4-氟-1,2-苯二胺 | 367-31-7

• 物质功能分类: 有机原料 - 氨基化合物
• 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-氟-1,2-苯二胺
• 中文别名: 3,4-二氨基氟苯；4-氟-1,2-亚苯基二胺；4-氟邻苯二胺；对氟邻苯二胺；1,2-二氨基-4-氟苯
• 英文名称: 4-fluoro-1,2-phenylenediamine
• 英文别名: 4-fluorobenzene-1,2-diamine；4-fluoro-o-phenylenediamine；5-fluoro-o-phenylenediamine；1,2-diamino 4-fluorobenzene
• CAS: 367-31-7
• 化学式: C₆H₇FN₂
• mdl: MFCD00042228
• 分子量: 126.133
• InChiKey: KWEWNOOZQVJONF-UHFFFAOYSA-N

物化性质

• 熔点：
  94-98 °C
• 沸点：
  266.1±20.0 °C(Predicted)
• 密度：
  1.284±0.06 g/cm3(Predicted)
• 溶解度：
  可溶于DMSO（少许）、甲醇（少许）

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  52
• 氢给体数：
  2
• 氢受体数：
  3

安全信息

• 危险等级：
  6.1
• 安全说明：
  S26,S36
• 危险品运输编号：
  UN2811
• WGK Germany：
  3
• 海关编码：
  2921590090
• 危险类别：
  6.1
• 危险品标志：
  Xi
• 危险类别码：
  R36/37/38
• 包装等级：
  III
• 危险标志：
  GHS07
• 危险性描述：
  H315,H319,H335
• 危险性防范说明：
  P261,P305 + P351 + P338
• 储存条件：
  | 室温 |

SDS

Name:	4-Fluoro-o-phenylenediamine Material Safety Data Sheet
Synonym:	3,4-Diaminofluorobenzene
CAS:	367-31-7

Section 1 - Chemical Product MSDS Name: 4-Fluoro-o-phenylenediamine Material Safety Data Sheet
Synonym: 3,4-Diaminofluorobenzene

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SECTION 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
367-31-7	4-Fluoro-o-phenylenediamine		206-691-7

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.
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.
Chronic:
Not available.

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SECTION 4 - FIRST AID MEASURES
Eyes:
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.
Ingestion:
Get medical aid. 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.
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.
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.

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SECTION 7 - HANDLING and STORAGE
Handling:
Avoid breathing dust, vapor, mist, or gas. Avoid contact with skin and eyes.
Storage:
Store in a cool, dry place. Store in a tightly closed container.

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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# 367-31-7: Personal Protective Equipment
Eyes:
Not available.
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: Solid
Color: Not available.
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 89 - 91 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:
Specific Gravity/Density:
Molecular Formula: C6H7FN2
Molecular Weight: 126.13

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SECTION 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not available.
Conditions to Avoid:
Incompatible materials.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Nitrogen oxides, carbon monoxide, carbon dioxide, hydrogen fluoride gas.
Hazardous Polymerization: Has not been reported

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SECTION 11 - TOXICOLOGICAL INFORMATION RTECS#: CAS# 367-31-7 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
4-Fluoro-o-phenylenediamine - 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 Not regulated as a hazardous material. IMO Not regulated as a hazardous material. RID/ADR Not regulated as a hazardous material.

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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# 367-31-7: No information available. Canada None of the chemicals in this product are listed on the DSL/NDSL list. CAS# 367-31-7 is not listed on Canada's Ingredient Disclosure List. US FEDERAL TSCA CAS# 367-31-7 is not listed on the TSCA inventory. It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
MSDS Creation Date: 4/03/2003 Revision #0 Date: Original. The information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any other warranty, express or implied, with respect to such information, and we assume no liability resulting from its use. Users should make their own investigations to determine the suitability of the information for their particular purposes. In no way shall the company be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary damages, howsoever arising, even if the company has been advised of the possibility of such damages.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

用途

4-氟-1,2-苯二胺是合成抗肿瘤新药西达苯胺、苯并咪唑、喹喔啉及1-H-1,5-苯并氮杂卓类化合物的重要中间体，因此研究其合成方法具有非常重要的意义。

合成方法

将135g（0.86mol）4-氟-2-硝基苯胺、1000mL无水乙醇和27g Raney镍加入到2000mL反应釜中，通入氢气，在1.0MPa压力下于室温反应8小时。TLC检测显示反应完全后，冷却并迅速抽滤，得到的滤渣为Raney镍，可回收循环使用。减压蒸馏后获得99.59g灰白色固体，收率为91.3%，熔点为97~98℃（文献值：90~92℃）。

