查看“︁苯并三唑”︁的源代码

{{chembox
| NameEn = Benzotriazole
| ImageFile = Benzotriazole - numbered.png
| ImageSize = 205px
| ImageName = 苯并三唑的结构和环原子的编号
| ImageFileL1 = Benzotriazole-3D-balls.png
| ImageSizeL1 = 170px
| ImageNameL1 = 苯并三唑的棒球模型
| ImageFileR1 = Benzotriazole-3D-spacefill.png
| ImageSizeR1 = 170px
| ImageNameR1 = 苯并三唑的填充模型
| IUPACName =
| OtherNames = 1''H''-苯并三唑；苯三氮唑；苯并三氮杂茂；连三氮杂茚；苯三唑；1,2,3-苯骈三氮唑
| Abbreviations = BtH
| Section1 = {{Chembox Identifiers
| CASNo = 95-14-7
| CASNo_Ref = {{cascite|correct|CAS}}
|  EINECS  = 
|  PubChem  =  7220
|  SMILES  = 
|  InChI  = 
|  RTECS  = 
|  MeSHName  = 
|  ChEBI  = 
|  KEGG  = 
|  ATCCode_prefix  = 
|  ATCCode_suffix  = 
|  ATC_Supplemental  = 
|  ChemSpiderID_Ref  = {{chemspidercite|correct|chemspider}}|  ChemSpiderID  =  6950
|  InChIKey  =  QRUDEWIWKLJBPS-UHFFFAOYAH
|  ChEMBL_Ref  = {{ebicite|correct|EBI}}|  ChEMBL  =  84963
|  StdInChI_Ref  = {{stdinchicite|correct|chemspider}}|  StdInChI  =  1S/C6H5N3/c1-2-4-6-5(3-1)7-9-8-6/h1-4H,(H,7,8,9)
|  StdInChIKey_Ref  = {{stdinchicite|correct|chemspider}}|  StdInChIKey  =  QRUDEWIWKLJBPS-UHFFFAOYSA-N
|  ChEBI_Ref  = {{ebicite|changed|EBI}}|  KEGG_Ref  = {{keggcite|correct|kegg}}
}}
| Section2 = {{Chembox Properties
| C=6|H=5|N=3
| Appearance = 白色到浅粉色针状结晶
| Density = 1.36 g/cm<sup>3</sup>&nbsp;<ref name="Merck">{{cite web|url=http://de.chemdat.info/mda/de|title=chemdat.info|accessdate=2009-10-02|archive-url=https://web.archive.org/web/20081026154431/http://de.chemdat.info/mda/de|archive-date=2008-10-26|dead-url=yes}}</ref>
| MeltingPt = 100 °C&nbsp;<ref name="SRC">{{cite web|publisher=SRC PhysProp Database|url=http://esc.syrres.com/interkow/webprop.exe?CAS=95-14-7|title=1H-Benzotriazole|accessdate=2009-10-02|deadurl=yes|archiveurl=https://web.archive.org/web/20070927230759/http://esc.syrres.com/interkow/webprop.exe?CAS=95-14-7|archivedate=2007-09-27}}</ref>
| Melting_notes =
| BoilingPt = 350 °C&nbsp;<ref name="SRC"/>
| Boiling_notes =
| Solubility = 溶于水 (20 g/l)&nbsp;<ref name="SRC"/>
| VaporPressure = 5.3 Pa (20 °C)
| SolubleOther =
| Solvent =
| pKa = 8.37&nbsp;<ref name="SRC"/>
| pKb =
  }}
| Section3 = {{Chembox Structure
| CrystalStruct =
| Coordination =
| MolShape =
  }}
| Section4 = {{Chembox Thermochemistry
| DeltaHf =
| DeltaHc =
| Entropy =
| HeatCapacity =
  }}
| Section5 = {{Chembox Pharmacology
| AdminRoutes =
| Bioavail =
| Metabolism =
| HalfLife =
| ProteinBound =
| Excretion =
| Legal_status =
| Legal_US =
| Legal_UK =
| Legal_AU =
| Legal_CA =
| PregCat =
| PregCat_AU =
| PregCat_US =
  }}
| Section6 = {{Chembox Explosive
| ShockSens =
| FrictionSens =
| ExplosiveV =
| REFactor =
  }}
| Section7 = {{Chembox Hazards
| ExternalMSDS =
| EUClass =
| EUIndex =
| MainHazards =
| EUHazardSymbol = {{Chembox EUHazardSymbol|Xn}}
| NFPA-H =
| NFPA-F =
| NFPA-R =
| NFPA-O =
| RPhrases = {{R20/22}}, {{R36}}, {{R52/53}}&nbsp;<ref name="Merck"/>
| SPhrases = –
| FlashPt =
| Autoignition =
| ExploLimits =
| PEL =
| LD50 = 560 mg/kg (大鼠经口)&nbsp;<ref name="sigma">{{cite web|url=http://www.sigmaaldrich.com/catalog/search/ProductDetail/ALDRICH/190446 Sicherheitsdatenblatt|title=Benzotriazole reagent grade, 97%|publisher=Sigma-Aldrich|accessdate=2009-10-02}}</ref><br />＞1000 mg/kg (大鼠经皮)&nbsp;<ref name="sigma"/>
  }}
| Section8 = {{Chembox Related
| OtherAnions =
| OtherCations =
| OtherFunctn =
| Function =
| OtherCpds =
  }}
}}

