查看“︁1,5-环辛二烯”︁的源代码

{{chembox
| Watchedfields = changed
| verifiedrevid = 401758250
|   Name = 1,5-环辛二烯
|   ImageFile = 1,5-Cyclooctadiene.svg
|   ImageSize = 120px
|   ImageName = Skeletal formula of 1,5-cyclooctadiene
|   ImageFile2 = 1,5-cyclooctadiene-ED-3D-balls.png
|   ImageSize2 = 
|   ImageName2 = Ball-and-stick model of 1,5-cyclooctadiene
|IUPACName = Cycloocta-1,5-diene<ref>{{Cite web|title = AC1L1QCE - Compound Summary|url = https://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=8135|work = PubChem Compound|publisher = National Center for Biotechnology Information|accessdate = 14 October 2011|location = USA|date = 26 March 2005|at = Identification and Related Records|archive-date = 2012-02-25|archive-url = https://web.archive.org/web/20120225190026/http://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=8135|dead-url = no}}</ref>
| Section1 = {{Chembox Identifiers
|   SMILES = C\1=C\CC/C=C\CC/1
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/C8H12/c1-2-4-6-8-7-5-3-1/h1-2,7-8H,3-6H2/b2-1-,8-7-
| CASNo = 111-78-4
|    CASNo_Ref = {{cascite|correct|CAS}}
|   ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 74815
|   EC-number = 203-907-1
|   InChI = 1/C8H12/c1-2-4-6-8-7-5-3-1/h1-2,7-8H,3-6H2/b2-1-,8-7-
|   InChIKey = VYXHVRARDIDEHS-QGTKBVGQBM
|   StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = VYXHVRARDIDEHS-QGTKBVGQSA-N
  }}
| Section2 = {{Chembox Properties
|   C = 8
|   H = 12
|   Appearance = 澄清无色液体
|   Density = 0.882 g cm<sup>&minus;3</sup>（液态）
|   Solubility = -
|   MeltingPtC = -69.5
|   BoilingPtC = 151
  }}
}}

'''1,5-环辛二烯'''是一种[[有机化合物]]，化学式为C<sub>8</sub>H<sub>12</sub>，通常可以简写成COD。这种[[二烯烃]]是制备其他有机物的重要前体，并在[[金属有机化学]]用作[[配体]]。<ref name="buehler" /><ref name="shriver" />

== 合成 ==
1,5-环辛二烯可由[[1,3-丁二烯]]在[[镍]]催化剂作用下[[二聚]]制得，同时得到的副产物还有[[乙烯基环己烯]]。2005年时全球大约生产了10,000吨1,5-环辛二烯。<ref name="thomas" />

== 有机反应 ==
1,5-环辛二烯与[[乙硼烷]][[二甲基硫醚]][[加合物]]（相当于甲硼烷）反应产生[[9-硼二环［3.3.1］壬烷|9-硼二环[3.3.1]壬烷]]，<ref name="john" /> 后者简称9-BBN，是有机化学中用于[[硼氢化-氧化反应|硼氢化反应]]的[[试剂]]：
:[[File:Synthesis of 9-BBN dimer.png|450px]]

1,5-环辛二烯与[[二氯化硫]]或类似试剂[[加成]]得到2,6-二氯代-9-硫代双环[3.3.1]壬烷：<ref name="bishop" />
:[[File:CODSCl2.png|450px|2,6-Dichloro-9-thiabicyclo[3.3.1]nonane, synthesis and reactions]]

得益于[[邻基参与效应]]，产生的二氯代物可以通过[[亲核取代反应]]生成二[[叠氮基]]或二[[氰基]]衍生物。

1,5-环辛二烯在[[五羰基铁]]的存在下可以发生异构化反应，反应完全。<ref>宋礼成, 王佰全. 金属有机化学原理及应用. 高等教育出版社, 2012. pp 411</ref>
:[[File:1,5-cyclooctadiene_isomerization.png|250px]]

