查看“︁氯甲酸苄酯”︁的源代码

{{chembox
|Watchedfields=changed
|verifiedrevid=464396150
|ImageFile=Benzyl-chloroformate-2D-skeletal.png
|ImageName=Skeletal formula of benzyl chloroformate
|ImageFile1=Benzyl-chloroformate-3D-balls.png
|ImageName1=Ball-and-stick model of the benzyl chloroformate molecule
|PIN=氯甲酸苄酯
|OtherNames=甲酸氯苄酯<br />苄基碳酰氯<br/>苯甲氧基甲酰氯<br/>Cbz-Cl
|Section1={{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 9958
| InChI = 1/C8H7ClO2/c9-8(10)11-6-7-4-2-1-3-5-7/h1-5H,6H2
| InChIKey = HSDAJNMJOMSNEV-UHFFFAOYAW
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/C8H7ClO2/c9-8(10)11-6-7-4-2-1-3-5-7/h1-5H,6H2
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = HSDAJNMJOMSNEV-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo =501-53-1
| PubChem =10387
| EC_number = 207-925-0
| RTECS = LQ5860000
| UNNumber = 1739
| UNII = 170BP0DD31
| SMILES = ClC(=O)OCc1ccccc1
}}|Section2={{Chembox Properties
| Appearance = 透明液體
| Odour = 刺鼻
| C=8 | H=7 | Cl=1 | O=2
| Density =1.195 g/cm<sup>3</sup>
| BoilingPtC = 103
| Boiling_notes = (20 [[Torr]])
| Solubility = 分解
| RefractIndex = 1.519 (589 nm)
 }}|Section7={{Chembox Hazards
| GHSPictograms = {{GHS06}}{{GHS09}}
| GHSSignalWord = Danger
| HPhrases = {{H-phrases|314|400|410}}
| PPhrases = {{P-phrases|260|264|273|280|301+330+331|303+361+353|304+340|305+351+338|310|321|363|391|405|501}}
| ExternalSDS = [http://msds.chem.ox.ac.uk/BE/benzyl_chloroformate.html External MSDS]
| FlashPtC = 80
 }}
}}
'''氯甲酸苄酯'''，化學式<chem>C8H7ClO2</chem>，是一種[[有机化合物|有機化合物]]。它是一種[[氯甲酸酯]]。氯甲酸苄酯是透明油狀液體，有刺激性氣味，而且遇水分解，遇熱分解成[[光氣]]等有毒氣體<ref name=":3"/>。在[[有機合成]]上，它被用於引入[[苄氧羰基]]（Cbz），即是一種保護[[胺|胺基]]的[[保護基]]。<ref name=":4">{{Cite web |title=氯甲酸苄酯 |url=https://www.chembk.com/cn/chem/%E6%B0%AF%E7%94%B2%E9%85%B8%E8%8B%84%E9%85%AF |website=化工百科 |access-date=2022-08-17}}</ref>同時，它可用作有機合成中間體。<ref name=":3">{{Cite web |title=氯甲酸苄酯 |url=https://www.chemicalbook.com/ChemicalProductProperty_CN_CB7853678.htm |website=ChemicalBook |access-date=2022-08-17 |archive-date=2022-08-17 |archive-url=https://web.archive.org/web/20220817152008/https://www.chemicalbook.com/ChemicalProductProperty_CN_CB7853678.htm |dead-url=no }}</ref>

== 製備 ==
氯甲酸苄酯可以由[[苄醇]]與[[光氣]]反應而成。<ref name=":2">{{cite journal |last1=Hough |first1=L. |last2=Priddle |first2=J. E. |date=1961 |title=Carbonate derivatives of methyl α-<small>D</small>-mannopyranoside and of <small>D</small>-mannose |url=https://archive.org/details/sim_journal-of-the-chemical-society_1961-08/page/3178 |journal=J. Chem. Soc. |volume=1961 |pages=3178–3181 |doi=10.1039/JR9610003178}}</ref><ref name=":4"/>反應式如下：
:PhCH<sub>2</sub>OH + COCl<sub>2</sub>  →  PhCH<sub>2</sub>OC(O)Cl  +  HCl

反應需要用到過量的光氣來盡量減少生成[[碳酸酯]](PhCH<sub>2</sub>O)<sub>2</sub>C=O。<ref name=":2"/>

== 保護基 ==
在[[有機合成]]中，氯甲酸苄酯常被用於引入[[苄氧羰基]]。苄氧羰基是一個[[胺|胺基]]的[[保護基]]，簡稱Cbz或Z。於1930年代初，化學家Leonidas Zervas製備了氯甲酸苄酯，並用它來引入苄氧羰基保護基。反應式如下：[[File:Cbz to protect N-terminus.svg|600x600px]]

