α-葎草烯

葎草烯
	IUPAC名; (1E,4E,8E)-2,6,6,9-Tetramethylcycloundeca-1,4-8-triene
別名	蛇麻烯、α-石竹烯
識別
CAS編號	6753-98-6
PubChem	5281520
ChemSpider	4444853
SMILES	C\1=C/C(C)(C)C/C=C(/CC/C=C(/C/1)C)C;
InChI	1/C15H24/c1-13-7-5-8-14(2)10-12-15(3,4)11-6-9-13/h6-7,10-11H,5,8-9,12H2,1-4H3/b11-6+,13-7+,14-10+;
InChIKey	FAMPSKZZVDUYOS-HRGUGZIWBF
ChEBI	5768
性質
化學式	C15H24
摩爾質量	204.35 g·mol−1
外觀	淡黃綠色的透明液體
密度	0.886 g/cm3
熔點	25 °C（298 K）
沸點	106 - 107 °C（272 K）
危險性
	致死量或濃度：
LD50（中位劑量）	>48 mg/kg
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

α-葎草烯（英語：Humulene）^{[註 1]}，又名蛇麻烯或α-石竹烯，是天然存在的單環倍半萜，分子式C₁₅H₂₄，可看作三個異戊二烯單元構成，分子有三個非共軛雙鍵。

Quick Facts 葎草烯, 識別 ...

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葎草烯最早從啤酒花（葎草屬，學名：Humulus）精油發現，因此得名^[1]。葎草烯有個雙環的同分異構體 β-石竹烯，在很多有香氣植物中，都能提取出兩者的混合物。

發現

葎草烯是蛇麻花精油成分之一，其濃度根據品種不同而變，最高可占精油40%^[2]。釀啤酒過程中會產生多種葎草烯的環氧化物，根據GC-MS及氣味分析研究，葎草烯環氧衍生物水解會散發出啤酒花香氣^[3]^[4]。

分佈

葎草烯與β-石竹烯在各大洲的許多植物中都能找到，能釋放葎草烯的植物有松樹^[5]、橘園^[6]、煙草 ^[7]和向日葵^[8]。在芳香氣氛的植物精油中也能找到葎草烯，如藥用鼠尾草 ^[9]、烏藥、人參屬的三七、花旗參 ^[10]、留蘭香（可占精油29.9 %）^[11]、姜科植物^[12]、霧社木姜子（一種中國月桂樹）^[13]、erva baleeira（馬鞭草科一種灌木，位於南美洲沿海）的葉片提取物中可達4 %，另有25%反式石竹烯^[14]是越南香菜和大麻屬植物的香氣成分^[15]。

合成

葎草烯衍生自法尼基焦磷酸（FPP），FPP合成葎草烯過程由倍半萜合成酶催化^[16]，FPP脫焦磷酸基團後產生烯丙基陽離子^[16]。

實驗室合成葎草烯的方法有很多，如模擬生物合成從法尼醇合成葎草烯（Corey合成）；閉合大環化合物不同位置的碳－碳鍵；鈦催化羰基偶聯反應（McMurry合成）；烯丙基鹵化物和受保護羥腈陰離子內烷基化（Takahashi合成）等^[17]。有研究報道了更簡單構建碳－碳鍵和環結構的方法，用四部份組裝和鈀介導環化兩步合成^[18]。

