Humulone

 ( Cyclohexadienes ) 

Humulone ( α-lupulic acid), a Vinylogy type of organic acid, is a bitter-tasting chemical compound found in the resin of mature hops ( Humulus lupulus). Humulone is a prevalent member of the class of compounds known as , which collectively give hopped beer its characteristic bitter flavor.

---

Chemistry In terms of structure, humulone is a phloroglucinol derivative with three isoprenoid side-chains. Two side-chains are prenyl groups and one is an isovaleryl group. The acidity of the ring enol moieties that give rise to its designation as an acid lie in their Vinylogy relationship with the ring and side chain carbonyl functional groups.

---

Isohumulone During the brewing process, humulone degrades to cis- and trans-isohumulone. These “alpha acids” survive the boiling process, although numerous oxidized derivatives are produced.Blanco, C. A.; Rojas, A; Caballero, P. A.; Ronda, F; Gomez, M; Caballero, I., “A better control of beer properties by predicting acidity of hop iso-α-acids”, Trends in Food Science & Technology, Volume 17, Issue 7, July 2006, Pages 373-377, ISSN 0924-2244, . The iso-alpha acids are significantly more soluble than humulone at the pH levels typically present in the brewing process.Esslinger, H. M. and Narziss, L. 2003. “Beer.” in- Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH Verlag GmbH & Co. KGaA, 2009

---

Laboratory synthesis

Humulone can be synthesized by the acylation of benzene-1,2,3,5-tetrol with isovaleryl chloride to give 2,3,4,6-tetrahydroxyisovalerophenone. This step is followed by prenylation with 1-bromo-3-methyl-2-butene to give humulone.

---

Biosynthesis

As determined by INADEQUATE 2D NMR, the biosynthesis of humulone in Humulus lupulus starts with an isovaleryl-CoA unit and 3 malonyl-CoA units catalyzed by phlorovalerophenone synthase. This conversion yields the benzenoid 3-methyl-1-(2,4,6-trihydroxyphenyl)butan-1-one. Dimethylallyl pyrophosphate is then obtained from the deoxyxylulose pathway, where prenylation of the benzenoid occurs, yielding humulone.

isovaleryl-CoA + 3 malonyl-CoA → 4 CoASH + 3 CO2 + 3-methyl-1-(2,4,6-trihydroxyphenyl)butan-1-one

3-methyl-1-(2,4,6-trihydroxyphenyl)butan-1-one + 2 DMAPP →C₂₁H₃₀O₅

---

Research

Humulone is under basic research with in vitro studies to determine if it has biological properties, such as possible GABAA receptor activity or antibacterial effects.

Categories: Cyclohexadienes, 3-hydroxypropenals, Terpeno-phenolic Compounds, Bitter Compounds, Triols, Secondary Alcohols, Tertiary Alcohols, Humulus

Post Comment