薁

薁
	IUPAC名; Azulene
	系統名; bicyclo[5.3.0]decapentaene; Azulene; 雙環[5.3.0]癸五烯
別名	藍烴、甘菊環
識別
CAS號	275-51-4
PubChem	9231
ChemSpider	8876
SMILES	C12=CC=CC=CC1=CC=C2;
InChI	1/C10H8/c1-2-5-9-7-4-8-10(9)6-3-1/h1-8H;
InChIKey	CUFNKYGDVFVPHO-UHFFFAOYAT
EINECS	205-993-6
ChEBI	31249
RTECS	CO4570000
KEGG	C13392
性質
化學式	C10H8
摩爾質量	128.17 g·mol⁻¹
外觀	青藍色片狀晶體
氣味	無
密度	1.037 g/cm3
熔點	99 °C（372 K）（）
沸點	242 °C（515 K）（）
溶解性（水）	幾乎不溶
溶解性	可溶於有機溶劑
磁化率	-98.5·10−6 cm3/mol
熱力學
ΔcHm⦵	−1266.5 kcal/mol
危險性
警示術語	R：R51/53
安全術語	S：S61
歐盟分類	N
主要危害	有毒
閃點	76.66 °C
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

薁（ou3）（英語：Azulene）又名藍烴，是萘的同分異構體，分子式為C₁₀H₈，為青藍色片狀晶體。它的偶極矩對碳氫化合物來說不尋常高。

化學性質[編輯]

薁的共振結構示意圖

薁是一種含有七元環與五元環的稠環芳烴。和萘相似，薁分子中含有10個π電子的共振結構，但是其共振穩定能只有萘的一半。薁可看做由環庚三烯正離子（䓬離子）和環戊二烯負離子構成，因此薁分子具有約1.08D的電偶極矩。^[8]由於極性，薁的五元環一側容易發生親電取代反應，七元環一側容易發生親核取代反應。薁的芳香性略低於萘，更容易加氫生成環戊烷並環庚烷。

薁在基態的極性反映在它的深色上，這對於小的不飽和芳族化合物來說是不尋常的。^[9]薁不符合卡莎規則，其許多衍生物也都不會在最低激發態發出熒光。^[10]

合成[編輯]

由於薁的特殊結構，科學家一直關注其合成方法。^[11]1939年，科學家St. Pfau和Plattner用茚滿和重氮乙酸乙酯首次人工合成薁。^[12]

有效的薁一鍋法涉及了環戊二烯與不飽和的C₅合成子的環化。^[13]環庚三烯前體的替代方法早已為人所知，下面顯示了一種說明性方法。^[14]^[15]

步驟：

環庚三烯和三氯乙酰氯生成的二氯乙烯酮的 2+2 環加成反應
重氮甲烷的插入反應（英語：Insertion reaction）
用二甲基甲酰胺脫鹵化氫
用硼氫化鈉通過Luche還原反應還原成醇
伯吉斯試劑的消除反應
四氯對苯醌氧化
用聚甲基氫矽氧烷（英語：polymethylhydrosiloxane）、乙酸鈀、磷酸鉀和DPDB配體脫鹵（英語：dehalogenation）

薁配合物[編輯]

在有機金屬化學中，薁可作為低價金屬中心的配體，其配合物包括 (azulene)Mo₂(CO)₆和(azulene)Fe₂(CO)₅。^[16]

參考資料[編輯]

