Allyl methyl disulfide

Fry/microwave Mainly diallyl disulfide, allyl methyl disulfide, vinyl dithiins... 

Among the main garlic-related compounds detected in the breath by GC-AED were allyl methyl sulfide, allyl metfiyl disulfide, diallyl sulfide, diallyl disulfide, 2-propenethiol, dimethyl disulfide, and diallyl trisulfide [54]. Measurements taken shortly after Ae ingestion of garlic and at four hourly intervals thereafter, indicating a more rapid decrease with time of diallyl disulfide than allyl methyl sulfide. Allyl methyl disulfide, diallyl sulfide, and diallyl trisulfide were reported to decrease slowly, while 2-propenethiol vanished rapidly. 

The breath of a test person was analyzed over a time period of about 30 hours by means of proton-transfer-reaction mass spectrometry [55]. After ingestion of cut raw garlic, tiie components allyl metfiyl sulfide, allyl methyl disulfide, diallyl sulfide, diallyl disulfide, diallyl trisulfide, dimethyl sulfide, and acetone were detected. While the concentrations of allyl mediyl disulfide, diallyl sulfide, diallyl disulfide, and diallyl trisulfide reached maximum concentration shortly after ingestion of garlic and declined to baseline values within the next 2-3 h, concentrations of allyl methyl sulfide, dimethyl sulfide, and acetone increased much more slowly... 

Steam distillation of garlic produces an oil that also has several different allyl sulfur constituents such garlic oils can contain about diallyl disulfide (DADS, -26%), diallyl trisulfide (DATS, 19%), allyl methyl trisulfide (15%), allyl methyl disulfide (13%), diallyl tetrasulfide (8%), allyl methyl tetrasulfide (6%), dimethyl pentasulfide (4%), dimethyl trisulfide (3%), and dimethyl hexasulfide (1%). The oil derived from macerated garlic contains vinyldithiins and ajoenes. Storage of garlic in ethanol for several months... 

Various organic sulfides present in Allium have been found to have anticar-cinogenic activity. For example, allyl sulfide, a constituent of garlic oil, inhibited colon cancer in mice exposed to 1,2-dimethylhydrazine, and allyl methyl trisulfide, allyl methyl disulfide, aUyl trisulfide, and allyl sulfide all inhibited benzo[a]pyrene-induced neoplasma of the forestomach and lung in female mice (55). Lam et al. (Chapter 22) investigated the ability of 2-n-butyl thiophene, a constituent of roast beef aroma, to inhibit chemically induced carcinogenesis in three different tumor systems. This compound was found to be effective in the forestomach, lung, and colon models. 

Similar to the S-allyl-L-cysteine sulfoxide in garlic, the C-S lyase can also catalyze the flavor formation from the 5 -methyl-L-cysteine sulfoxide. Therefore, when garlic is cut or crushed, methyl sulfenic acid and allyl sulfenic acid can be produced from 5 -methyl-L-cysteine sulfoxide and S-allyl-L-cysteine sulfoxide, respectively (Figure 18.5). As sulfenic acids are quite reactive, methyl sulfenic acid and allyl sulfenic acid will quickly form the metiiyl 2-propenethiosulfinate and allyl methaneth-iosulfinate. With the similar reaction to that from diallyl thiosulfinate, these thiosulfinates produce allyl methyl disulfide and allyl methyl trisulfide. 

Treatments tested inclnded combinations of whole plants, leaves, and leaf extracts. Valencia orange. Citrus sinensis L., plants were grown in 3.78-L pots in a temperature-controlled greenhouse. Plant samples were composed of 10-week-old whole plants or 2-g samples of fresh leaves. DMDS ( 98% purity), DMTS ( 98.5% purity), and allyl methyl sulfide (AMS) ( 98% purity) were obtained from Sigma-Aldrich, St. Louis, Missouri. Allyl methyl disulfide (AMDS) ( 98% purity) and allyl disulfide (ADS) ( 80.0% purity) were obtained from Frutarom Ltd., Billingham, United Kingdom, and Penta Chemical Company, United States. 

