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[ CAS No. 539-86-6 ] {[proInfo.proName]}

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3d Animation Molecule Structure of 539-86-6
Chemical Structure| 539-86-6
Chemical Structure| 539-86-6
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Product Details of [ 539-86-6 ]

CAS No. :539-86-6 MDL No. :MFCD00468100
Formula : C6H10OS2 Boiling Point : -
Linear Structure Formula :- InChI Key :JDLKFOPOAOFWQN-UHFFFAOYSA-N
M.W : 162.27 Pubchem ID :65036
Synonyms :
Diallyl thiosulfinate
Chemical Name :S-Allyl prop-2-ene-1-sulfinothioate

Calculated chemistry of [ 539-86-6 ]

Physicochemical Properties

Num. heavy atoms : 9
Num. arom. heavy atoms : 0
Fraction Csp3 : 0.33
Num. rotatable bonds : 5
Num. H-bond acceptors : 1.0
Num. H-bond donors : 0.0
Molar Refractivity : 45.88
TPSA : 61.58 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -6.36 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.95
Log Po/w (XLOGP3) : 1.31
Log Po/w (WLOGP) : 2.62
Log Po/w (MLOGP) : 1.18
Log Po/w (SILICOS-IT) : 0.96
Consensus Log Po/w : 1.61

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -1.34
Solubility : 7.39 mg/ml ; 0.0456 mol/l
Class : Very soluble
Log S (Ali) : -2.2
Solubility : 1.02 mg/ml ; 0.00626 mol/l
Class : Soluble
Log S (SILICOS-IT) : -1.7
Solubility : 3.24 mg/ml ; 0.02 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 2.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 3.6

Safety of [ 539-86-6 ]

Signal Word:Danger Class:6.1
Precautionary Statements:P261-P264-P270-P271-P280-P302+P352-P304+P340-P310-P330-P361-P403+P233-P405-P501 UN#:2810
Hazard Statements:H301-H311-H331 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 539-86-6 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 539-86-6 ]

