗涤和干燥，最终得到化合物3b（两步总产率64％）。

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  4-溴二氢吲哚	4-bromoindoline	86626-38-2	C8H8BrN	198.062
  1-(2-氨基-6-溴苯基)乙酮	1-(2-amino-6-bromophenyl)ethan-1-one	55830-09-6	C8H8BrNO	214.062

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  5-氯-1H-吲哚-2,3-二酮	4-bromo-5-chloroisatin	65971-75-7	C8H3BrClNO2	260.474
  4-溴-1-甲基吲哚-2,3-二酮	4-bromo-1-methylindoline-2,3-dione	884855-67-8	C9H6BrNO2	240.056
  4-溴吲哚-2-酮	4-bromoindolin-2-one	99365-48-7	C8H6BrNO	212.046
  ——	4-bromo-N-allyl isatin	1020972-97-7	C11H8BrNO2	266.094
  ——	4-bromo-1-dimethylaminomethyl-1H-indole-2,3-dione	1198782-87-4	C11H11BrN2O2	283.125
  ——	4-bromo-1-diethylaminomethyl-1H-indole-2,3-dione	1198782-88-5	C13H15BrN2O2	311.178
  ——	1-benzyl-4-bromoindoline-2,3-dione	1020972-38-6	C15H10BrNO2	316.154
  ——	4-bromo-1-piperidin-1-ylmethyl-1H-indole-2,3-dione	1031137-88-8	C14H15BrN2O2	323.189
  ——	4-bromo-1-morpholin-4-ylmethyl-1H-indole-2,3-dione	1198782-90-9	C13H13BrN2O3	325.162
  4-溴-1,3-二氢-1-甲基-2H-吲哚-2-酮	4-bromo-1-methylindolin-2-one	884855-68-9	C9H8BrNO	226.073

反应信息

• 作为反应物：
  描述：

  4-溴靛红 在 四(三苯基膦)钯 、 1,1'-双(二苯膦基)二茂铁二氯化钯(II)二氯甲烷复合物 双氧水 、 碳酸氢钠 、 potassium carbonate 、 溶剂黄146 、 N,N-二甲基苯胺 、 三乙胺 、 sodium hydroxide 、 三氯氧磷 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙二醇二甲醚 、 水 为溶剂， 反应 73.25h， 生成 5-(5-苯基-4-((吡啶-2-甲基)氨基)喹唑啉-2-基)吡啶-3-磺酰胺
  参考文献：
  名称：

  [EN] QUINAZOLINES AS POTASSIUM ION CHANNEL INHIBITORS
  [FR] QUINAZOLINES COMME INHIBITEURS DES CANAUX IONIQUES POTASSIQUES

  摘要：

  其中A、X、Y、Z、R1和R24如所述的(I)式化合物。这些化合物作为钾通道功能的抑制剂以及用于治疗和预防心律不齐、IKur相关疾病和其他由离子通道功能介导的疾病是有用的。

  公开号：

  WO2011028741A1
• 作为产物：
  描述：

  N-(3-bromophenyl)-2-hydroxyiminacetamide 在 硫酸 作用下， 反应 0.5h， 生成 4-溴靛红
  参考文献：
  名称：

  作为 SARS-CoV 3C 样蛋白酶抑制剂的 5-磺酰基靛红衍生物的合成、修饰和对接研究

  摘要：

  严重急性呼吸系统综合症 (SARS) 是由 SARS-CoV 引起的严重危及生命且致命的呼吸道疾病。SARS-CoV 含有与主要小核糖核酸病毒蛋白酶 3CL pro类似的胰凝乳蛋白酶样主要蛋白酶。3CL pro在病毒复制周期中起着关键作用，是 SARS 抑制剂开发的潜在目标。设计、合成了一系列靛红衍生物作为可能的 SARS-CoV 3CL pro抑制剂，并通过使用荧光底物肽的体外蛋白酶测定进行评估，其中几种对 3CL pro显示出有效的抑制作用. 分析了构效关系，并通过分子对接研究提出了可能的结合相互作用模式。在所有化合物中，8k 1对 3CL pro显示出最有效的抑制活性(IC 50  = 1.04 μM)。这些结果表明，这些抑制剂有可能被开发成抗 SARS 药物。

  DOI：

  10.1016/j.bmc.2013.11.028

文献信息

• Construction of Chiral Quaternary Carbon through Morita-Baylis-Hillman Reaction: An Enantioselective Approach to 3-Substituted 3-Hydroxyoxindole Derivatives
  作者：Xiao-Yang Guan、Yin Wei、Min Shi

  DOI：10.1002/chem.201002240

  日期：2010.12.10

  A new enantioselective approach to obtain a tetrasubstituted chiral center at the C3 position of oxindoles via a catalytic asymmetric Morita–Baylis–Hillman reaction has been demonstrated. This reaction provides 3‐substituted 3‐hydroxy‐2‐oxindoles in good to excellent yields and ee values, which could be facilely transformed to pharmaceutically more interesting compounds.