後來他與另一科學家Max Bergmann以此作基礎，開發了一種新的方法來合成[[肽]]。<ref name=":0">{{Cite book|url=https://org.chem.uoa.gr/istoriki_exelixi_toy_ergastirioy_organikis_chimeias_historical_development_of_organic_chemistry_laboratory/afieroma_ston_leonida_zerba_dedication_to_prof_leonidas_zervas/i_symboli_toy_l_zerba_stin_epistimi_tis_chimeias_contribution_of_l_zervas_in_the_science_of_chemistry/|title=The Chemistry of Polypeptides|publisher=Plenum Press|year=1973|isbn=978-1-4613-4571-8|editor-last=Katsoyannis|editor-first=P. G.|location=New York|doi=10.1007/978-1-4613-4571-8|s2cid=35144893|access-date=2022-08-17|archive-date=2022-10-13|archive-url=https://web.archive.org/web/20221013010830/https://org.chem.uoa.gr/istoriki_exelixi_toy_ergastirioy_organikis_chimeias_historical_development_of_organic_chemistry_laboratory/afieroma_ston_leonida_zerba_dedication_to_prof_leonidas_zervas/i_symboli_toy_l_zerba_stin_epistimi_tis_chimeias_contribution_of_l_zervas_in_the_science_of_chemistry/|dead-url=no}}</ref><ref name=":1"/>在1950年代之前，這是多肽合成最常用的步驟。<ref name=":0"/>

除了[[多肽合成]]，氯甲酸苄酯亦常用於保護一般的胺基，使氮的[[碱|鹼性]]與[[亲核性|親核性]]減弱。[[File:Cbz-Protection_V1.svg|500x500px]]

=== 上保護基 ===
以下是常用的方法：

* 於0 °C環境，[[胺]]與氯甲酸苄酯和[[鹼]]（如[[碳酸鈉]]）於[[水]]中作用。<ref name=":1">{{cite journal |last1=Bergmann |first1=Max |last2=Zervas |first2=Leonidas |year=1932 |title=Über ein allgemeines Verfahren der Peptid-Synthese |trans-title=On a general method of peptide synthesis |journal=Berichte der deutschen chemischen Gesellschaft |volume=65 |issue=7 |pages=1192–1201 |doi=10.1002/cber.19320650722}}</ref>
* 胺與氯甲酸苄酯和[[氧化鎂]]於[[乙酸乙酯]]中反應。<ref>{{Cite journal |last=Dymicky |first=M. |date=1989-02-01 |title=Preparation of Carbobenzoxy-<small>L</small>-Tyrosine Methyl and Ethyl Esters and of the Corresponding Carbobenzoxy Hydrazides |journal=Organic Preparations and Procedures International |volume=21 |issue=1 |pages=83–90 |doi=10.1080/00304948909356350 |issn=0030-4948}}</ref>

: [[File:Cbz ref2-en.svg|none|500x500px]]

* 胺與氯甲酸苄酯、[[N,N-二異丙基乙基胺]]、[[乙腈]]和[[三氟甲磺酸鈧]]作用。<ref>{{Cite journal |last1=Aggarwal |first1=Varinder K. |last2=Humphries |first2=Paul S. |last3=Fenwick |first3=Ashley |date=1999 |title=A Formal Asymmetric Synthesis of Anatoxin-a Using an Enantioselective Deprotonation Strategy on an Eight-Membered Ring |journal=Angewandte Chemie International Edition |volume=38 |issue=13–14 |pages=1985–1986 |doi=10.1002/(SICI)1521-3773(19990712)38:13/14<1985::AID-ANIE1985>3.0.CO;2-7}}</ref>

: [[File:Cbz proticetion-en.svg|none|442x442px]]

=== 脫保護基 ===
以下是常用的方法：

* [[氫解]]。以鈀化合物作爲[[催化劑]]<ref>{{cite book|url=https://books.google.com/books?id=doe9NwgJTAsC&pg=PA46|title=Peptides from A to Z: A Concise Encyclopedia|first1=Hans-Dieter|last1=Jakubke|first2=Norbert|last2=Sewald|date=2008|publisher=John Wiley & Sons|isbn=978-3-527-62117-0}}</ref><ref name=":0"/>，常用的催化劑如[[钯碳催化剂|鈀碳催化劑]]<ref>{{Cite journal |last1=Felpin |first1=François-Xavier |last2=Fouquet |first2=Eric |date=2010-11-02 |title=A Useful, Reliable and Safer Protocol for Hydrogenation and the Hydrogenolysis of O-Benzyl Groups: The ''In Situ'' Preparation of an Active Pd<sup>0</sup>/C Catalyst with Well-Defined Properties |journal=Chemistry – A European Journal |language=en |volume=16 |issue=41 |pages=12440–12445 |doi=10.1002/chem.201001377 |issn=1521-3765 |pmid=20845414}}</ref>。
*: [[File:Cbz deprot-en.svg|none|540x540px]]

* 以[[溴化氫]]的[[乙酸]]溶液處理。<ref>{{Cite book|title=基礎有機化學|last=邢|first=其毅|year=2017|isbn=9787301279434|location=北京|pages=997|last2=裴|first2=偉偉|last3=徐|first3=瑞秋|last4=裴|first4=堅|chapter=第21章 氨基酸、多肽、蛋白質以及核酸}}</ref>

受保護的胺經過以上方法處理，首先生成[[氨基甲酸]]，再經過[[脱羧反应|脫羧]]，生成原來的胺。

== 參考資料 ==
{{reflist}}

[[Category:氯甲酸酯]]
[[Category:有机化学试剂]]
[[Category:苄酯]]