[ 539-86-6 ] Synthesis Path-Downstream   1~47

  • 3
  • [ 2179-57-9 ]
  • [ 539-86-6 ]
YieldReaction ConditionsOperation in experiment
96% With 3,3-dimethyldioxirane; In acetone; at -50 - -20℃; for 0.75h;Inert atmosphere;Product distribution / selectivity; Example 1: Synthesis of compound (3). allicin.An acetone solution of DMDO (31 mL, 0.07M, 2.2 mmol) was added dropwise over 15 min to compound (2), diallyldisulphide (0.29 g, 2.0 mmol) in acetone (1 mL) at -50 C under argon. The resulting light yellow reaction mixture was allowed to stir for 30 min while slowly warming to -20 C. The resulting clear reaction mixture was concentrated in vacuo. The crude residue (0.31g, 98%) was further purified by column chromatography (eluting with 5% Et20 in pentane) to yield compound (3), allicin (0.31g, 1.9 mmol, 96% yield, purity >95% and up to 99.9%) as a light yellow liquid.
92% With Peroxyformic acid; In methanol; at 0℃; for 0.25h; Distilled diallyl-disulfide (DADS; 0.5 g, 3.5 mmol) was mixed in 2.5 mL methanol and stirred for 5 min at 0 C. Performic acid solution (2.0 mL) (as described in Section 3.2.6.) was added slowly tothe mixture. The reaction was quenched after 15 min by addition of 25 mL distilled water and themixture was extracted three times with DCM. The solvent was removed under reduced pressure andthe product was dissolved in a mixture of n-hexane and ethyl-acetate (2:1).Separation was performed via liquid chromatography using 150 mm silica gel 60 in a columnwith a diameter of 30 mm and n-hexane and ethyl acetate (2:1) as eluent. Fractions were collectedinto tubes cooled in an ice bath and TLC was used to identify fractions solely containing allicin.Those fractions were combined, dried over an anhydrous sulfate, and filtered. The solvents wereremoved under reduced pressure at RT to yield a clear, oily substance that smells like garlic. Yield: 0.52 g, 3.204 mmol, 92%. 1H-NMR (500 MHz, CDCl3): delta 3.70-3.75 (m, 4H); 5.14-5.42 (m, 4H); 5.68-5.88 (m, 2H); 13C-NMR(125 MHz, CDCl3): 35.08, 59.82, 119.11, 124.10, 125.78, 132.8.
31% With 3H-2,1-benzoxaselenole Se-oxide; dihydrogen peroxide; In methanol; dichloromethane; at 20℃; for 3h; General procedure: Dibenzyl disulfide (245 mg, 1.00 mmol) and cyclic seleninate ester 1 (20 mg, 0.10 mmol) weredissolved in 10 mL of dichloromethane at room temperature with stirring. Hydrogen peroxide (127 muL,26.4% w/v, 1.00 mmol) was added to the solution. The mixture was stirred at room temperature andprogress was monitored by TLC. After 3 h, the reaction was diluted with dichloromethane, washed withbrine and dried with Na2SO4. The product was purified by flash chromatography on silica gel (hexane-ethylacetate, 10:1) to afford 139 mg (53%) of 2a. The product had properties identical to those reportedpreviously [18]. When the reaction was repeated in dichloromethane-methanol (95:5), a slightly higher yieldof 64% was obtained. The other thiolsulfinates in Tables 2 and 3 were prepared similarly, with any changesto the above conditions as noted in the Tables. Characterization data for the other products follows.
23% With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at -78℃; for 3h;Inert atmosphere; General procedure: The selected disulfide (3.0 mmol) was dissolved in dry DCM(5 mL) under a N2 atmosphere at -78 C. m-CPBA (0.52 g, 3.0mmol), dissolved in dry DCM (5 mL), was then slowly addeddropwise. Once the addition was complete, the reaction wasleft to stir for 3 h, slowly warming to 0 C. The reaction wasquenched with saturated NaHCO3, and the resulting aqueoussolution was extracted 3 times with DCM. The combinedorganic fractions were then dried over anhydrous MgSO4and evaporated under reduced pressure. The crude productwas then purified by silica gel flash column chromatography(n-hexane/ethyl acetate). After purification, all thiosulfinateswere stored at -80 C until required. All stock solutions wereprepared in DMSO and stored at -20 C. Allicin, S-allyl prop-2-ene-1-sulfinothioate (1b)[39]Yield: 23%, as a yellow oil; IR vmax cm-1: 1060 (S=O); 1H NMR delta(500 MHz, D2O): 6.05-5.94 (m, 2H, SCH2CH), 5.53-4.79 (m, 4H,CH=CH2), 4.05-3.82 (m, 4H, SCH2) ppm; 13C NMR delta (500 MHz,D2O): 136.01, 128.07, 127.87, 121.00, 61.07, 38.47 ppm; HRMSm/z: calcd. for C6H10OS2 (M+H)+: 163.0246; found: 163.0245