核磁共振氢谱（DMSO-d6，400MHz）数据如下：

• δ：4.27（s，2H），4.75（s，2H），6.11（t，1H，J=8.54Hz），6.29（d，1H，J=10.92Hz），6.42（t，1H，J=7.14Hz）。
• 质谱数据：m/z 127.1［M+H］+。

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
  3-氟苯胺	3-Fluoroaniline	372-19-0	C6H6FN	111.119
  4-氟苯胺	4-fluoroaniline	371-40-4	C6H6FN	111.119

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  4,5-二氟苯-1,2-二胺	2-amino-4,5-difluoroaniline	76179-40-3	C6H6F2N2	144.124
  ——	4-fluoro-N1-(prop-2-ynyl)benzene-1,2-diamine	195614-44-9	C9H9FN2	164.182
  ——	4-fluoro-2-phenylazoaniline	313485-92-6	C12H10FN3	215.23

反应信息

• 作为反应物：
  描述：

  4-氟-1,2-苯二胺 在 氯化亚砜 、 三乙胺 作用下， 以 氯仿 为溶剂， 反应 8.0h， 以75%的产率得到5-氟苯-[2,1,3]-噻重氮
  参考文献：
  名称：

  用于有机太阳能电池应用的硒酚取代苯并二噻吩和氟化苯并噻二唑基共轭聚合物的合成

  摘要：

  通过Stille缩聚反应合成了一系列含有硒酚改性苯并二噻吩和含氟苯并噻二唑的交替共轭共聚物，以研究取代苯并噻二唑的氟原子数的影响。三种不同的聚合物，PBDTSe-BT、PBDTSe-FBT和PBDTSe-FFBT, 被报道并检查了它们的电化学、光谱电化学和光伏行为。对模型四聚体结构进行了密度泛函理论计算，以阐明氟原子取代受体结构单元如何影响聚合物的结构、电子和光学性质。计算研究的结果与实验研究进行了比较。通过氟取代苯并噻二唑部分实现的结构调整揭示了对具有更负 HOMO 能级的聚合物的电子结构的影响。针对PBDTSe-FFBT检查所得光伏器件的高 V OC。二氟聚合物PBDTSe-FFBT :PC 71BM 有机太阳能电池表现出最高的光伏性能，为 2.63%，J SC为 7.24 mA cm -2，V OC为 0.72 V，FF 为 50.6%。PBDTSe-BT :PC 71 BM 显示出最佳

  DOI：

  10.1016/j.electacta.2021.139298
• 作为产物：
  描述：

  4-氟苯胺 在 镍 盐酸 、 氢气 、 硝酸 作用下， 以 乙醇 为溶剂， 反应 2.5h， 生成 4-氟-1,2-苯二胺
  参考文献：
  名称：

  Structure-Activity Relationship of Omeprazole and Analogs as Helicobacter pylori Urease Inhibitors

  摘要：

  Helicobacter pylori urease belongs to a family of highly conserved urea-hydrolyzing enzymes. A common feature of these enzymes is the presence of two Lewis acid nickel ions and a reactive cysteine residue in the active site. The H+/K(+)-ATPase inhibitor omeprazole is a prodrug of a sulfenamide which covalently modifies cysteine residues on the luminal side of the H+/K(+)-ATPase of gastric parietal cells. Omeprazole and eight analogues were selected based on their chemical, electronic, and kinetic properties, and each was incubated with viable H. pylori in phosphate-buffered saline at pH 7.4 for 30 min, after which 100 mM urea was added and the amount of ammonia formed analyzed after a further 10 min. Inhibition between 0% and 100% at a 0.1 mM concentration was observed for the different analogues and could be expressed as a function of the pKa-value of the pyridine, the pKa-value of the benzimidazole, the overall lipophilicity, and, most importantly, the rate of sulfenamide formation, in a quantitative structure-activity relationship. The inhibition was potentiated by a lower pH (favoring the formation of the sulfenamide) but abolished in the presence of beta-mercaptoethanol (a scavenger of the sulfenamide). Structural analogues incapable of yielding the sulfenamide did not inhibit ammonia production. Treatment of Helicobacter felis-infected mice with 230 mumol/kg flurofamide b.i.d. for 4 weeks, known to potently inhibit urease activity in vivo, as a means of eradicating the infection, was tested and compared with the effect of 125 mumol/kg omeprazole b.i.d. for 4 weeks. Neither treatment proved efficacious.

