2,5-二氟苯肼盐酸盐 | 175135-73-6

• 物质功能分类: 化学试剂 - 有机试剂 - 肼
• 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: 2,5-二氟苯肼盐酸盐
• 英文名称: 2,5-difluorophenylhydrazine hydrochloride
• 英文别名: (2,5-difluorophenyl)hydrazine;hydrochloride
• CAS: 175135-73-6
• 化学式: C₆H₆F₂N₂*ClH
• mdl: MFCD00013385
• 分子量: 180.585
• InChiKey: LZKLZCSHMDRKJH-UHFFFAOYSA-N

物化性质

• 熔点：
  210°C
• 稳定性/保质期：
  避氧化物

计算性质

• 辛醇/水分配系数(LogP)：
  1.65
• 重原子数：
  11
• 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：
  39.7
• 氢给体数：
  2
• 氢受体数：
  4

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S22,S36/37/39
• 危险类别码：
  R36/37/38
• 海关编码：
  29280000,2928000090
• 包装等级：
  III
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: 2,5-Difluorophenylhydrazine, HCl
Synonyms:

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Section 2. Hazards identification
Harmful by inhalation, in contact with skin, and if swallowed.
H302: Harmful 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: 2,5-Difluorophenylhydrazine, HCl
CAS number: 175135-73-6

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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.
Immediately wash skin with copious amounts of water for at least 15 minutes. Assure adequate
Eye contact:
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.
Storage: Store in closed vessels.

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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
No data
Boiling point:
Melting point: No data
Flash point: No data
Density: No data
Molecular formula: C6H6F2N2.ClH
Molecular weight: 180.6

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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 chloride, 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

制备方法与用途

简介

2,5-二氟苯肼盐酸盐是制备新型除草剂唑酮草酯的关键中间体。唑酮草酯（Carfentrazone-ethyl）是由美国FMC公司研发的一种三唑啉酮类触杀型除草剂，具有低毒、用量少、除草快、杀草谱广、选择性好且不易产生抗性的特点，其除草效果优于以往的磺酰脲类等常规除草剂。

制备

以2,5-二氟苯胺为原料，在3倍量的浓盐酸中加入冰乙酸作为助溶剂，并加入3%原料质量的PEG-400作为相转移催化剂。使用1.05摩尔当量的亚硝酸钠（配制成水溶液），在-5～0℃条件下进行重氮化反应，持续1小时；再以亚硫酸氢钠为还原剂，在75℃下进行还原反应1小时，得到的还原产物在85℃条件下用浓盐酸酸析2小时，从而制备得到2,5-二氟苯肼盐酸盐。最后通过氢氧化钠碱解2,5-二氟苯肼盐酸盐即可获得2,5-二氟苯肼，其含量≥96%（HPLC），收率≥74%（以2,5-二氟苯胺计）。

反应信息

• 作为反应物：
  描述：

  2,5-二氟苯肼盐酸盐 在 盐酸 、 N,N-二异丙基乙胺 、 N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate 作用下， 以 乙醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 32.5h， 生成 (6,9-difluoro-1,3,4,5-tetrahydro-2H-pyrido[4,3-b]indol-2-yl)-(5-(trifluoromethyl)-1H-pyrazol-3-yl)methanone
  参考文献：
  名称：

  Identification, Structure–Activity Relationship, and Biological Characterization of 2,3,4,5-Tetrahydro-1H-pyrido[4,3-b]indoles as a Novel Class of CFTR Potentiators

  摘要：

  Cystic fibrosis (CF) is a life-threatening autosomal recessive disease, caused by mutations in the CF transmembrane conductance regulator (CFTR) chloride channel. CFTR modulators have been reported to address the basic defects associated with CF-causing mutations, partially restoring the CFTR function in terms of protein processing and/or channel gating. Small-molecule compounds, called potentiators, are known to ameliorate the gating defect. In this study, we describe the identification of the 2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole core as a novel chemotype of potentiators. In-depth structure-activity relationship studies led to the discovery of enantiomerically pure 39 endowed with a good efficacy in rescuing the gating defect of F508del- and G551D-CFTR and a promising in vitro druglike profile. The in vivo characterization of gamma-carboline 39 showed considerable exposure levels and good oral bioavailability, with detectable distribution to the lungs after oral administration to rats. Overall, these findings may represent an encouraging starting point to further expand this chemical class, adding a new chemotype to the existing classes of CFTR potentiators.

  DOI：

  10.1021/acs.jmedchem.0c01050

文献信息

• Continuous Flow Process For the Synthesis of Phenylhydrazine Salts and Substituted Phenylhydrazine Salts
  申请人：SHANGHAI HYBRID-CHEM TECHNOLOGIES

  公开号：US20190152896A1

  公开（公告）日：2019-05-23

  The present invention provided a continuous flow process for the synthesis of phenylhydrazine salts and substituted phenylhydrazine salts. Diazotization, reduction, acidic hydrolysis and salifying with acids are innovatively integrated together. Using acidic liquids of aniline or substituted aniline, diazotization reagents, reductants and acids as raw materials, phenylhydrazine derivative salts is obtained through the synthesis process, which is a three-step continuous tandem reaction including diazotization, reduction, acidic hydrolysis and salifying. The described synthesis process is a kind of integrated solutions, which is carried out in an integrated reactor. The feed inlets of the integrated reactor are continuously filled with raw materials. In the integrated reactor, diazotization, reduction, acidic hydrolysis and salifying are carried out continuously and orderly, and phenylhydrazine salts or substituted phenylhydrazine salts is obtained in the outlet of the integrated reactor without interruption. The total reaction time is no more than 20 min.