With dihydrogen peroxide; In acetonitrile; at 20℃; for 1h;Aqueous phosphate buffer;Reactivity; 7.2.3.2 Allicin Formation within the Cell Membrane Because allicin is known to react rapidly with thiols (and AllylSH is a thiol), the formation of allicin from AllylSH in the presence of H2O2 was suspected of being limited by a significant reverse formation of DADS from the allicin: allicin+2 AllylSH->2 DADS+H2O The environment within the membrane had now been determined to have a higher concentration of DADS than AllylSH, due to the lipophilic nature of DADS, so it was decided to perform another experiment to see if less H2O2 was needed for allicin production when the starting DADS concentration was significantly higher than the starting AllylSH concentration (which is the opposite of the starting condition of the experiment with H2O2 that was previously performed). An experiment starting with 0.2 mM of DADS in the presence of 5.0 mM of H202 and performed at room temperature proved this to be the case (FIG. 12). In the absence of AllylSH the rate of allicin formation was increased and was essentially linear with time. Another experiment was performed at approximate body temperature (37 degrees C.) and calculated membrane AllylSH concentration. Starting with 0.2 mM of DADS and 0.022 mM of AllylSH in the presence of 5.0 mM of H2O2 the allicin yield was 0.015 mM at 11 minutes (FIG. 13). In comparison with the previous experimental discovery of significant allicin formation from AllylSH in the presence of high H2O2 (e.g. in the extracellular environment adjacent to an activated neutrophil, see section 7.2.2), this new aspect of the present invention indicates the potential use of the formation of allicin (or other form of thiosulfinate) within the cell membrane as a defense against H2O2 and other ROS, particularly during oxidative stress events. The production of allicin has now been shown to occur at a significantly lower H2O2 concentration than was used in the previous experiment, which would extend the anti-inflammatory range to a significantly greater distance from the source of ROS than was calculated in section 7.2.2.
With prop-2-ene-1-thiol; dihydrogen peroxide; In acetonitrile; at 37℃; for 0.183333h;Aqueous phosphate buffer;Reactivity; 7.2.3.2 Allicin Formation within the Cell Membrane Because allicin is known to react rapidly with thiols (and AllylSH is a thiol), the formation of allicin from AllylSH in the presence of H2O2 was suspected of being limited by a significant reverse formation of DADS from the allicin: allicin+2 AllylSH->2 DADS+H2O The environment within the membrane had now been determined to have a higher concentration of DADS than AllylSH, due to the lipophilic nature of DADS, so it was decided to perform another experiment to see if less H2O2 was needed for allicin production when the starting DADS concentration was significantly higher than the starting AllylSH concentration (which is the opposite of the starting condition of the experiment with H2O2 that was previously performed). An experiment starting with 0.2 mM of DADS in the presence of 5.0 mM of H202 and performed at room temperature proved this to be the case (FIG. 12). In the absence of AllylSH the rate of allicin formation was increased and was essentially linear with time. Another experiment was performed at approximate body temperature (37 degrees C.) and calculated membrane AllylSH concentration. Starting with 0.2 mM of DADS and 0.022 mM of AllylSH in the presence of 5.0 mM of H2O2 the allicin yield