  DOI：

  10.1021/jm00025a008
• 作为试剂：
  描述：

  乙基4-(4-甲氧基苯基)-2,4-二氧代丁酸酯 在 sodium metabisulfite 、 lithium aluminium tetrahydride 、 盐酸肼 、 4-氟-1,2-苯二胺 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 乙醇 、 二甲基亚砜 为溶剂， 反应 4.0h， 生成 5-chloro-2-(3-(4-methoxyphenyl)-1H-pyrazol-5-yl)-1H-benzo[d]imidazole
  参考文献：
  名称：

  Synthesis of arylpyrazole linked benzimidazole conjugates as potential microtubule disruptors

  摘要：

  In an attempt to develop potent and selective anticancer agents, a series of twenty arylpyrazole linked benzimidazole conjugates (10a-t) were designed and synthesized as microtubule destabilizing agents. The joining of arylpyrazole to the benzimidazole moiety resulted in a four ring (A, B, C and D) molecular scaffold that comprises of polar heterocyclic rings in the middle associated with rotatable single bonds and substituted aryl rings placed in the opposite directions. These conjugates were evaluated for their ability to inhibit the growth of sixty cancer cell line panel of the NCI. Among these some conjugates like 10a, 10b, 10d, 10e, 10p and 10r exhibited significant growth inhibitory activity against most of the cell lines ranging from 0.3 to 13 mu M. Interestingly, the conjugate 10b with methoxy group on D-ring expressed appreciable cytotoxic potential. A549 cells treated with some of the potent conjugates like 10a, 10b and 10d arrested cells at G2/M phase apart from activating cyclin-B1 protein levels and disrupting microtubule network. Moreover, these conjugates effectively inhibited tubulin polymerization with IC50 values of 1.3-3.8 mu M. Whereas, the caspase assay revealed that they activate the casepase-3 leading to apoptosis. Particularly 10b having methoxy substituent induced activity almost 3 folds higher than CA-4. Furthermore, a competitive colchicine binding assay and molecular modeling analysis suggests that these conjugates bind to the tubulin successfully at the colchicine binding site. These investigations reveal that such conjugates having pyrazole and benzimidazole moieties have the potential in the development of newer chemotherapeutic agents. (C) 2015 Published by Elsevier Ltd.

  DOI：

  10.1016/j.bmc.2015.01.004

文献信息

• [EN] CALPAIN MODULATORS AND THERAPEUTIC USES THEREOF<br/>[FR] MODULATEURS DE CALPAÏNE ET LEURS UTILISATIONS THÉRAPEUTIQUES
  申请人：BLADE THERAPEUTICS INC

  公开号：WO2019190885A1

  公开（公告）日：2019-10-03

  Small molecule calpain modulator compounds, including their pharmaceutically acceptable salts, can be included in pharmaceutical compositions. The compounds can be useful in inhibiting calpain, or competitive binding with calpastatin, by contacting them with CAPN1, CAPN2, and/or CAPN9 enzymes residing inside a subject. The compounds and composition can also be administered to a subject in order to treat a fibrotic disease or a secondary disease state or condition of a fibrotic disease.

  小分子钙蛋白酶调节剂化合物，包括其药用可接受的盐，可以包含在药物组合物中。这些化合物可以通过与主体内的CAPN1、CAPN2和/或CAPN9酶接触来抑制钙蛋白酶，或与钙蛋白酶抑制剂竞争性结合。这些化合物和组合物也可以被用于治疗纤维化疾病或纤维化疾病的继发疾病状态或病情。
• [EN] ARYL-1,3-AZOLE DERIVATIVES AND METHODS FOR INHIBITING HEPARNASE ACTIVITY<br/>[FR] DERIVES D'ARYL-1,3-AZOLE ET PROCEDES PERMETTANT D'INHIBER L'ACTIVITE DE L'HEPARANASE
  申请人：IMCLONE SYSTEMS INC

  公开号：WO2005030206A1

  公开（公告）日：2005-04-07

  The present invention encompasses heparanase inhibitors, particularly to certain 2-substituted heteroaryl-fused and aryl-fused carbazole derivatives that inhibit heparanase, pharmaceutical compositions that contain the compounds, methods for making the compounds, and methods of treating heparanase-dependent diseases and conditions in mammals by administering a therapeutically effective amount of the compounds to the mammals.

