抄録
Garlic, Allium sativum L. (Liliaceae) occupies the top spot of the National Cancer Institute list of designer foods that protect cancer. The various biological activities of these foods are classified into roughly 2 functions: cardiovascular disease prevention and cancer prevention. The chemistry of garlic sulfides is summarized in the text book editted by Block. Commercial Chinese garlic was roughly chopped and blended in a mixer along with acetone; subsequently, the mixture was soaked in acetone for 3 days at room temperature. The filtrate was evaporated at 40℃ in vacuo to obtain a residue that was then subjected to polystyrene gel (Diaion HP-20) column chromatography. It was first eluted with water and then with Me0H. The methanolic eluate was partitioned between AcOEt and water. The organic residues, which showed the ability to control macrophage activation, were separated repeatedly to provide several novel sulfides named garlicnins B_1, B_2, B_3, at, C_1, C_2, C_3, D, and E. Garlicnin B_1 (1) is the first example of cyclic sulfoxides carrying a tetrahydrothiphene skeleton together with garlicnin A from garlic. The proposed production of this compound is shown in Chart 1: allicin would then be transformed to 1-propenyl 1-propene-thiosulfinate and then become converted to 2,3-dimethylbutanedithial 1-oxide by [3,3]-sigmatropic rearrangement. Next, that compound may be ring-closed to a thiophene derivative, which would be further attached by 1-propenesulfenic acid derived from allicin to finally produce garlicnin B_1 (1). Garlicnin C_1 (2) is a characteristic cyclic sulfoxide equipping an ally! dithiin group and a propenyl sufoxide group at C-2 and C-5, respectively. Garlicnin D (3) is 2-vinyl-4H-1,3-dithiin derivative and would be produced from 2 moles of thioacrolein. Garlicnin E (4) is regarded as analogous substance increasing each 3 atoms in carbon and sulfur than those of azoene. Finding of these novel sufoxides from garlic accumulates new chemistry to the Allium sulfide field, and their pharmacological investigations would be develop natural, healthy foods that potentially prevent and combat disease.