== 金属配合物 ==
1,5-环辛二烯可以与低价金属通过碳碳[[双键]]形成典型的[[不饱和烃配合物]]。配合物[[二(环辛二烯)合镍|Ni(cod)<sub>2</sub>]]是制备多种Ni(0)和Ni(II)配合物的前体。金属环辛二烯配合物很具有吸引力，因为它们足够稳定可以被分离出来，稳定性通常超过类似的[[乙烯]][[配合物]]。环辛二烯配合物的稳定性是[[螯合效应]]造成的。环辛二烯配体很容易被其他[[配体]]取代，例如[[膦]]。
:[[File:M(cod)2.png|thumb|240px|right|M(cod)<sub>2</sub>的结构（M = Ni、Pd、Pt）]]

Ni(COD)<sub>2</sub>可以在环辛二烯配体存在条件下，用[[三乙基铝]]还原无水二([[乙酰丙酮]])合镍制得<ref name="ittel" />：
:1/3 [Ni(C<sub>5</sub>H<sub>7</sub>O<sub>2</sub>)<sub>2</sub>]<sub>3</sub>  +  2 COD  +  2 Al(C<sub>2</sub>H<sub>5</sub>)<sub>3</sub>  →  Ni(COD)<sub>2</sub>  +  2 Al(C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>(C<sub>5</sub>H<sub>7</sub>O<sub>2</sub>)  +  C<sub>2</sub>H<sub>4</sub>  +  C<sub>2</sub>H<sub>6</sub>

类似的Pt(COD)<sub>2</sub>需要用迂回的路线制备，反应中需使用[[环辛四烯]]基二锂<ref name="crascall" />：
:Li<sub>2</sub>C<sub>8</sub>H<sub>8</sub>  +  PtCl<sub>2</sub>(COD)  +  3 C<sub>7</sub>H<sub>10</sub> → [Pt(C<sub>7</sub>H<sub>10</sub>)<sub>3</sub>] +  2 LiCl  +  C<sub>8</sub>H<sub>8</sub>  +  C<sub>8</sub>H<sub>12</sub>
:Pt(C<sub>7</sub>H<sub>10</sub>)<sub>3</sub> + 2 COD  →  Pt(COD)<sub>2</sub>  +  3 C<sub>7</sub>H<sub>10</sub>

目前已有大量关于环辛二烯配合物的研究报道，其中许多发表在[[无机合成 (书籍)|无机合成]]（Inorganic Syntheses）第25、26和28卷上。铂配合物已经使用在许多配合物的合成中：
:Pt(COD)<sub>2</sub>  +  3 C<sub>2</sub>H<sub>4</sub>  →  Pt(C<sub>2</sub>H<sub>4</sub>)<sub>3</sub>  +  2 COD

环辛二烯配合物是有用的起始原料，以下反应是一个值得注意的例子：
:Ni(cod)<sub>2</sub>  +  4 CO<sub>(g)</sub> <math>\rightleftharpoons</math> Ni(CO)<sub>4</sub>  +  2 COD
生成物Ni(CO)<sub>4</sub>有剧毒，因此在反应容器中生成它比直接配制更安全。其他低价金属的环辛二烯配合物包括Mo(COD)(CO)<sub>4</sub>、[RuCl<sub>2</sub>(COD)]<sub>n</sub>和Fe(COD)(CO)<sub>3</sub>。环辛二烯在Rh(I)和Ir(I)的[[配位化学]]中特别重要，例如{{link-en|克拉布特里催化剂|Crabtree's catalyst}}和[[环辛二烯氯化铑二聚体]]。平面四边形的配合物[M(COD)<sub>2</sub>]<sup>+</sup>也是已知的（M = Rh、Ir）。