Figure 16.8 Responses of female adult Diaphorina citri presented with sulfur volatiles at (a) 0.25%, (b) 0.5%, or (c) 1.0% concentrations with or without citrus odors. Allyl methyl sulfide (AMS), allyl disulfide (ADS), allyl methyl disulfide (AMDS), dimethyl disulfide (DMDS), and dimethyl trisulfide (DMTS). Black bars followed by same letters are not significantly different (Tukey s honest significant difference, p <.05).

Examination of 37 basidiomycetous yeasts indicated formation of several sulfur volatiles 3-(methylthio)-l-propanol, methanethiol (MT), S-methyl thio-acetate, dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS), allyl methyl sulfide and 4,5-dihydro-3(2//)-thiophenone. The component produced in the largest amounts, 40 100 mg L-1, was 3-(methylthio)-l-propanol29 Cheeseripening yeasts are considered later (Section 11.1.2.4.5). 

Recently, Germain et al. (90) studied the in vivo metabolism of diallyl disulfide (DADS), a garlic compound claimed to have anticarcinogenic effects. After oral administration of a single dose of 200mg/kg, metabolites were measured in the stomach, liver, plasma, and urine by GC coupled with MS over 15 days. DADS was detected in almost all analyzed tissues within the first hours. In addition, the metabolites allylmercaptan (AM) and allyl methyl sulfide (AMS) were detected. The Cmav of the metabolites were higher than that of DADS (1.46 pg/mL). The %ax for DADS was estimated to be less than one hour, whereas this time increased to 24 hours for AM and AMS (90). 

Mixed bimetallic reagents possess two carbon-metal bonds of different reactivity, and a selective and sequential reaction with two different electrophiles should be possible. Thus, the treatment of the l,l-bimetailic compound 15 with iodine, at — 78"C, affords an intermediate zinc carbenoid 16 that, after hydrolysis, furnishes an unsaturated alkyl iodide in 61% yield [Eq. (15) 8]. The reverse addition sequence [AcOH (1 equiv), —80 to — 40 C iodine (1 equiv)] leads to the desired product, with equally high yield [8]. A range of electrophile couples can be added, and the stannylation of 15 is an especially efficient process [Eq. (16) 8]. A smooth oxidation of the bimetallic functionality by using methyl disulfide, followed by an acidic hydrolysis, produces the aldehyde 17 (53%), whereas the treatment with methyl disulfide, followed by the addition of allyl bromide, furnishes a dienic thioether in 76% yield [Eq. (17) 8]. The addition of allylzinc bromide to 1-octenyllithium produces the lithium-zinc bimetallic reagent 18, which can be treated with an excess of methyl iodide, leading to only the monomethylated product 19. The carbon zinc bond is unreactive toward methyl iodide and, after hydrolysis, the alkene 19... 

Boiled Mainly diallyl trisulfide, diallyl disulfide, allyl methyl trisulfide... 

Thermal desorption of purged and trapped garlic breath was studied by GC/MS [53] in which allyl methyl sulfide, diallyl sulfide, diallyl disulfide, -cymene and D-limonene were found consistently in all subjects, however, allyl thiol was detected occasionally. Preliminary evidence suggest that stomach acid caused increased evolution of hydrogen sulfide, a potential breath odor compound, during digestion. 

Three heterocyclic aromatic amines, 2-amino-3-methyl-imidazo[4, 5-f]quinoline (IQ),2-amino-3,4-dimethylimidazo[4,5-f]quinoxaline and 2-amino-3,4-dimethylimidazo[4,5-f]quinoline, have been found in boiled pork juice [109]. Six organosulfur compoimds - diallyl disulfide (DAD), dipropyl disulfide (DPD), diallyl sulftde (DAS), allyl methyl sulfide (AMS), allyl mercaptan (AM) and cysteine - were added separately to the pork juice before reflux boiling and then the mutagenicity of each sample was examined with the Salmonella typhimurium strain TA98 in the presence of S9 mix. All six compounds were found to inhibit the mutagenicity of boiled pork juice. The greatest inhibitory effect was observed with DAD and DPD, and this was 111-fold higher than that of... 