  本发明提供了一种连续流程，用于合成苯肼盐和取代苯肼盐。重氮化、还原、酸性水解和酸化与酸类创新地集成在一起。使用苯胺或取代苯胺的酸性液体、重氮化试剂、还原剂和酸类作为原料，通过合成过程获得苯肼衍生物盐，这是一个包括重氮化、还原、酸性水解和酸化的三步连续串联反应。所述的合成过程是一种集成解决方案，是在一个集成反应器中进行的。集成反应器的进料口连续填充原料。在集成反应器中，重氮化、还原、酸性水解和酸化被连续有序地进行，苯肼盐或取代苯肼盐在集成反应器的出口处获得，没有中断。总反应时间不超过20分钟。
• 5-Membered heterocyclic compound
  申请人：Nishida Haruyuki

  公开号：US20090156642A1

  公开（公告）日：2009-06-18

  The present invention provides 5-membered heterocycle compounds represented by the following general formula (I): The present compounds have a superior acid secretion inhibitory effect, and shows an antiulcer activity and the like.

  本发明提供了以下通式(I)表示的5元杂环化合物： 本化合物具有优异的抑制胃酸分泌效果，并显示出抗溃疡活性等。
• Therapeutic pyrazolo[3,4-B]pyridines and indazoles
  申请人：Schelkun M. Robert

  公开号：US20060116376A1

  公开（公告）日：2006-06-01

  The present invention provides for compounds of Formula I: wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X, and L have any of the values defined in the specification, and pharmaceutically acceptable salts thereof, that are useful as agents in the treatment of central nervous disorders and conditions including attention deficit hyperactivity disorder, neuropathic pain, urinary incontinence, anxiety, depression, and schizophrenia and fibromyalgia. Also provided are pharmaceutical compositions comprising one or more compounds of Formula I.

  本发明提供了以下式I的化合物： 其中R2、R3、R4、R5、R6、R7、X和L具有规范中定义的任何值，以及其药学上可接受的盐，这些化合物在治疗中枢神经系统紊乱和症状，包括注意力缺陷多动障碍、神经病性疼痛、尿失禁、焦虑、抑郁、精神分裂症和纤维肌痛中作为药剂是有用的。还提供了包含一个或多个式I化合物的药物组合物。
• Design and stereoselective synthesis of novel isosteviol-fused pyrazolines and pyrazoles as potential anticancer agents
  作者：Song-Lin Zhu、Ya Wu、Cong-Jun Liu、Chang-Yong Wei、Jing-Chao Tao、Hong-Min Liu

  DOI：10.1016/j.ejmech.2013.04.044

  日期：2013.7

  Two series of novel isosteviol-fused pyrazoline and pyrazole derivatives were facilely synthesized via intramolecular 1,3-dipolar cycloaddition and condensation reaction, respectively. All compounds were characterized by NMR, IR and HRMS spectra. The stereochemistry of compounds 9b, 10, 11a and 11v were further confirmed by X-ray crystallographic analysis. The antiproliferative activities of the structurally

  分别通过分子内的1,3-偶极环加成和缩合反应轻松合成了两个新的异戊烯醇稠合的吡唑啉和吡唑衍生物。所有化合物均通过NMR，IR和HRMS光谱进行表征。化合物的立体化学9b的，10，11A和11V用X射线结晶学分析进一步证实。在体外测试了与结构相关的吡唑啉和吡唑衍生物的抗增殖活性在四种人类恶性细胞系（SGC 7901，A549，Raji和HeLa）上：我们的结果表明，异戊四醇融合的吡唑衍生物表现出值得注意的细胞毒活性。其中，与顺铂相比，针对SGC 7901，A549，Raji和HeLa的2,4-二-Cl-苯基吡唑衍生物11t表现出更好的细胞毒性，IC 50值分别为2.71、3.18、1.09和13.52μM，IC50值与顺铂相比（IC 50值：分别为7.56、17.78、17.32和14.31μM）。
• A New Germanium-Based Linker for Solid Phase Synthesis of Aromatics:  Synthesis of a Pyrazole Library
  作者：Alan C. Spivey、Christopher M. Diaper、Harry Adams、Andrew J. Rudge

  DOI：10.1021/jo000401x

  日期：2000.8.1

  An efficient synthesis of chlorogermane linker 12 is described. Economic introduction of germanium into this linker is accomplished by insertion of dichlorogermylene [from germanium(IV) chloride] into the homobenzylic C-Cl bond of 4-(2-chloroethyl)phenol 1. Using linker 12, transmetalation with lithiated 4-acetophenone, 3-acetophenone, and 4-(4'methoxy)biphenyl followed by Mitsunobu-type coupling to

  描述了氯锗烷接头12的有效合成。通过将二氯锗苯[来自氯化锗（IV）]插入4-（2-氯乙基）苯酚1的均苄基C-Cl键中，可将锗经济引入该连接基中。使用连接基12，使用锂化的4-苯乙酮进行重金属化， 3-苯乙酮和4-（4'甲氧基）联苯，然后通过Mitsunobu型偶联到Argogel，分别得到官能化的树脂14、16和18。用TFA，ICl，Br2或NCS处理树脂18会产生干净的ipso-去甲酰化反应，分别释放出联苯19-22。树脂14和16用于通过烯胺酮形成（使用Bredereck试剂），缩合的闭环（使用一系列单取代的肼）和裂解（使用TFA和Br2）并行合成吡唑库。