==(''E'',''E'')-COD==
[[File:EE-COD synthesis.svg|thumb|600px|center|(''E'',''E'')-COD合成（斯托克曼等人，2011年）]]
1,5-环辛二烯张力很大的[[顺反异构|反-反异构体]]是一种已知的化合物。(''E'',''E'')-COD最早由[[乔治·怀特塞兹]]和[[阿瑟·科普]]在1969年通过顺式异构体的[[光异构化]]制得。<ref>''Irradiation of cis,cis-1,5-cyclooctadiene in the presence of copper(I) chloride'' [[George M. Whitesides]], Gerald L. Goe, [[Arthur C. Cope]] J. Am. Chem. Soc., 1969, 91 (10), pp 2608–2616 {{DOI|10.1021/ja01038a036}}</ref>另一种合成路线（八元环的双[[消除反应]]）由[[罗尔夫·胡伊斯根]]于1987年报道。<ref>''Preparation and conformation of (E,E)-1,5-cyclooctadiene''  Dieter Boeckh, [[Rolf Huisgen]], Heinrich Noeth J. Am. Chem. Soc., 1987, 109 (4), pp 1248–1249 {{DOI|10.1021/ja00238a046}}</ref>(''E'',''E'')-COD的[[构象]]是扭船式而不是椅式的。这种化合物已被研究用于[[点击化学]]的介质。<ref>''(E,E)-1,5-Cyclooctadiene: a small and fast click-chemistry multitalent'' Henning Stöckmann, André A. Neves, Henry A. Day, Shaun Stairs, Kevin M. Brindle and Finian J. Leeper Chem. Commun., 2011 {{DOI|10.1039/C1CC12161H}}</ref>

== 参考文献 ==
{{Reflist|refs=
<ref name="buehler">Buehler, C; Pearson, D.Survey of Organic Syntheses. Wiley-Intersciene, New York. '''1970'''.</ref>
<ref name="shriver">Shriver, D; Atkins, P.Inorganic Chemistry. W. H. Freeman and Co., New York. '''1999'''.</ref>
<ref name="john">{{OrgSynth | collvol = 9 | collvolpages = 95 | year= 1998 | title = <nowiki>9-Borabicyclo[3.3.1]nonane Dimer</nowiki> | author = John A. Soderquist and Alvin Negron | prep = cv9p0095}}</ref>
<ref name="bishop">{{OrgSynth | author = Roger Bishop | collvol = 9 | collvolpages = 692 | prep = CV9P0692| title = 9-Thiabicyclo[3.3.1]nonane-2,6-dione}}{{cite journal | title = 2,6-Dichloro-9-thiabicyclo[3.3.1]nonane: Multigram Display of Azide and Cyanide Components on a Versatile Scaffold | journal = [[Molecules (journal)|Molecules]] | year = 2006 | volume = 11 | pages = 212–218 | url = http://www.mdpi.org/molecules/papers/11040212.pdf | doi = 10.3390/11040212 | author = Díaz, David Díaz | last2 = Converso | first2 = Antonella | last3 = Sharpless | first3 = K. Barry | last4 = Finn | first4 = M. G. | access-date = 2011-10-03 | archive-date = 2011-09-27 | archive-url = https://web.archive.org/web/20110927022535/http://www.mdpi.org/molecules/papers/11040212.pdf | dead-url = no }}</ref>
<ref name="ittel">{{cite journal | author = Schunn, R; Ittel, S. | title = Bis(1,5-Cyclooctadiene) Nickel(0) | journal = [[Inorg. Synth.]] | volume = 28 | year = 1990 | doi = 10.1002/9780470132593.ch25 | pages = 94}}</ref>
<ref name="thomas">Thomas Schiffer, Georg Oenbrink -{“Cyclododecatriene, Cyclooctadiene, and 4-Vinylcyclohexene”}- in Ullmann’s Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim.</ref>
<ref name="crascall">{{cite journal | author = Crascall, L; Spencer, J. | doi = 10.1002/9780470132593.ch34 | journal = [[Inorg. Synth.]] | year = 1990 | volume = 28 | title = Olefin Complexes of Platinum | pages = 126}}</ref>
}}

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{{环烯烃}}

{{DEFAULTSORT:Cyclooctadiene, 1,5-}}
[[Category:环辛二烯]]
[[Category:环辛二烯配合物|*]]