^ International Union of Pure and Applied Chemistry. Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. 2014: 207. ISBN 978-0-85404-182-4. doi:10.1039/9781849733069.
^ ^2.0 ^2.1 Entry on Azulene. at: Römpp Online. Georg Thieme Verlag, retrieved 2019-02-14.
^ ^3.0 ^3.1 ^3.2 Datenblatt Azulene, 99% bei AlfaAesar, abgerufen am {{{Abruf}}}.
^ Sweet, L. I.; Meier, P. G. Lethal and Sublethal Effects of Azulene and Longifolene to Microtox®, Ceriodaphnia dubia, Daphnia magna, and Pimephales promelas (PDF). Bulletin of Environmental Contamination and Toxicology. 1997, 58 (2): 268–274 [2021-08-30]. PMID 8975804. doi:10.1007/s001289900330. hdl:2027.42/42354 . （原始內容存檔 (PDF)於2012-03-30）.
^ 來源：Sigma-Aldrich Co., product no. a97203 .. [2021-09-15]
^ Salter, Carl; Foresman, James B. Naphthalene and Azulene I: Semimicro Bomb Calorimetry and Quantum Mechanical Calculations. Journal of Chemical Education. 1998, 75 (10): 1341. Bibcode:1998JChEd..75.1341S. doi:10.1021/ed075p1341.
^ Harmon, A. D.; Weisgraber, K. H.; Weiss, U. Preformed azulene pigments of Lactarius indigo (Schw.) Fries (Russulaceae, Basidiomycetes). Experientia. 1980, 36: 54–56. S2CID 21207966. doi:10.1007/BF02003967.
^ Anderson, Arthur G.; Steckler, Bernard M. Azulene. VIII. A Study of the Visible Absorption Spectra and Dipole Moments of Some 1- and 1,3-Substituted Azulenes. Journal of the American Chemical Society. 1959, 81 (18): 4941–4946. doi:10.1021/ja01527a046.
^ Michl, Joseph; Thulstrup, E. W. Why is azulene blue and anthracene white? A simple mo picture. Tetrahedron. 1976, 32 (2): 205. doi:10.1016/0040-4020(76)87002-0.
^ Tétreault, N.; Muthyala, R. S.; Liu, R. S. H.; Steer, R.P. Control of the Photophysical Properties of Polyatomic Molecules by Substitution and Solvation: The Second Excited Singlet State of Azulene. Journal of Physical Chemistry A. 1999, 103 (15): 2524–31. Bibcode:1999JPCA..103.2524T. doi:10.1021/jp984407q.
^ Gordon, Maxwell. The Azulenes. Chemical Reviews. 1 February 1952, 50 (1): 127–200. doi:10.1021/cr60155a004.
^ St. Pfau, Alexander; Plattner, Pl. A. Zur Kenntnis der flüchtigen Pflanzenstoffe VIII. Synthese des Vetivazulens. Helvetica Chimica Acta. 1939, 22: 202–208. doi:10.1002/hlca.19390220126.
^ Hafner, Klaus; Meinhardt, Klaus-Peter. Azulene. Organic Syntheses. 1984, 62: 134. doi:10.15227/orgsyn.062.0134.
^ Carret, Sébastien; Blanc, Aurélien; Coquerel, Yoann; Berthod, Mikaël; Greene, Andrew E.; Deprés, Jean-Pierre. Approach to the Blues: A Highly Flexible Route to the Azulenes. Angewandte Chemie International Edition. 2005, 44 (32): 5130–5133. PMID 16013070. doi:10.1002/anie.200501276.
^ Lemal, David M.; Goldman, Glenn D. Synthesis of azulene, a blue hydrocarbon. Journal of Chemical Education. 1988, 65 (10): 923. Bibcode:1988JChEd..65..923L. doi:10.1021/ed065p923.
^ Churchill, Melvyn R. Transition Metal Complexes of Azulene and Related Ligands. Progress in Inorganic Chemistry. 2007: 53–98. ISBN 9780470166123. doi:10.1002/9780470166123.ch2.
^ Asao, Toyonobu; Shunji Ito; Noboru Morita. 1-Hydroxyazulene and 3-hydroxyguaiazulene: Synthesis and their properties. Tetrahedron Letters. 1989, 30 (48): 6693–6696. doi:10.1016/S0040-4039(00)70653-8.
^ ^18.0 ^18.1 Takase, Kahei; Toyonobu Asao; Yoshikazu Takagi; Tetsuo Nozoe. Syntheses and some properties of 2- and 6-hydroxyazulenes. Chemical Communications. 1968, (7): 368b–370. doi:10.1039/C1968000368B.
^ Yamamura, Kimiaki; Kawabata, Shizuka; Kimura, Takatomo; Eda, Kazuo; Hashimoto, Masao. Novel Synthesis of Benzalacetone Analogues of Naphth[a]azulenes by Intramolecular Tropylium Ion-Mediated Furan Ring-Opening Reaction and X-ray Investigation of a Naphth[1,2-a]azulene Derivative. The Journal of Organic Chemistry. 2005, 70 (22): 8902–6. PMID 16238325. doi:10.1021/jo051409f.

[1] International Union of Pure and Applied Chemistry. Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. 2014: 207. ISBN 978-0-85404-182-4. doi:10.1039/9781849733069.

[Römpp-2] 2.0 ^2.1 Entry on Azulene. at: Römpp Online. Georg Thieme Verlag, retrieved 2019-02-14.

[Alfa-3] 3.0 ^3.1 ^3.2 Datenblatt Azulene, 99% bei AlfaAesar, abgerufen am {{{Abruf}}}.

[4] Sweet, L. I.; Meier, P. G. Lethal and Sublethal Effects of Azulene and Longifolene to Microtox®, Ceriodaphnia dubia, Daphnia magna, and Pimephales promelas (PDF). Bulletin of Environmental Contamination and Toxicology. 1997, 58 (2): 268–274 [2021-08-30]. PMID 8975804. doi:10.1007/s001289900330. hdl:2027.42/42354 . （原始內容存檔 (PDF)於2012-03-30）.