'''苯并三唑'''是由一个[[苯環|苯环]]与一个[[1,2,3-三唑]]环[[稠合]]而成的双环含[[氮]][[杂环化合物]]。

== 性质 ==

白色到浅粉色针状结晶粉末。微溶于冷水，溶于热水、[[甲醇]]、[[乙醇]]、[[乙醚]]、[[丙酮]]、[[苯]]、[[甲苯]]、[[氯仿]]及[[二甲基甲酰胺]]。露置于空气中时逐渐[[氧化]]变红。在真空中[[蒸馏]]能发生爆炸<ref>{{cite web|url=http://www.chemyq.com/xz/xz11/105702umhgg.htm|title=苯丙三唑；1H-苯并三唑；苯三氮唑；苯丙三氮唑；苯并三氮杂茂；连三氮杂茚；苯三唑；苯并三唑；1,2,3-苯骈三氮唑|publisher=化工引擎|accessdate=2009-10-02|archive-date=2019-10-29|archive-url=https://web.archive.org/web/20191029173426/http://www.chemyq.com/xz/xz11/105702umhgg.htm|dead-url=no}}</ref>。

与1,2,3-三唑相似，苯并三唑也有三个[[互变异构体]]，即两个1''H''-构型和一个2''H''-构型。实验数据和量子化学结果显示在溶液和固态中苯并三唑的上述平衡几乎完全移向 1''H''-一侧，即 1''H''-异构体是更为稳定的异构体<ref name="Tomas">{{cite journal en|title=Tautomerism and aromaticity in 1,2,3-triazoles: the case of benzotriazole|author=Francisco Tomas, Jose Luis M. Abboud, Jose Laynez, Rafael Notario, Lucia Santos, Sven Ove Nilsson, Javier Catalan, Rosa Maria Claramunt, Jose Elguero|journal=[[J. Am. Chem. Soc.]]|year=1989|volume=111|issue=19|pages=7348–7353|doi=10.1021/ja00201a011}}</ref><ref name="Catalan"/><ref>{{cite journal en|title=Ab initio and semiempirical calculations on the tautomeric equilibria of ''N''-unsubstituted and ''N''-substituted benzotriazoles|author=Alan R. Katritzky, Konstantina Yannakopoulou, Ernst Anders, John Stevens, Miroslaw Szafran|journal=[[J. Org. Chem.]]|year=1990|volume=55|issue=22|pages=5683–5687|doi=10.1021/jo00309a009}}</ref>。但光激发[[三线态]]中苯并三唑的 2''H''-型更为稳定<ref name="Catalan">{{cite journal en|title=Theoretical and experimental evidence on the structure of benzotriazole in its first triplet electronic state|author=J. Catalán, and P. Pérez|journal=[[Chem. Phys. Letters]]|year=2005|volume=404|issue=4-6|pages=304–308|doi=10.1016/j.cplett.2005.01.107 }}</ref>。

<br />
[[File:Benzotriazole tautomerism.png|375px|苯并三唑的互变异构，左为 1H-苯并三唑，右为 2H-苯并三唑。]]