Known active constituents of garlic (there are at least 35 other constituents whose actions are unknown) ajoene, allicin, aliin, allixin, allyl mercaptan, allyl methyl thiosulfmate, allyl methyl trisulfide, allyl propyl disulfide, diallyl disulfide, diallyl hepta sulfide, diallyl hexa sulfide, diallyl penta sulfide, diallyl sulfide, diallyl tetra sulfide, diallyl tri sulfide, dimethyl disulfide, dimethyl trisulfide, dirpopyl disulfide, methyl ajoene, methyl allyl thiosulfmate, propyline sulfide, 2-vinyl-4H-l, 3-tithiin, 3-vinyl-4H-1, 2dithiin, S-allyl cysteine sulfoxide, S-allyl mercapto, cysteine. 

Fourteen members of this group of flavouring substances, ethane-1,1 -dithiol (No. 1660), 4-mercapto-2-pentanone (No. 1670), diisopentyl thiomalate (No. 1672), cis- and frans-mercapto-p-menthan-3-one (No. 1673), 2,4,6-trithiaheptane (No. 1684), ( )-2,8-epithio-c/s-p-menthane (No. 1685), mixture of 3,6-diethyl-1,2,4,5-tetrathiane and 3,5-diethyl-1,2,4-trithiolane (No. 1687), ( )-3-(methylthio)heptanal (No. 1692), ethyl methyl disulfide (No. 1693), ethyl propyl trisulfide (No. 1695), methyl isopentyl disulfide (No. 1696), butyl ethyl disulfide (No. 1698), allyl propyl disulfide (No. 1700) and bis(1-mercaptopropyl)sulfide (No. 1709), have assay values of <95%. Information on the safety of the secondary components of these 14 compounds is summarized in Annex 5 (Summary of the safety evaluation of secondary components for flavouring agents with minimum assay values of less than 95%). The secondary component of diisopentyl thiomalate, diisopentyl thiotartronate, is expected to share the same metabolic fate as the primary substance. The secondary components of frans-mercapto-p-menthan-3-one, piperitone (No. 435) and a-terpineol (No. 366), are expected to undergo rapid absorption, distribution, metabolism and excretion and were evaluated at previous... 

Allyl mercaptan and allyl methyl sulfide were identified as metabolites of diallyl disulfide when primary rat hepatocytes were incubated with either diallyl disulfide or diallyl sulfide. The highest identified concentration of allyl methyl sulfide (0.93 0.08 pg/ml at 90 min) was markedly lower than that of allyl mercaptan (46.2 6.6 pg/ml at 60 min). The results also showed that allyl methyl sulfide is a metabolite of diallyl sulfide (Sheen et al., 1999). 

Treatment of 2-methylthiirane with t-butyl hydroperoxide at 150 °C in a sealed vessel gave very low yields of allyl disulfide, 2-propenethiol and thioacetone. The allyl derivatives may be derived from abstraction of a hydrogen atom from the methyl group followed by ring opening to the allylthio radical. Percarbonate derivatives of 2-hydroxymethylthiirane decompose via a free radical pathway to tar. Acrylate esters of 2-hydroxymethylthiirane undergo free radical polymerization through the double bond. 

Nishimura and coworkers57-59 studied the y-radiolysis of aqueous solutions of sulfoxide amino acids. Sulfoxide amino acids are the precursors of the flavors of onions (S-propyl-L-cysteine sulfoxide, S-methyl-L-cysteine sulfoxide and S-(l-propenyl)-L-cysteine sulfoxide) and garlic (S-allyl-L-cysteine sulfoxide). In studies on sprout inhibition of onion by /-irradiation it was found that the characteristic flavor of onions became milder. In the y-radiolysis of an aqueous solution of S-propyl-L-cysteine sulfoxide (PCSO)57,58 they identified as the main products alanine, cysteic acid, dipropyl disulfide and dipropyl sulfide. In the radiolysis of S-allyl-L-cysteine sulfoxide (ACSO) they found that the main products are S-allyl-L-cysteine, cysteic acid, cystine, allyl alcohol, propyl allyl sulfide and diallyl sulfide. The mechanisms of formation of the products were partly elucidated by the study of the radiolysis in the presence of N20 and Br- as eaq - and OH radicals scavengers, respectively. 

The complex also undergoes a variety of addition reactions with reagents such as methyl iodide, hydrochloric acid, benzoyl chloride, and allyl chloride.8 In a reaction similar to that of the decarboxylation of aldehydes, the complex will abstract CS from carbon disulfide to give the irans-thiocarbonyl complex rans-RhClCS[P(C8H6)5]2.9... 

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