[Sigma-5] 來源：Sigma-Aldrich Co., product no. a97203 .. [2021-09-15]

[6] Salter, Carl; Foresman, James B. Naphthalene and Azulene I: Semimicro Bomb Calorimetry and Quantum Mechanical Calculations. Journal of Chemical Education. 1998, 75 (10): 1341. Bibcode:1998JChEd..75.1341S. doi:10.1021/ed075p1341.

[7] Harmon, A. D.; Weisgraber, K. H.; Weiss, U. Preformed azulene pigments of Lactarius indigo (Schw.) Fries (Russulaceae, Basidiomycetes). Experientia. 1980, 36: 54–56. S2CID 21207966. doi:10.1007/BF02003967.

[8] Anderson, Arthur G.; Steckler, Bernard M. Azulene. VIII. A Study of the Visible Absorption Spectra and Dipole Moments of Some 1- and 1,3-Substituted Azulenes. Journal of the American Chemical Society. 1959, 81 (18): 4941–4946. doi:10.1021/ja01527a046.

[9] Michl, Joseph; Thulstrup, E. W. Why is azulene blue and anthracene white? A simple mo picture. Tetrahedron. 1976, 32 (2): 205. doi:10.1016/0040-4020(76)87002-0.

[10] Tétreault, N.; Muthyala, R. S.; Liu, R. S. H.; Steer, R.P. Control of the Photophysical Properties of Polyatomic Molecules by Substitution and Solvation: The Second Excited Singlet State of Azulene. Journal of Physical Chemistry A. 1999, 103 (15): 2524–31. Bibcode:1999JPCA..103.2524T. doi:10.1021/jp984407q.

[11] Gordon, Maxwell. The Azulenes. Chemical Reviews. 1 February 1952, 50 (1): 127–200. doi:10.1021/cr60155a004.

[12] St. Pfau, Alexander; Plattner, Pl. A. Zur Kenntnis der flüchtigen Pflanzenstoffe VIII. Synthese des Vetivazulens. Helvetica Chimica Acta. 1939, 22: 202–208. doi:10.1002/hlca.19390220126.

[13] Hafner, Klaus; Meinhardt, Klaus-Peter. Azulene. Organic Syntheses. 1984, 62: 134. doi:10.15227/orgsyn.062.0134.

[14] Carret, Sébastien; Blanc, Aurélien; Coquerel, Yoann; Berthod, Mikaël; Greene, Andrew E.; Deprés, Jean-Pierre. Approach to the Blues: A Highly Flexible Route to the Azulenes. Angewandte Chemie International Edition. 2005, 44 (32): 5130–5133. PMID 16013070. doi:10.1002/anie.200501276.

[Lemal-15] Lemal, David M.; Goldman, Glenn D. Synthesis of azulene, a blue hydrocarbon. Journal of Chemical Education. 1988, 65 (10): 923. Bibcode:1988JChEd..65..923L. doi:10.1021/ed065p923.

[16] Churchill, Melvyn R. Transition Metal Complexes of Azulene and Related Ligands. Progress in Inorganic Chemistry. 2007: 53–98. ISBN 9780470166123. doi:10.1002/9780470166123.ch2.

[17] Asao, Toyonobu; Shunji Ito; Noboru Morita. 1-Hydroxyazulene and 3-hydroxyguaiazulene: Synthesis and their properties. Tetrahedron Letters. 1989, 30 (48): 6693–6696. doi:10.1016/S0040-4039(00)70653-8.

[2-_and_6-_hydroxyazulene-18] 18.0 ^18.1 Takase, Kahei; Toyonobu Asao; Yoshikazu Takagi; Tetsuo Nozoe. Syntheses and some properties of 2- and 6-hydroxyazulenes. Chemical Communications. 1968, (7): 368b–370. doi:10.1039/C1968000368B.

[19] Yamamura, Kimiaki; Kawabata, Shizuka; Kimura, Takatomo; Eda, Kazuo; Hashimoto, Masao. Novel Synthesis of Benzalacetone Analogues of Naphth[a]azulenes by Intramolecular Tropylium Ion-Mediated Furan Ring-Opening Reaction and X-ray Investigation of a Naphth[1,2-a]azulene Derivative. The Journal of Organic Chemistry. 2005, 70 (22): 8902–6. PMID 16238325. doi:10.1021/jo051409f.

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化學性質[編輯]

合成[編輯]

薁配合物[編輯]

相關化合物[編輯]

參考資料[編輯]