薁

薁
	IUPAC名めい; Azulene
	系けい统名; bicyclo[5.3.0]decapentaene; Azulene; 双そう环[5.3.0]癸みずのと五ご烯
别名	蓝烃、甘あま菊きく環たまき
识别
CAS号ごう	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
性せい质
化学かがく式しき	C10H8
摩ま尔质量りょう	128.17 g·mol⁻¹
外そと观	青あお蓝色片へん状じょう晶あきら体からだ
氣味きみ	无
密度みつど	1.037 g/cm3
熔点	99 °C（372 K）（）
沸点ふってん	242 °C（515 K）（）
溶解ようかい性せい（水みず）	几乎不溶ふよう
溶解ようかい性せい	可か溶于有ゆう机つくえ溶剂
磁化じか率りつ	-98.5·10−6 cm3/mol
热力学がく
ΔでるたcHm⦵	−1266.5 kcal/mol
危险性せい
警示术语	R：R51/53
安全あんぜん术语	S：S61
欧おう盟めい分ぶん类	N
主要しゅよう危害きがい	有毒ゆうどく
闪点	76.66 °C
	若わか非ひ注ちゅう明あかり，所有しょゆう数すう据すえ均ひとし出自しゅつじ标准状じょう态（25 ℃，100 kPa）下した。

薁（ào）（英語えいご：Azulene）又また名な蓝烃，是ぜ萘的てき同どう分ぶん异构体たい，分子ぶんし式しき為ためC₁₀H₈，為ため青あお蓝色片へん状じょう晶あきら体からだ。它的偶极矩のり对碳氢化合かごう物ぶつ来らい说不寻常高だか。

化学かがく性せい质

薁的共振きょうしん结构示しめせ意い图

薁是一种含有七元环与五元环的稠环芳よし烃。和わ萘相似そうじ，薁分子中こなか含有がんゆう10个πぱい电子的てき共振きょうしん结构，但ただし是ぜ其共振きょうしん稳定能のう只ただ有ゆう萘的てき一半いっぱん。薁可看み做由环庚三さん烯正离子（䓬离子こ）和かず环戊二烯负离子构成，因いん此薁分子ぶんし具有ぐゆう约1.08D的てき电偶极矩。^[8]由よし于极性せい，薁的五元环一侧容易发生亲电取代だい反はん应，七元环一侧容易发生亲核取と代だい反はん应。薁的芳香ほうこう性せい略りゃく低てい于萘，更さら容易たやす加か氢生成せいせい环戊烷并环庚烷。

薁在基もと态的极性反映はんえい在ざい它的深ふか色しょく上じょう，这对于小的てき不ふ饱和芳よし族ぞく化合かごう物ぶつ来らい说是不ふ寻常的てき。^[9]薁不符合ふごう卡莎规则，其许多た衍生物せいぶつ也都不ふ会かい在ざい最低さいてい激げき发态发出荧光。^[10]

合成ごうせい

由よし于薁的てき特殊とくしゅ结构，科学かがく家か一直关注其合成方法。^[11]1939年ねん，科学かがく家かSt. Pfau和わPlattner用よう茚满和わ重じゅう氮乙酸さん乙おつ酯首くび次じ人工じんこう合成ごうせい薁。^[12]

有效ゆうこう的てき薁一いち锅法涉わたる及了环戊二に烯与あずか不ふ饱和的てきC₅合成ごうせい子こ的てき环化。^[13]环庚三さん烯前ぜん体からだ的てき替がえ代だい方法ほうほう早はや已やめ为人所しょ知ち，下面かめん显示了りょう一いち种说明あかり性せい方法ほうほう。^[14]^[15]

步ふ骤：

环庚三さん烯和わ三さん氯乙酰氯生成せいせい的てき二に氯乙烯酮的てき 2+2 环加成なり反はん应
重じゅう氮甲烷的てき插入そうにゅう反はん应（英えい语：Insertion reaction）
用よう二甲基甲酰胺脱だつ卤化氢
用よう硼氢化か钠通つう过Luche还原反はん应还原成なり醇あつし
伯はく吉きち斯试剂的てき消しょう除じょ反はん应
四よん氯对苯醌氧化
用よう聚甲基もと氢硅氧烷（英えい语：polymethylhydrosiloxane）、乙おつ酸さん钯、磷酸钾和わDPDB配はい体たい脱だつ卤（英えい语：dehalogenation）

薁配合はいごう物ぶつ

在ざい有ゆう机つくえ金属きんぞく化学かがく中なか，薁可作さく为低价金属きんぞく中心ちゅうしん的てき配はい体たい，其配合はいごう物ぶつ包括ほうかつ (azulene)Mo₂(CO)₆和かず(azulene)Fe₂(CO)₅。^[16]

相あい关化合かごう物ぶつ

1-羟基薁是不ふ稳定的てき绿色油状ゆじょう液体えきたい，没ぼつ有ゆう酮-烯醇互变异构。^[17]稳定的てき2-羟基薁可以由2-甲きのえ氧基薁和氢溴酸さん反はん应而成なり，有ゆう酮-烯醇互变异构。^[18]它的酸性さんせい比ひ苯酚和わ萘酚强つよ，在ざい水中すいちゅう的てきpK_a为8.71。6-羟基薁的酸性さんせい更さら强きょう，在ざい水中すいちゅう的てき pK_a为7.38。^[18]

在ざい萘并[a]薁中，萘环和薁的1,2-位置いち键合。这个系けい统与[4]螺にし烯类似，并非一いち个平面めん。^[19]

參考さんこう資料しりょう

^ 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 . （原始げんし内容ないよう存そん档 (PDF)于2012-03-30）.
^ 来らい源みなもと：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 . （原始げんし内容ないよう存そん档 (PDF)于2012-03-30）.

[Sigma-5] 来らい源みなもと：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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