  本发明涵盖了抑制肝素酶的抑制剂，特别是特定的2-取代杂芳基融合和芳基融合的咔唑衍生物，这些衍生物抑制肝素酶，包含这些化合物的药物组合物，制备这些化合物的方法，以及通过向哺乳动物施用这些化合物的治疗有效量来治疗依赖肝素酶的疾病和病况的方法。
• Rhodium catalyzed 2‐alkyl‐benzimidazoles synthesis from benzene‐1,2‐diamines and tertiary alkylamines as alkylating agents
  作者：Yamini、Saurabh Sharma、Pralay Das

  DOI：10.1002/aoc.6278

  日期：2021.8

  synthesized from benzene-1,2-diamine and tertiary amines as alkylating agent under polystyrene supported rhodium (Rh@PS) nanoparticles (NPs) catalyzed conditions. The heterogeneous rhodium catalyst was applied first time for the synthesis of 2-alkyl-benzimidazoles. The reaction followed through oxidation of alkylamines, transamination, and oxidative cyclisation with benzene-1,2-diamines for the corresponding

  在聚苯乙烯负载的铑（Rh@PS）纳米颗粒（NPs）催化条件下，以苯-1,2-二胺和叔胺为烷基化剂合成了取代的2-烷基-苯并咪唑。多相铑催化剂首次用于合成2-烷基-苯并咪唑。该反应通过烷基胺的氧化、氨基转移和与苯-1,2-二胺的氧化环化以良好的产率合成相应的产物。该工艺适用于广泛的底物范围，可以容忍多个官能团，并且 Rh@PS 催化剂最多可循环使用 4 次，催化活性没有显着损失。
• [EN] ANALGESIC COMPOUNDS<br/>[FR] COMPOSÉS ANALGÉSIQUES
  申请人：ZENO ROYALTIES & MILESTONES LLC

  公开号：WO2018213140A1

  公开（公告）日：2018-11-22

  Disclosed herein are compounds of Formulae (la), (lb), (Ic), (Id), (le), (If), (Ig), (Ih), (Ik), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is) and (It), methods of synthesizing compounds of Formulae (la), (lb), (Ic), (Id), (le), (If), (Ig), (Ih), (Ik), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is) and (It), and methods of using compounds of Formulae (la), (lb), (Ic), (Id), (le), (If), (Ig), (Ih), (Ik), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is) and (It) as an analgesic.

  本文披露了化合物的化学式（Ia）、（Ib）、（Ic）、（Id）、（Ie）、（If）、（Ig）、（Ih）、（Ik）、（Im）、（In）、（Io）、（Ip）、（Iq）、（Ir）、（Is）和（It），合成化合物的方法的化学式（Ia）、（Ib）、（Ic）、（Id）、（Ie）、（If）、（Ig）、（Ih）、（Ik）、（Im）、（In）、（Io）、（Ip）、（Iq）、（Ir）、（Is）和（It），以及使用化合物的方法的化学式（Ia）、（Ib）、（Ic）、（Id）、（Ie）、（If）、（Ig）、（Ih）、（Ik）、（Im）、（In）、（Io）、（Ip）、（Iq）、（Ir）、（Is）和（It）作为镇痛剂。
• From a Multipotent Stilbene to Soluble Epoxide Hydrolase Inhibitors with Antiproliferative Properties
  作者：Estel.la Buscató、Dominik Büttner、Astrid Brüggerhoff、Franca-Maria Klingler、Julia Weber、Bastian Scholz、Aleksandra Živković、Rolf Marschalek、Holger Stark、Dieter Steinhilber、Helge B. Bode、Ewgenij Proschak

  DOI：10.1002/cmdc.201300057

  日期：2013.6

  Inspired by nature: Natural product isopropylstilbene was identified as an inhibitor of soluble epoxide hydrolase exhibiting antiproliferative properties. Following the natural product inspired design approach, a library of (E)‐styryl‐1H‐benzo[d]imidazoles was synthesized and evaluated with recombinant enzyme and on several cancer cell lines.

  受自然界的启发：天然产物异丙基苯乙烯被鉴定为具有抗增殖特性的可溶性环氧化物水解酶的抑制剂。遵循天然产物的设计方法，合成了（E）-styryl-1 H-苯并[ d ]咪唑文库，并用重组酶和在几种癌细胞系上进行了评估。