虽然 2''H''-苯并三唑有一个邻位[[醌]]式结构，但其 2 位给取代后 π 电子离域程度仍然很大，这与 2-甲基[[吲唑]]相同。

1''H''-苯并三唑是白色结晶粉末，在真空中重复升华纯化后得到的晶体测得熔点为100.5°C<ref>{{cite journal en|title=Raman-Effekt und Konstitutions-Probleme, XIII. Mitteil.: Naphthalinartig kondensierte Hetero-bicyclen|author=K. W. Fritz Kohlrausch, Reinhard Seka|journal=[[Chemische Berichte]]|year=1938|volume=71|issue=8|pages=1563–1570|doi=10.1002/cber.19380710803}}</ref>。[[单斜晶系]]<ref>{{cite journal en|title=Structure cristalline et moléculaire du benzotriazole|author=A. Escande, J. L. Galigné et J. Lapasset|journal=[[Acta Cryst.]]|year=1974|volume=B30|issue=6|pages=1490–1495|doi=10.1107/S0567740874005139}}</ref>。53.4～71.7°C 之间的蒸气压在 0.000695～0.0048 Torr 之间，可以用如下公式来描述<ref>{{cite journal en|title=Thermochemical properties of ''N''-heterocyclic compounds II. Enthalpies of combustion, vapour pressures, enthalpies of sublimation, and enthalpies of formation of 1,2,4-triazole and benzotriazole|author=P. Jiménez, M. V. Roux and C. Turrión|journal=[[J. Chem. Thermodynamics]]|year=1989|volume=21|issue=7|pages=759–764|doi=10.1016/0021-9614(89)90060-8 }}</ref>：

: <math>\rm \ lg (\mathit{p}/Pa) \ = \ \frac{5159.5}{(\mathit{T}/K)} \ + \ 14.77</math>

25°C 时升华焓 Δ<sub>sub</sub>H = 98.15 kJ/mol，63.4°C 时 Δ<sub>sub</sub>H = 96.30 kJ/mol<ref>{{cite journal en|title=Energetics of Intramolecular Bonds in 1''H''-1,2,4-Triazole and 1''H''-Benzotriazole|author=Raphaël Sabbah and Laurence Perez|journal=[[Austr. J. Chem.]]|year=1999|volume=52|issue=4|pages=235–240|doi=10.1071/C99006 }}</ref>。

本品在熔点以上剧烈放热分解<ref name="Malow et.al.">{{cite journal en|title=On the explosive properties of 1''H''-benzotriazole and 1''H''-1,2,3-triazole|author=Marcus Malow, Klaus D. Wehrstedt, and Steffen Neuenfeld|journal=[[Tetrahedron Lett.]]|year=2007|volume=48|issue=7|pages=1233–1235 |doi=10.1016/j.tetlet.2006.12.046}}</ref>，故不应蒸馏。240°C 时苯并三唑的分解反应放热 &minus;1590 kJ/kg<ref name="Malow et.al."/>。曾有一吨苯并三唑样品在 160°C 和 2.5 mbar 条件下蒸馏时发生爆炸性分解的记录<ref>Anon., ''Chem. Eng. News'', '''34''', 2450 (1956).</ref>。

苯并三唑既有[[酸性]]也有[[碱性]]，其碱性极弱，但其 NH 的酸性比[[吲唑]]、[[苯并咪唑]]或[[1,2,3-三唑]]强。稠合的苯环使[[共軛鹼|共轭碱]]更加稳定。[[pKa|p''K''<sub>a1</sub>]] = 0.42，p''K''<sub>a2</sub> = 8.27<ref>{{cite journal en|title=Photochemistry of 1''H''-Benzotriazole in Aqueous Solution:  A Photolatent Base|author=Hong Wang, Clemens Burda, Gaby Persy, and Jakob Wirz|journal=J. Am. Chem. Soc.|year=2000|volume=122|issue=24|pages=5849–5855|doi=10.1021/ja994464c}}</ref>。

: [[File:Benzotriazole protonation-deprotonation.svg|645px|none|1H-苯并三唑的酸性与碱性]]

苯并三唑可与许多金属形成[[配合物]]，通常作为[[桥连配体]]，以 N-1 和 N-3 为配位原子。

苯并三唑[[烷基化]]生成 1-烷基化和 2-烷基化产物的混合物，产物比例取决于烷基化试剂。[[酰化反应|酰化]]和[[磺化]]反应发生在 1-位氮上。[[亲电取代反应]]只发生在苯环上。

[[Graebe-Ullmann反应]]：1-苯基苯并三唑的去重氮化反应形成[[咔唑]]，反应经[[双自由基]]中间体，产率几乎定量。

== 制取 ==
将[[邻苯二胺]]在[[乙酸]]中用[[亚硝酸钠]]经[[重氮化]]环合是制取苯并三唑环的标准方法。<ref>Marie S. Chan, Wood E. Hunter (1981). "[http://www.google.com/patents?id=CzICAAAAEBAJ Preparation of benzotriazole]". ''U.S. Patent'' 4299965.</ref>
:[[File:Benzotriazole synthesis 01.svg|750px|center|苯并三唑的合成]]

