(E)-二苯基乙烯
(E)-二苯基乙烯 | |
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IUPAC名 (E)-Stilbene[1] | |
英文名 | trans-stilbene |
識別 | |
CAS號 | 103-30-0 ![]() |
PubChem | 638088 |
ChemSpider | 553649 |
SMILES |
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InChI |
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InChIKey | PJANXHGTPQOBST-VAWYXSNFBV |
ChEBI | 36007 |
性質 | |
化學式 | C14H12 |
摩爾質量 | 180.25 g·mol−1 |
外觀 | 固體 |
密度 | 0.9707 g/cm3 |
熔點 | 122-125 °C |
沸點 | 305-307 °C |
溶解性(水) | 幾乎不溶 |
危險性 | |
MSDS | External MSDS |
NFPA 704 | |
閃點 | >112 °C |
若非註明,所有數據均出自標準狀態(25 ℃,100 kPa)下。 |
(E)-二苯基乙烯是一種二芳基乙烯,這種烴類由反式的乙烯連接苯基基團所組成。與(Z)-二苯基乙烯互為順反異構體。(E)-二苯基乙烯是白色晶體,極易溶於有機溶劑。它可以通過光化學的方法變成(Z)-二苯基乙烯,它可以繼續被轉化成菲。
(E)-二苯基乙烯於1843年由法國化學家奧古斯特·羅朗發現。[2]二苯基乙烯的英文名稱「stilbene」來自希臘文 στίλβω (stilbo),意為閃耀,這來自於該化合物有光澤的外觀。[3]
異構體
![](http://images.weserv.nl/?url=//upload.wikimedia.org/wikipedia/commons/thumb/1/1e/Cis-trans-stilbene.svg/400px-Cis-trans-stilbene.svg.png)
二苯基乙烯有兩種可能的立體異構體。一種是反式-1,2-二苯基乙烯,又稱(E)-二苯基乙烯;另一種是順式-1,2-二苯基乙烯,又稱(Z)-二苯基乙烯,它的位阻效應使得兩個芳環不在一個平面上,共軛體系消失,更加不穩定。[4](Z)-二苯基乙烯是液體,熔點5—6 °C(41—43 °F),而(E)-二苯基乙烯是固體,熔點125 °C(257 °F),顯示了它們明顯不同的物理性質。[5][6]
製備
(E)-二苯基乙烯有多種製備方法。常見的方法包括使用鋅汞齊還原苯偶姻:[6]
- C6H5–CH(OH)–C(=O)–C6H5 trans-C6H5–CH=CH–C6H5
二苯基乙烯的兩種異構體都可以由α-苯基肉桂酸的脫羧反應而成。其中,(E)-二苯基乙烯是由這種酸的(Z)-異構體脫羧而成的。[5]
理查德·赫克[7]和溝呂木勉[8]獨立報告了(E)-二苯基乙烯可以由碘苯和苯乙烯在鈀(II)催化劑下偶聯而成,也就是溝呂木-赫克反應。[9][10]溝呂木勉的方法產率較高。
反應
(E)-二苯基乙烯會被過氧磷酸(H3PO5)環氧化,在1,4-二氧六環中形成反式-二苯基環氧乙烷,產率74%。[11]這種環氧化物是外消旋混合物,由1,2-二苯基環氧乙烷的兩種對映異構體組成。這種非手性的內消旋化合物 (1R,2S)-1,2-二苯基環氧乙烷來自(Z)-二苯基乙烯,儘管順式異構體的環氧化會產生順式和反式異構體的混合物。舉個例子,過氧化叔丁醇氧化(Z)-二苯基乙烯會產生0.8% 順式-二苯基環氧乙烷、13.5% 反式-二苯基環氧乙烷和 6.1% 苯甲醛。[12][13]諾貝爾獎得主巴里·夏普萊斯製備了純二苯基環氧乙烷的一種對映異構體。[14]
二苯基乙烯可以被臭氧化反應[15]或勒米厄-約翰遜氧化反應乾淨的氧化成苯甲醛,而更強的氧化劑,如高錳酸鉀的氧化會產生苯甲酸。鄰位二醇可以通過厄普約翰雙羥基化反應或夏普萊斯不對稱雙羥基化反應製備,[16][17]對映體過量百分數高達100%。[18][19][20]
溴化(E)-二苯基乙烯主要產生內消旋-1,2-二溴-1,2-二苯基乙烯,符合親電溴加成反應會產生環狀的溴釒翁離子中間體的機制。[21]
在紫外線照射下,(E)-二苯基乙烯會異構化成(Z)-二苯基乙烯。這是典型的光化學反應,涉及了順反異構。它還可以繼續轉變成菲。[22]
衍生物和用處
(E)-二苯基乙烯本身的用處不多,但它的衍生物可用於染料、熒光增白劑、磷光體和閃爍體探測器。[23]二苯基乙烯是一種有源激光介質,用於染料激光器。[24]
![](http://images.weserv.nl/?url=//upload.wikimedia.org/wikipedia/commons/thumb/7/74/Diaminostilbene_disulfonic_acid.svg/220px-Diaminostilbene_disulfonic_acid.svg.png)
4,4'-二硝基二苯基乙烯-2,2'-二磺酸鈉可以由4-硝基甲苯的磺化先形成4-硝基甲苯-2-磺酸,然後被次氯酸鈉氧化偶聯成(E)-二苯基乙烯的衍生物。[25]這個過程最初是由Arthur George Green和André Wahl在19世紀開發的。[26][27]已經開發出更高產率的工藝改進,那就是在液氨中使用空氣氧化。[28]這種物質很有用,和苯胺衍生物反應會得到偶氮染料。衍生於此化合物的重要染料包括Direct Red 76、Direct Brown 78和Direct Orange 40。[24]
參考資料
- ^ International Union of Pure and Applied Chemistry. Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. 2014: 379. ISBN 978-0-85404-182-4. doi:10.1039/9781849733069.