was 0.015 mM at 11 minutes (FIG. 13). In comparison with the previous experimental discovery of significant allicin formation from AllylSH in the presence of high H2O2 (e.g. in the extracellular environment adjacent to an activated neutrophil, see section 7.2.2), this new aspect of the present invention indicates the potential use of the formation of allicin (or other form of thiosulfinate) within the cell membrane as a defense against H2O2 and other ROS, particularly during oxidative stress events. The production of allicin has now been shown to occur at a significantly lower H2O2 concentration than was used in the previous experiment, which would extend the anti-inflammatory range to a significantly greater distance from the source of ROS than was calculated in section 7.2.2.
With Oxone; In ethanol; water; at 10℃; Example 6; 10ml of <strong>[2179-57-9]diallyl disulphide</strong> (DADS) were stirred into 100ml ethanol/water (1 :1 ). 20 grams of potassium peroxymonosulfate (Oxone RTM) was added slowly over 2 hours, and stirred at below 10QC until no further reaction was observed. The resultant solution was then filtered, and then extracted with diethyl ether (2 x 50 ml). The diethyl ether layers were combined and washed with 10 % brine solution 2 x 50 ml. The ether layer was dried with magnesium sulfate then reduced to under vacuum. Removal of the solvent produced a yellow oil of pure allicin better than 90% (expressed as a % of pure material). The pure allicin may then be treated as per Example 1 for conversion to ajoene.
With dihydrogen peroxide; acetic acid; at 20℃; for 3h; Allicin was obtained by oxidation of<strong>[2179-57-9]diallyl disulfide</strong> with H2O2 as reported previously with the followingmodifications (18). 2 g of <strong>[2179-57-9]diallyl disulfide</strong> and 3 ml of 30%H2O2 were dissolved in 5 ml of glacial acetic acid prior to shakingat room temperature for 4 h. The reaction was stopped byaddition of 25 ml of distilled water. Extraction was performedtwo times with 30 ml of diethyl ether prior to evaporation in vacuo. The remaining volume was resuspended in 25 ml ofmethanol (90%, v/v), and remaining <strong>[2179-57-9]diallyl disulfide</strong> wasextracted several times with 10 ml of n-hexane until no diallyldisulfide was detectable by HPLC. The methanolic phase wasremoved by evaporation. The remaining volume was mixedwith distilled water and extracted against diethyl ether. Theether phase was then dried with dry copper sulfate until nofurther discoloration from white to blue was observable. Theether was separated from the copper sulfate by filtration priorto evaporation. The resulting allicin had a purity of 95% as analyzedby HPLC.
With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at -10 - 20℃; for 2h; Allicin was synthesized and analyzed according to Jansen et al., 1987 [1]. Briefly, 200 muL purediallyldisulfide (Sigma Aldrich, St. Louis, USA) was dissolved in 14 mL dichloromethane to which 6 mLsolution containing 357.7 mg 3-chloroperbenzoic (Sigma-Adrich, St. Louis, USA) was added dropwiseunder vigorous stirring in a cooling bath at -10 C during one hour. Following this, the resulting solutionwas further kept at room temperature for one hour and washed two times with 2.5% sodium bicarbonateand water and then the organic phase was treated with anhydrous sodium sulfate for water removal. Thesolvent was removed under vacuum at room temperature and the resulting clear, oily and garlic-smellingsubstance was aliquoted and kept at -80 C. MS and 1H, 13C NMR analysis proved it was allicin at purityhigher than 96%. 1H-NMR (400 MHz, CDCl3): delta3.70-3.85 (m, 4, J = 4.74 Hz, =CH-CH2-S-S(=O) and =CHCH2-S(=O)-); 5.16-5.40 (m, 2, J = 6.64 Hz, =CH-CH2-S-S(=O) and =CH-CH2-S(=O)-); 5.80-5.90 (m, 4, J = 1.64Hz, CH2=CH-CH2-S-S(=O)-S- and CH2=CH-CH2-S(=O)-); 13C-NMR: (125 MHz, CDCl3) delta 35.04, 59.78,119.05, 124.05, 125.82, 132.91.