葎草烯上兩個已取代雙鍵更活潑，計算結果顯示有四種不同構象^[19]。

應用

有研究報道植物精油的葎草烯有潛在抗炎作用^[20]^[21]。2015年，巴西研究員用氣相色譜法證明鼠尾草葉油的葎草烯可抑制埃及伊蚊繁殖^[22]^[23]。

備註

[註 1]
下文中如無說明，皆以葎草烯指代α-葎草烯。

參考文獻

[1]
Glenn Tinseth, "Hop Aroma and Flavor", January/February 1993, Brewing Techniques. <http://realbeer.com/hops/aroma.html （頁面存檔備份，存於互聯網檔案館）> Accessed July 21, 2010
[2]
Katsiotis, S. T.; Langezaal, C. R.; Scheffe, J. J. C. Analysis of the Volatile Compounds from Cones of Ten Humulus lupulus Cultivars. Planta Med. 1989, 55 (7): 634. doi:10.1055/s-2006-962205.
[3]
Yange, Xiaogen; Lederer, Cindy; McDaniel, Mina; Deinzer, Max. Evaluation of hydrolysis products of humulene epoxides II and III. Journal of Agricultural and Food Chemistry. 1993, 41 (8): 1300–1304. doi:10.1021/jf00032a026.
[4]
Peackock, Val; Deinzer, Max. Chemistry of hop aroma in beer. Journal of the American Society of Brewing Chemists. 1981, 39. （原始內容存檔於2013-12-30）.
[5]
D. Helmig; J. Ortega; T. Duhl; D. Tanner; A. Guenther; P. Harley; C. Wiedinmyer; J. Milford; T. Sakulyanontvittaya. Sesquiterpene emissions from pine trees--identifications, emission rates and flux estimates for the contiguous United States. Environ. Sci. Technol. 2007, 41 (5): 1545–1553 [2022-07-11]. Bibcode:2007EnST...41.1545H. PMID 17396639. doi:10.1021/es0618907. （原始內容存檔於2022-07-11）.
[6]
P. Ciccioli; E. Brancaleoni; M. Frattoni; V. Di Palo; R. Valentini; G. Tirone; G. Seufert; N. Bertin; U. Hansen; O. Csiky; R. Lenz; M. Sharma. Emission of reactive terpene compounds from orange orchards and their removal by within-canopy processes. J. Geophys. Res. 1999, 104 (D7): 8077–8094. Bibcode:1999JGR...104.8077C. doi:10.1029/1998JD100026 .
[7]
C. De Moraes; M. Mescher; J. Tumlinson. Caterpillar-induced nocturnal plant volatiles repel conspecific females. Nature. 2001, 410 (6828): 577–580. Bibcode:2001Natur.410..577D. PMID 11279494. S2CID 4408480. doi:10.1038/35069058.
[8]
G. Schuh; A. Heiden; T. Hoffmann; J. Kahl; P. Rockel; J. Rudolph; J. Wildt. Emissions of Volatile Organic Compounds from Sunflower and Beech: Dependence on Temperature and Light Intensity. J. Atmos. Chem. 1997, 27 (3): 291–318. Bibcode:1997JAtC...27..291S. S2CID 94314856. doi:10.1023/A:1005850710257.
[9]
Bouajaj, S; Benyamna, A; Bouamama, H; Romane, A; Falconieri, D; Piras, A; Marongiu, B. Antibacterial, allelopathic and antioxidant activities of essential oil of Salvia officinalis L. growing wild in the Atlas Mountains of Morocco. Nat Prod Res. 2013, 27 (18): 1673–6. PMID 23240623. S2CID 29522122. doi:10.1080/14786419.2012.751600.
[10]
Cho, IH; Lee, HJ; Kim, YS. Differences in the volatile compositions of ginseng species (Panax sp.). J Agric Food Chem. Aug 2012, 60 (31): 7616–22. PMID 22804575. doi:10.1021/jf301835v.
[11]
Chauhan, SS; Prakash, O; Padalia, RC; Vivekanand, Pant AK; Mathela, CS. Chemical diversity in Mentha spicata: antioxidant and potato sprout inhibition activity of its essential oils. Nat Prod Commun. 2011, 6 (9): 1373–8. PMID 21941918.
[12]