也可由[[邻硝基苯肼]]和[[苯并咪唑酮]]合成。

== 用途 ==
[[File:PolyCubtri.svg|thumb|苯并三唑与铜形成的聚苯并三唑铜(Ⅰ)]]
苯并三唑是一种有用的[[防蚀剂]]，尤其是[[铜]]的防蚀剂，它可与铜形成一层不溶性的苯并三唑铜(Ⅰ)。对铝、铸铁、钢、镍、锌等金属材料也有同样的防蚀效果，可加入到汽车引擎的[[防冻剂]]、研磨和切削的[[润滑油]]以及铜及铜合金的清洗液中，达到防止腐蚀，提高缓蚀效果的目的<ref>{{cite web|url=http://www.ebotest.cn/html/huaxue/huaxuexiangmu/2009/0425/52.html|title=苯并三唑（Benzotriazole）|date=2009-04-25|publisher=亿博检测机构(EBO)|accessdate=2009-10-02|deadurl=yes|archiveurl=https://web.archive.org/web/20090519094118/http://www.ebotest.cn/html/huaxue/huaxuexiangmu/2009/0425/52.html|archivedate=2009-05-19}}</ref>。

苯并三唑和[[5-氯苯并三唑]]、[[5-硝基苯并三唑]]都是感光材料中有效的防灰雾剂及稳定剂，广泛应用于照相纸乳剂和显影液中<ref name="有机杂环化合物">{{cite book|pages=209–210|author=陈敏为，甘礼骓|title=有机杂环化合物|edition=第一版|location=北京|publisher=高等教育出版社|isbn=7-04-001122-0|date=1990年6月}}</ref>。

苯并三唑类属于[[紫外线吸收剂]]，是[[光稳定剂]]中最主要的一类，常见的有[[2-(2'-羟基-5'-甲基苯基)苯并三唑]]（UV-P）、[[2-(2'-羟基-3'-叔丁基-5'-甲基苯基)-5-氯苯并三唑]]（UV-326）、[[2-(2'-羟基-3',5'-二叔丁基苯基)-5-氯苯并三唑]]（UV-327）等，目前用于[[聚烯烃]]、[[聚氯乙烯]]、[[聚苯乙烯]]、[[丙烯酸树脂]]、[[聚酯]]、[[聚酰胺]]、[[纤维素酯]]等塑料中用作[[防老化剂]]，也用作[[防晒剂]]<ref name="有机杂环化合物" />。

苯并三唑及其衍生物也可用于[[有机合成]]。[[1-羟基苯并三唑]]是[[多肽合成]]中的羧基活化试剂，在[[二环己基碳二亚胺|DCC]]合成肽时用作辅助试剂<ref name="Eicher">{{cite book|pages=169–171|title=杂环化学——结构、反应、合成与应用（''The Chemistry of Heterocycles: Structures, Reactions, Synthesis and Applications''）|author=T. Eicher, S. Hauptmann 著，李润涛、葛泽梅、王欣 译|edition=第二版|publisher=化学工业出版社|location=北京|isbn=7-5025-7960-5|date=2005年11月}}</ref>。[[1-氯苯并三唑]]可用作[[氯化]]试剂，它可向底物转移一个 Cl<sup>+</sup><ref name="Eicher" />，也可用作[[氧化剂]]，将伯醇和仲醇氧化为醛酮<ref name="有机杂环化合物" />。

与相同程度苯化合物的苯甲基位置相比，苯并三唑对 α-[[碳正离子]]和 α-[[碳负离子]]都有稳定作用。苯并三唑基阴离子也是很好的[[离去基团]]，也有好的反应性和稳定性，易于操作。这些性质都用于合成中<ref>{{cite book|pages=606–609|title=杂环化学（''Heterocyclic Chemistry''）|author=J. A. Joule, K. Mills 著，由业诚、高大彬等译|publisher=科学出版社|location=北京|edition=4th ed.|isbn=7-03-012736-6|date=2004年7月}}</ref>。

== 参见 ==

* [[苯并咪唑]]

== 参考资料 ==
{{reflist}}

{{环状化合物}}

[[Category:缓蚀剂]]
[[Category:螯合配体]]
[[Category:苯并三唑]]
[[Category:照相药品]]
[[Category:保护与恢复材料]]