- ^ Laurent, Auguste. Mémoire sur la série stilbique [Memoir on the stilbene series]. Comptes rendus. 1843, 16: 856–860 [2019-01-25]. (原始內容存檔於2021-09-17) (法語). From p. 857: "En soumettant ce sulfure à la distillation, il donne plusieurs produits, et entre autres, un composé fort remarquable que je nomme stilbène." (On submitting this sulfide [i.e., phenyl thioaldehyde, C6H5(CS)H] to [dry] distillation, it gives several products, and among others, a very remarkable compound which I name "stilbene".)
- ^ Miller, William Allen. Elements of Chemistry: Theoretical and Practical 3 5th. London, England: Longmans, Green and Co. 1880: 366 [2019-01-25]. (原始內容存檔於2021-08-01).
- ^ Eliel, Ernest L.; Wilen, Samuel H. Stereochemistry of Organic Compounds
. John Wiley and Sons. 1994: 566-567. ISBN 0-471-01670-5.
- ^ 5.0 5.1 (1953) "cis-Stilbene". Org. Synth. 33: 88; Coll. Vol. 4: 857.
- ^ 6.0 6.1 (1943) "trans-Stilbene". Org. Synth. 23: 86; Coll. Vol. 3: 786.
- ^ Heck, R. F.; Nolley, J. P. Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides. J. Org. Chem. 1972, 37 (14): 2320–2322. doi:10.1021/jo00979a024.
- ^ Mizoroki, Tsutomu; Mori, Kunio; Ozaki, Atsumu. Arylation of Olefin with Aryl Iodide Catalyzed by Palladium. Bull. Chem. Soc. Jpn. 1971, 44 (2): 581. doi:10.1246/bcsj.44.581
.
- ^ Heck, Richard F. Palladium-catalyzed vinylation of organic halides. Org. React. 1982, 27: 345–390. ISBN 0471264180. doi:10.1002/0471264180.or027.02.
- ^ Beletskaya, Irina P.; Cheprakov, Andrei V. The Heck Reaction as a Sharpening Stone of Palladium Catalysis. Chem. Rev. 2000, 100 (8): 3009–3066. PMID 11749313. doi:10.1021/cr9903048.
- ^ Ogata, Yoshiro; Tomizawa, Kohtaro; Ikeda, Toshiyuki. Oxidation of trans-stilbene with peroxymonophosphoric acid. J. Org. Chem. 1979, 44 (14): 2362–2364. doi:10.1021/jo01328a006.
- ^ Yin, Guochuan; Danby, Andrew M.; Kitko, David; Carter, John D.; Scheper, William M.; Busch, Daryle H. Olefin Epoxidation by Alkyl Hydroperoxide with a Novel Cross-Bridged Cyclam Manganese Complex: Demonstration of Oxygenation by Two Distinct Reactive Intermediates. Inorg. Chem. 2007, 46 (6): 2173–2180. PMID 17295471. doi:10.1021/ic061957r.
- ^ Busch, Daryle H.; Yin, Guochuan; Less, Hyun-Jin. Lewis Acid Catalyzed Epoxidation of Olefins Using Hydrogen Peroxide: Growing Prominence and Expanding Range. Oyama, S. Ted (編). Mechanisms in Homogeneous and Heterogeneous Epoxidation Catalysis. Elsevier. 2011: 119–153 [2021-08-01]. ISBN 9780080558011. (原始內容存檔於2021-09-07).