Suthisut, D; Fields, PG; Chandrapatya, A. Contact toxicity, feeding reduction, and repellency of essential oils from three plants from the ginger family (Zingiberaceae) and their major components against Sitophilus zeamais and Tribolium castaneum. J Econ Entomol. 2011, 104 (4): 1445–54. PMID 21882715. S2CID 45872520. doi:10.1603/ec11050.
[13]
Ho, CL; Wang, EI; Tseng, YH; Liao, PC; Lin, CN; Chou, JC; Su, YC. Composition and antimicrobial activity of the leaf and twig oils of Litsea mushaensis and L. linii from Taiwan. Nat Prod Commun. 2010, 5 (11): 1823–8. PMID 21213991.
[14]
de Carvalho, Jr.; Rodrigues, R.F.; Sawaya, A.C.; Marques, M.O.; Shimizu, M.T. Chemical composition and antimicrobial activity of the essential oil of Cordia verbenacea D.C. Journal of Ethnopharmacology. 2004, 95 (2–3): 297–301. PMID 15507352. doi:10.1016/j.jep.2004.07.028.
[15]
Hillig, Karl W. A chemotaxonomic analysis of terpenoid variation in Cannabis. Biochemical Systematics and Ecology. October 2004, 32 (10): 875–891. ISSN 0305-1978. doi:10.1016/j.bse.2004.04.004.
[16]
Moss, G.P., "Humulene derived sesquiterpenoid biosynthesis." International Union of Biochemistry and Molecular Biology Enzyme Nomenclature. Accessed April 10, 2011. http://www.enzyme-database.org/reaction/terp/humul.html （頁面存檔備份，存於互聯網檔案館）
[17]
Goldsmith, David. "The total synthesis of natural products". Canada: John Wiley & Sons. 1997 pp 129-133
[18]
Hu, Tao & Corey, E.J. Short Syntheses of (±)-δ-Araneosene and Humulene Utilizing a Combination of Four-Component Assembly and Palladium-Mediated Cyclization. Organic Letters. 2002, 4 (14): 2441–2443. PMID 12098267. doi:10.1021/ol026205p.
[19]
Neuenschwander, U; et al. Origin of Regioselectivity in α-Humulene Functionalization. J. Org. Chem. 2012, 77 (6): 2865–2869. PMID 22332847. doi:10.1021/jo3000942.
[20]
Passosa, G.F.; Fernandesa, ES.; et al. Anti-inflammatory and anti-allergic properties of the essential oil and active compounds from Cordia verbenacea. Journal of Ethnopharmacology. 2007, 110 (2): 323–333. PMID 17084568. doi:10.1016/j.jep.2006.09.032.
[21]
Fernandes E.S.; Passos G.F.; Medeiros R.; da Cunha F.M.; Ferreira J.; Campos M.M.; Pianowski L.F.; Calixto J.B. Anti-inflammatory effects of compounds alpha-humulene and (−)-trans-caryophyllene isolated from the essential oil of Cordia verbenacea. European Journal of Pharmacology. 2007, 569 (3): 228–236. PMID 17559833. doi:10.1016/j.ejphar.2007.04.059.
[22]
Janelle Lassalle. Humulene. The Cannigma. 2020-09-19 [2021-01-27]. （原始內容存檔於2022-07-11）.
[23]
Santos da Silva, R.C.; Milet-Pinheiro, P.; Bezerra da Silva, P.C.; Gomes da Silva, A.; Vanusa da Silva, M.; Amaral Ferraz Navarro, D.M.; da Silva, N.H.; et al. Boudko, Dmitri , 編. (E)-Caryophyllene and α-Humulene: Aedes aegypti Oviposition Deterrents Elucidated by Gas Chromatography-Electrophysiological Assay of Commiphora leptophloeos Leaf Oil. PLOS ONE. 2015-12-19, 10 (12): e0144586. Bibcode:2015PLoSO..1044586D. PMC 4674132 . PMID 26650757. doi:10.1371/journal.pone.0144586 .