  已经证明了一种新的对映选择性方法，该方法通过催化不对称Morita-Baylis-Hillman反应获得在羟吲哚C3位置的四取代手性中心。该反应可提供3-取代的3-羟基-2-氧吲哚，其收率和ee值都非常好，并且可以很容易地转化为药学上更有趣的化合物。
• Asymmetric cross aldol addition of isatins with α,β-unsaturated ketones catalyzed by a bifunctional Brønsted acid–Brønsted base organocatalyst
  作者：Guo-Gui Liu、Hua Zhao、Yu-Bao Lan、Bin Wu、Xiao-Fei Huang、Jian Chen、Jing-Chao Tao、Xing-Wang Wang

  DOI：10.1016/j.tet.2012.03.042

  日期：2012.5

  The asymmetric cross-aldol reaction of isatins with α,β-unsaturated ketones has been developed under catalysis by a Cinchona alkaloid-derivated bifunctional Brønsted acid–Brønsted base catalyst, affording the aldol adducts in moderate to good yields (18–98%) with moderate to good enantioselectivities (30–97%). The noncovalent organo-catalyzed asymmetric cross-aldol reaction displays a broad substrate

  在金鸡纳生物碱衍生的双官能布朗斯台德酸-布朗斯台德碱催化剂的催化下，开发出了靛红与α，β-不饱和酮的不对称交叉羟醛反应，提供了中等至良好收率（18-98％）的羟醛加合物。中度到良好的对映选择性（30–97％）。尽管两个反应伙伴的电子和位阻性质对反应性和立体控制都具有相当大且规则的影响，但非共价有机催化的不对称交叉羟醛缩醛反应显示出较宽的底物范围和宽泛的官能团耐受性。
• Conjugated Thiophene-Fused Isatin Dyes through Intramolecular Direct Arylation
  作者：Andrea Nitti、Marco Signorile、Massimo Boiocchi、Gabriele Bianchi、Riccardo Po、Dario Pasini

  DOI：10.1021/acs.joc.6b01922

  日期：2016.11.18

  design, synthesis, and properties of innovative, planar, π-conjugated compounds in which a thiophene ring is fused with the skeleton of the naturally occurring dye isatin. The synthesis is achieved in high yields making use of an intramolecular direct arylation reaction as the key step, making the overall process potentially scalable. The synthetic sequence has been demonstrated also for an isatin bearing

  我们报告的创新，平面，π-共轭化合物的设计，合成和属性，其中噻吩环与天然染料isatin的骨架融合。利用分子内直接芳基化反应作为关键步骤，可以高收率实现合成，从而使整个过程具有潜在的可扩展性。对于在芳族环上带有氟取代基的靛红也已经证明了合成顺序。NMR和X射线研究表明，在融合，共面和共轭部分之间发生了串扰，使这些新型染料具有供体-受体特性。循环伏安法和UV-vis研究证实了新化合物的HOMO-LUMO水平和能隙非常有趣。
• [EN] NOVEL HETEROCYCLIC DERIVATIVES USEFUL AS SHP2 INHIBITORS<br/>[FR] NOUVEAUX DÉRIVÉS HÉTÉROCYCLIQUES UTILES EN TANT QU'INHIBITEURS DE SHP2
  申请人：JACOBIO PHARMACEUTICALS CO LTD

  公开号：WO2017211303A1

  公开（公告）日：2017-12-14

  Provided are certain pyrazine derivatives (I) as SHP2 inhibitors which is shown as formula (I), their synthesis and their use for treating a SHP2 mediated disorder. More particularly, provided are fused heterocyclic derivatives useful as inhibitors of SHP2, methods for producing such compounds and methods for treating a SHP2-mediated disorder.

  提供了某些吡嗪衍生物（I）作为SHP2抑制剂，其化学式如下（I），以及它们的合成和用于治疗SHP2介导的疾病。更具体地，提供了有用作为SHP2抑制剂的融合杂环衍生物，生产这类化合物的方法以及治疗SHP2介导的疾病的方法。
• Counter-Current chromatography separation of isatin derivatives using the sandmeyer methodology
  作者：Márcia R. Almeida、Gilda G. Leitão、Bárbara V. Silva、Jussara P. Barbosa、Angelo C. Pinto

  DOI：10.1590/s0103-50532010000400025

  日期：——

  method, using high-speed counter-current chromatography (HSCCC) technique, was developed for the separation of isomeric isatin derivatives, prepared following the Sandmeyer route. The biphasic solvent system composed of hexane:ethyl acetate:ethanol:water 1:0.5:0.5:1 (v/v/v/v) was used for all separations.

  开发了一种快速高效的方法，使用高速逆流色谱（HSCCC）技术分离按照Sandmeyer路线制备的同分异构的Isatin衍生物。所有分离均使用由己烷：乙酸乙酯：乙醇：水1：0.5：0.5：1（v / v / v / v）组成的双相溶剂系统。