2-溴-N-丁基-4-硝基苯胺 | 2436-93-3

• 物质功能分类: 医药中间体 - 喹啉类化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 中文名称: 2-溴-N-丁基-4-硝基苯胺
• 英文名称: 6,8-dimethyl-quinoline
• 英文别名: 6,8-Dimethyl-chinolin；6,8-Dimethylquinoline
• CAS: 2436-93-3
• 化学式: C₁₁H₁₁N
• 分子量: 157.215
• InChiKey: RLZSSWLXBLSQKI-UHFFFAOYSA-N

物化性质

• 熔点：
  51.53°C (estimate)
• 沸点：
  268.55°C
• 密度：
  1.0665
• 保留指数：
  1408;1422;1408;1422

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2933499090

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: 2-Bromo-N-butyl-4-nitroaniline
Synonyms: 2-Bromo-1-butylamino-4-nitrobenzene

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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-Bromo-N-butyl-4-nitroaniline
CAS number: 2436-93-3

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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: C10H13BrN2O2
Molecular weight: 273.1

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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

反应信息

• 作为反应物：
  描述：

  2-溴-N-丁基-4-硝基苯胺 在 乙醇 、 sodium 作用下， 生成 6,8-二甲基-1,2,3,4-四氢喹啉
  参考文献：
  名称：

  Ewins, Journal of the Chemical Society, 1913, vol. 103, p. 101

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl 1-(2,4,6-trimethylphenyl)-1H-1,2,3-triazole-4-carboxylate 在 氢氧化钾 、 氯化亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 2-溴-N-丁基-4-硝基苯胺
  参考文献：
  名称：

  N-Mesityl-C-酰基酮亚胺：1,5- Sigmatropic转变和电环化成喹啉。

  摘要：

  三唑6a-c的快速真空热解（FVT）产生α-氧杂环丁酮10，酯10a是可分离的。吡咯二酮8的FVT产生异构的酰亚胺基亚油基烯9a。在适度的FVT条件下（约350-400摄氏度），Ketenes 9和ketenimines 10通过甲氧基和二甲基氨基的1，3-移位进行热转化。9和10均可通过红外光谱在77 K或在12 K的Ar基质隔离下直接观察到。在400℃下，酮亚胺10经历1，5-H转变为邻喹啉亚胺12/13，然后电环化为二氢喹啉14（未观察到）和15（通过NMR观察）。后者容易被大气氧氧化为烷基喹啉-3-羧酸盐或喹啉-3-羧酰胺16。从头开始对模型化合物18-23进行的计算预测约有4.8的能垒。38 kcal mol（-）（1）（161 kJ mol（-）（1））通过过渡态TS19在N-（邻甲基苯基）酮亚胺中的1,5-H转移，随后是对二氢喹啉23a的电环化势垒通过ca的TS22a 16 kcal

  DOI：

  10.1021/jo9722562

文献信息

• Ru(<scp>ii</scp>)-catalyzed amidation reactions of 8-methylquinolines with azides via C(sp³)–H activation
  作者：Bingxian Liu、Bin Li、Baiquan Wang

  DOI：10.1039/c5cc06230f

  日期：——

  The Ru(II)-catalyzed amidation reactions of 8-methylquinolines with azides have been developed. It is the first example of [(p-cymene)RuCl2]2-catalyzed C(sp3)-H bond intermolecular amidation reaction which give quinolin-8-ylmethanamines under mild reaction conditions...

  已经开发了Ru（II）催化的8-甲基喹啉与叠氮化物的酰胺化反应。这是[（对-异丙基）RuCl2] 2-催化的C（sp3）-H键分子间酰胺化反应的第一个例子，该反应在温和的反应条件下产生了喹啉-8-基甲胺。
• Ru(II)/Rh(III)-Catalyzed C(sp³)–C(sp³) Bond Formation through C(sp³)–H Activation: Selective Linear Alkylation of 8-Methylquinolines and Ketoximes with Olefins
  作者：Rohit Kumar、Rakesh Kumar、Diksha Parmar、Shiv Shankar Gupta、Upendra Sharma

  DOI：10.1021/acs.joc.9b03257

  日期：2020.1.17

  Herein, [RuCl2(p-cymene)]2/[Cp*RhIIICl2]2-catalyzed direct alkylation of C(sp3)-H bond of 8-methylquinolines with olefins (acrylates, styrenes, and aliphatic) is reported. The alkylation also proceeds with other conjugated systems such as malemides and α,β-unsaturated ketones. The reaction is highly regioselective, forms only a linear product, and tolerates a variety of functional groups on quinoline