[1] [註 1]
下文中如無說明，皆以葎草烯指代α-葎草烯。

[2] [1]
Glenn Tinseth, "Hop Aroma and Flavor", January/February 1993, Brewing Techniques. <http://realbeer.com/hops/aroma.html （頁面存檔備份，存於互聯網檔案館）> Accessed July 21, 2010

[3] [2]
Katsiotis, S. T.; Langezaal, C. R.; Scheffe, J. J. C. Analysis of the Volatile Compounds from Cones of Ten Humulus lupulus Cultivars. Planta Med. 1989, 55 (7): 634. doi:10.1055/s-2006-962205.

[4] [3]
Yange, Xiaogen; Lederer, Cindy; McDaniel, Mina; Deinzer, Max. Evaluation of hydrolysis products of humulene epoxides II and III. Journal of Agricultural and Food Chemistry. 1993, 41 (8): 1300–1304. doi:10.1021/jf00032a026.

[5] [4]
Peackock, Val; Deinzer, Max. Chemistry of hop aroma in beer. Journal of the American Society of Brewing Chemists. 1981, 39. （原始內容存檔於2013-12-30）.

[6] [5]
D. Helmig; J. Ortega; T. Duhl; D. Tanner; A. Guenther; P. Harley; C. Wiedinmyer; J. Milford; T. Sakulyanontvittaya. Sesquiterpene emissions from pine trees--identifications, emission rates and flux estimates for the contiguous United States. Environ. Sci. Technol. 2007, 41 (5): 1545–1553 [2022-07-11]. Bibcode:2007EnST...41.1545H. PMID 17396639. doi:10.1021/es0618907. （原始內容存檔於2022-07-11）.

[7] [6]
P. Ciccioli; E. Brancaleoni; M. Frattoni; V. Di Palo; R. Valentini; G. Tirone; G. Seufert; N. Bertin; U. Hansen; O. Csiky; R. Lenz; M. Sharma. Emission of reactive terpene compounds from orange orchards and their removal by within-canopy processes. J. Geophys. Res. 1999, 104 (D7): 8077–8094. Bibcode:1999JGR...104.8077C. doi:10.1029/1998JD100026 .

[8] [7]
C. De Moraes; M. Mescher; J. Tumlinson. Caterpillar-induced nocturnal plant volatiles repel conspecific females. Nature. 2001, 410 (6828): 577–580. Bibcode:2001Natur.410..577D. PMID 11279494. S2CID 4408480. doi:10.1038/35069058.

[9] [8]
G. Schuh; A. Heiden; T. Hoffmann; J. Kahl; P. Rockel; J. Rudolph; J. Wildt. Emissions of Volatile Organic Compounds from Sunflower and Beech: Dependence on Temperature and Light Intensity. J. Atmos. Chem. 1997, 27 (3): 291–318. Bibcode:1997JAtC...27..291S. S2CID 94314856. doi:10.1023/A:1005850710257.

[10] [9]
Bouajaj, S; Benyamna, A; Bouamama, H; Romane, A; Falconieri, D; Piras, A; Marongiu, B. Antibacterial, allelopathic and antioxidant activities of essential oil of Salvia officinalis L. growing wild in the Atlas Mountains of Morocco. Nat Prod Res. 2013, 27 (18): 1673–6. PMID 23240623. S2CID 29522122. doi:10.1080/14786419.2012.751600.

[11] [10]
Cho, IH; Lee, HJ; Kim, YS. Differences in the volatile compositions of ginseng species (Panax sp.). J Agric Food Chem. Aug 2012, 60 (31): 7616–22. PMID 22804575. doi:10.1021/jf301835v.

[12] [11]
Chauhan, SS; Prakash, O; Padalia, RC; Vivekanand, Pant AK; Mathela, CS. Chemical diversity in Mentha spicata: antioxidant and potato sprout inhibition activity of its essential oils. Nat Prod Commun. 2011, 6 (9): 1373–8. PMID 21941918.

[13] [12]
Suthisut, D; Fields, PG; Chandrapatya, A. Contact toxicity, feeding reduction, and repellency of essential oils from three plants from the ginger family (Zingiberaceae) and their major components against Sitophilus zeamais and Tribolium castaneum. J Econ Entomol. 2011, 104 (4): 1445–54. PMID 21882715. S2CID 45872520. doi:10.1603/ec11050.