- ^ Chang, Han-Ting; Sharpless, K. Barry. Molar Scale Synthesis of Enantiopure Stilbene Oxide. J. Org. Chem. 1996, 61 (18): 6456–6457. PMID 11667495. doi:10.1021/jo960718q.
- ^ Bishop, Clyde E.; Denson, Donald D.; Story, Paul R. Mechanisms of ozonolysis. The cis, trans-stilbene system. Tetrahedron Lett. 1968, 9 (55): 5739–5742. doi:10.1016/S0040-4039(00)76338-6.
- ^ Jacobsen, Eric N.; Marko, Istvan; Mungall, William S.; Schroeder, Georg; Sharpless, K. Barry. Asymmetric dihydroxylation via ligand-accelerated catalysis. J. Am. Chem. Soc. 1988, 110 (6): 1968–1970. doi:10.1021/ja00214a053.
- ^ Kolb, Hartmuth C.; VanNieuwenhze, Michael S.; Sharpless, K. Barry. Catalytic Asymmetric Dihydroxylation. Chem. Rev. 1994, 94 (8): 2483–2547. doi:10.1021/cr00032a009.
- ^ Wang, Zhi-Min; Sharpless, K. Barry. A Solid-to-Solid Asymmetric Dihydroxylation Procedure for Kilogram-Scale Preparation of Enantiopure Hydrobenzoin. J. Org. Chem. 1994, 59 (26): 8302–8303. doi:10.1021/jo00105a065.
- ^ (1992) "(R,R)-1,2-Diphenyl-1,2-ethanediol (Stilbene Diol)". Org. Synth. 70: 47; Coll. Vol. 9: 383.
- ^ Atta-ur-Rahman; Shah, Zahir. Asymmetric Hydroxylations. Stereoselectove Synthesis in Organic Chemistry. Springer-Verlag. 1993: 406–410 [2021-08-01]. ISBN 9781461383277. (原始內容存檔於2021-08-01).
- ^ Gilbert, John C.; Martin, Stephen F. 10.6 – Bromination of Alkenes. Experimental Organic Chemistry: A Miniscale and Microscale Approach 5th. Cengage Learning. 2010: 376–383 [2021-08-01]. ISBN 9781439049143. (原始內容存檔於2021-08-28).
- ^ Kwasniewski, S. P.; Claes, L.; François, J.-P.; Deleuze, M. S. High level theoretical study of the structure and rotational barriers of trans-stilbene. J. Chem. Phys. 2003, 118 (17): 7823–7836. Bibcode:2003JChPh.118.7823K. doi:10.1063/1.1563617.
- ^ Vogt, Peter F.; Gerulis, John J. Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. 2000. ISBN 3527306730. doi:10.1002/14356007.a02_037.
|chapter=
被忽略 (幫助) - ^ 24.0 24.1 Hunger, Klaus; Mischke, Peter; Rieper, Wolfgang; Raue, Roderich; Kunde, Klaus; Engel, Aloys. Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. 2005. ISBN 3527306730. doi:10.1002/14356007.a03_245.
|chapter=
被忽略 (幫助) - ^ Cumming, William M.; Hopper, I. Vance; Wheeler, T. Sherlock. Preparation 294.—Dinitro-Stilbene-Disulphonic Acid (Na salt). Systematic Organic Chemistry: Modern Methods of Preparation and Estimation. New York: D. Van Nostrand Company. 1926: 314.
- ^ Green, Arthur G.; Wahl, André R. Ueber die Oxydation von Paranitrotoluolsulfosäure [On the oxidation of para-nitrotoluenesulfonic acid]. Ber. Dtsch. Chem. Ges. 1897, 30 (3): 3097–3101 [2021-08-01]. doi:10.1002/cber.189703003128. (原始內容存檔於2021-11-28) (德語).
- ^ Green, Arthur G.; Wahl, André R. Ueber die Oxydation der Paranitrotoluolsulfosäure [On the oxidation of para-nitrotoluenesulfonic acid]. Ber. Dtsch. Chem. Ges. 1898, 31 (1): 1078–1080 [2021-08-01]. doi:10.1002/cber.189803101195. (原始內容存檔於2021-11-28) (德語).
- ^ US patent 5041632,Guglielmetti, Leonardo,「Process for the preparation of 4,4'-dinitrostilbene-2,2-disulfonic acid」,發表於1991-08-20,發行於1991-08-20,指定於Ciba-Geigy Corporation