  在本文中，报道了[RuCl 2（对异丙基）] 2 / [Cp * RhIIICl 2] 2催化的8-甲基喹啉的C（sp3）-H键与烯烃（丙烯酸酯，苯乙烯和脂肪族）的直接烷基化。烷基化还与其他共轭体系（例如马来酰亚胺和α，β-不饱和酮）一起进行。该反应是高度区域选择性的，仅形成线性产物，并且耐受喹啉和烯烃部分上的多种官能团。为了初步了解反应途径，已经进行了对照实验，氘标记和动力学研究。该反应可能在氧化还原中性条件下通过五元金属环进行。还已经进行了烷基化产物的多样化和（-）-桑托宁的酮肟衍生物的后期官能化，以证明所开发方法的适用性。
• Rh(<scp>iii</scp>)-Catalyzed straightforward arylation of 8-methyl/formylquinolines using diazo compounds
  作者：Bidhan Ghosh、Rajarshi Samanta

  DOI：10.1039/c9cc02391g

  日期：——

  A straightforward Rh(III)-catalyzed general strategy was developed for the introduction of naphthol/phenol moieties to the C(sp3)–H bond of 8-methylquinoline using diazonaphthalen-2(1H)-ones/quinone diazides. The developed method was further extended towards the arylation of 8-formylquinolines to accomplish diarylketone derivatives. The method is simple, relatively rapid, and chemo and regioselective

  开发了一种简单的Rh（III）催化的一般策略，即使用重氮萘-2（1 H）-ones /醌二叠氮化物将萘酚/苯酚部分引入8-甲基喹啉的C（sp 3）-H键。所开发的方法进一步扩展到8-甲酰基喹啉的芳基化反应，以完成二芳基酮衍生物。该方法简单，相对快速，并且具有广泛的范围和功能基团耐受性，具有化学和区域选择性。通过克规模的合成和生物活性分子的建设建立了合成实用程序。
• Iodonium Ylides as Carbene Precursors in Rh(III)-Catalyzed C–H Activation
  作者：Yuqin Jiang、Pengfei Li、Jie Zhao、Bingxian Liu、Xingwei Li

  DOI：10.1021/acs.orglett.0c02618

  日期：2020.10.2

  The rhodium(III)-catalyzed coupling of C–H substrates with iodonium ylides has been realized for the efficient synthesis of diverse cyclic skeletons, where the iodonium ylides have been identified as efficient and outstanding carbene precursors. The reaction systems are applicable to both sp2 and sp3 C–H substrates under mild and redox-neutral conditions. The catalyst loading can be as low as 0.5 mol

  铑（III）催化的C–H底物与碘鎓碘化物的偶联已经实现了各种环状骨架的有效合成，其中碘鎓碘化物已被认为是有效且出色的卡宾前体。该反应系统适用于在轻度和氧化还原中性条件下的sp 2和sp 3 C–H底物。在克规模的反应中，催化剂的负载量可以低至0.5mol％。代表性产品在纳摩尔水平下对人癌细胞具有细胞毒性。
• Anthranil: An Aminating Reagent Leading to Bifunctionality for Both C(sp³)−H and C(sp²)−H under Rhodium(III) Catalysis
  作者：Songjie Yu、Guodong Tang、Yingzi Li、Xukai Zhou、Yu Lan、Xingwei Li

  DOI：10.1002/anie.201602224

  日期：2016.7.18

  nitrogenation suffered from simple amidation/amination with limited atom‐economy and is mostly limited to C(sp2)−H substrates. In this work, anthranil was designed as a novel bifunctional aminating reagent for both C(sp2)−H and C(sp3)−H bonds under rhodium(III) catalysis, thus affording a nucleophilic aniline tethered to an electrophilic carbonyl. A tridendate rhodium(III) complex has been isolated as the

  以前的直接CH H氮化反应受简单的酰胺化/胺化作用和原子经济的限制，并且大多限于C（sp 2）-H底物。在这项工作中，将蒽醌设计为在铑（III）催化下同时用于C（sp 2）-H和C（sp 3）-H键的新型双功能胺化试剂，从而提供了拴接到亲电羰基的亲核苯胺。已经分离出三登酸盐铑（III）配合物作为催化剂的静止状态，DFT研究确定了亚硝基物质的中间体。

表征谱图