[14] [13]
Ho, CL; Wang, EI; Tseng, YH; Liao, PC; Lin, CN; Chou, JC; Su, YC. Composition and antimicrobial activity of the leaf and twig oils of Litsea mushaensis and L. linii from Taiwan. Nat Prod Commun. 2010, 5 (11): 1823–8. PMID 21213991.

[15] [14]
de Carvalho, Jr.; Rodrigues, R.F.; Sawaya, A.C.; Marques, M.O.; Shimizu, M.T. Chemical composition and antimicrobial activity of the essential oil of Cordia verbenacea D.C. Journal of Ethnopharmacology. 2004, 95 (2–3): 297–301. PMID 15507352. doi:10.1016/j.jep.2004.07.028.

[16] [15]
Hillig, Karl W. A chemotaxonomic analysis of terpenoid variation in Cannabis. Biochemical Systematics and Ecology. October 2004, 32 (10): 875–891. ISSN 0305-1978. doi:10.1016/j.bse.2004.04.004.

[biosynthesis-17] [16]
Moss, G.P., "Humulene derived sesquiterpenoid biosynthesis." International Union of Biochemistry and Molecular Biology Enzyme Nomenclature. Accessed April 10, 2011. http://www.enzyme-database.org/reaction/terp/humul.html （頁面存檔備份，存於互聯網檔案館）

[18] [17]
Goldsmith, David. "The total synthesis of natural products". Canada: John Wiley & Sons. 1997 pp 129-133

[19] [18]
Hu, Tao & Corey, E.J. Short Syntheses of (±)-δ-Araneosene and Humulene Utilizing a Combination of Four-Component Assembly and Palladium-Mediated Cyclization. Organic Letters. 2002, 4 (14): 2441–2443. PMID 12098267. doi:10.1021/ol026205p.

[20] [19]
Neuenschwander, U; et al. Origin of Regioselectivity in α-Humulene Functionalization. J. Org. Chem. 2012, 77 (6): 2865–2869. PMID 22332847. doi:10.1021/jo3000942.

[21] [20]
Passosa, G.F.; Fernandesa, ES.; et al. Anti-inflammatory and anti-allergic properties of the essential oil and active compounds from Cordia verbenacea. Journal of Ethnopharmacology. 2007, 110 (2): 323–333. PMID 17084568. doi:10.1016/j.jep.2006.09.032.

[22] [21]
Fernandes E.S.; Passos G.F.; Medeiros R.; da Cunha F.M.; Ferreira J.; Campos M.M.; Pianowski L.F.; Calixto J.B. Anti-inflammatory effects of compounds alpha-humulene and (−)-trans-caryophyllene isolated from the essential oil of Cordia verbenacea. European Journal of Pharmacology. 2007, 569 (3): 228–236. PMID 17559833. doi:10.1016/j.ejphar.2007.04.059.

[JLassalle-23] [22]
Janelle Lassalle. Humulene. The Cannigma. 2020-09-19 [2021-01-27]. （原始內容存檔於2022-07-11）.

[24] [23]
Santos da Silva, R.C.; Milet-Pinheiro, P.; Bezerra da Silva, P.C.; Gomes da Silva, A.; Vanusa da Silva, M.; Amaral Ferraz Navarro, D.M.; da Silva, N.H.; et al. Boudko, Dmitri , 編. (E)-Caryophyllene and α-Humulene: Aedes aegypti Oviposition Deterrents Elucidated by Gas Chromatography-Electrophysiological Assay of Commiphora leptophloeos Leaf Oil. PLOS ONE. 2015-12-19, 10 (12): e0144586. Bibcode:2015PLoSO..1044586D. PMC 4674132 . PMID 26650757. doi:10.1371/journal.pone.0144586 .

[註 1]

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

[11]

[12]

[13]

[14]

[15]

[16]

[17]

[18]

[19]

[20]

[21]

[22]

[23]