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[2]Molecules,2017,vol. 22
[3]Journal of the American Chemical Society,1986,vol. 108,p. 7045
[4]European Journal of Organic Chemistry,2018,vol. 2018,p. 2134 - 2137
[5]Bioorganic and Medicinal Chemistry Letters,2010,vol. 20,p. 5541 - 5543
[6]International Journal of Molecular Sciences,2016,vol. 17
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[8]Acta Pharmacologica Sinica,2017,vol. 38,p. 1353 - 1368
[9]Journal of Medicinal Chemistry,2017,vol. 60,p. 215 - 227
[10]Experientia,1947,vol. 3,p. 114
    Helvetica Chimica Acta,1949,vol. 32,p. 198
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[13]Journal of Organic Chemistry,1994,vol. 59,p. 3227 - 3229
[14]Journal of Agricultural and Food Chemistry,1995,vol. 43,p. 2332 - 2338
[15]European Journal of Pharmacology,1995,vol. 276,p. 21 - 26
[16]Pharmazie,2004,vol. 59,p. 10 - 14
[17]Patent: US2005/260250,2005,A1 .Location in patent: Page/Page column 25; Sheet 7
[18]Patent: US2005/260250,2005,A1 .Location in patent: Page/Page column 25; Sheet 7
[19]Angewandte Chemie - International Edition,2009,vol. 48,p. 157 - 160
[20]Patent: WO2010/100486,2010,A2 .Location in patent: Page/Page column 26
[21]Journal of Agricultural and Food Chemistry,2010,vol. 58,p. 11226 - 11233
[22]Journal of Agricultural and Food Chemistry,2015,vol. 63,p. 787 - 794
[23]Journal of Biological Chemistry,2016,vol. 291,p. 11477 - 11490
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[25]Molecules,2019,vol. 24
  • 4
  • [ 556-27-4 ]
  • [ 539-86-6 ]
YieldReaction ConditionsOperation in experiment
alliinase rich garlic juice extract; at 30℃; for 3h;Enzymatic reaction;Product distribution / selectivity; Example 1; 5 litres of alliinase rich garlic juice extract prepared using a centrifugal juicer (JE700 Proline (RTM) Domestic Juicer extractor), was blended with 35 litres of 10% AIINn solution in a reactor and stirred for 3 hours. The garlic was a pre peeled Spanish white variety obtained from the local market. The reaction temperature was maintained at 30QC with a water jacket. Reaction completion was determined by HPLC using the method described above. The resulting 40 litre solution was determined to have an allicin concentration of 15,000 ppm. The 40 litres of allicin solution was left to sediment at 4QC for 48 hours. The clear supernatant was decanted off. The liquid from the remaining sediment was removed by centrifuging at 3000 rpm for 30 minutes at 0QC and was combined with the supernatant. The clarified solution was filtered though a Whatman 1 13 filter paper then placed in a 100 litres reactor. 40 litres of Ice-cold Acetone was added to the reactor and the two liquids were stirred for 2 hours to ensure total homogenisation. The temperature was kept below 5QC at all times. The aqueous acetone solution was then left to sediment for 24 hours at -10QC. Any sediment was decanted off. 15 kg of sodium chloride was added to the clarified solution and the mixture was stirred for 3 hours in a baffled reactor. The solution was allowed to stand for 12 hours and cooled to less than 10QC, which was sufficient time for the immiscible acetone layer to separate from the brine layer. The allicin concentration of the top acetone layer and the bottom brine layer was determined to be 3 % (w/v) and 0.1 % (w/V) respectively.The acetone layer was dried with magnesium sulphate and filtered through celite. This left 25 litres of acetone. The acetone layer was then mixed with a 25 litre solution of acetone/water/acetic acid (65/34/1 (v/v)) in a 100 litres reactor. The solution was then heated at 60 degrees for 5 hours. The reaction was monitored by the HPLC ajoene method described above. The reaction mixture was then paper filtered through a 30 cm 1 13 Whatman paper filter. The filtrate was then reduced under vacuum at 50QC to remove solvent. The residue was centrifuged at 2000 ppm for 5 minutes. The sediment liquid was placed in a separating funnel and the bottom oil was removed. The oil was reduced under vacuum at 80QC degrees to remove any residual solvent. A total of 275g of oil was obtained the ajoene content was determined to be 35 % (w/v) and the E/Z ratio was determined to be 3:1 by HPLC (as described above).
With Petiveria alliacea L. alliinase; Petiveria alliacea lachrymatory factor synthase; pyridoxal 5'-phosphate; NAD; at 20℃; for 0.333333h;pH 8.0;aq. phosphate buffer; General procedure: Sulfenic acid substrates with which the LFS could react were generated in situ through the action of a P. alliacea alliinase/LFS complex on cysteine sulfoxide derivatives as reported in the thesis of He (2010). The reaction mixtures in 10 mM phosphate buffer, pH 8.0 (in a total volume of 1.0 mL), were minimally comprised of 1.5 mM substrate, 25 muM pyridoxal 50-phosphate (PLP), 3.0 mug of purified alliinase (~21 nM) and 5.7 mug of purified LFS (~34 nM). In those cases where the effects of cofactors were determined, 0.32 mM NAD(P)+, FAD or FMN was also present. The mixtures were incubated for 20 min at room temperature, and then 10-20 muL of the reaction solution was analyzed by HPLC using an analytical RP C-18 column (Microsorb-MV 100 A, 250 x 4.6 mm, 5 lm, Varian, Palo Alto, CA, USA) under the following conditions: flow rate: 1.0 mL min-1; mobile phase: water:acetonitrile (30:70, v/v); detection wavelength: 210 nm. Eluted products were analyzed by UV-Vis and ESI-TOF. The reaction between the alliinase/LFS complex and petiveriin was also conducted in 10 mM phosphate buffer prepared with D2O, and the HPLC eluted products were analyzed by ESI-TOF.
  • 5
  • [ 539-86-6 ]
  • [ 52-89-1 ]
  • [ 2281-22-3 ]
YieldReaction ConditionsOperation in experiment
90% With sodium hydrogencarbonate In water for 0.33h; 15 In a 100 mL eggplant-shaped flask, add 450 mg of crude compound 6b and water (40 mL), add cysteine hydrochloride, and stir vigorously. Add sodium bicarbonate solid to the mixed system, adjust the pH of the reaction solution to 6, accompanied by the generation of white solid, and let it stand for 0.33 h.Filter, wash with water, and wash with ether to obtain a white solid. The solid was dissolved in 9% HCl, yellow droplets were suspended, extracted with ether, separated, the aqueous phase was added with sodium bicarbonate solid to adjust the pH to 6, a white solid precipitated, filtered, the solid was washed with water and ether, and dried. 480 mg of white solid (6c) was obtained with a yield of 90%.
With sodium hydrogencarbonate
480 mg With sodium hydrogencarbonate In water for 0.33h; 2.1. Chemical synthesis of 5P39 Target compound 5P39 was prepared via the synthetic route described in Fig. 1B. The oxidation of diallyl disulfide (1) with 30% H2O2 afforded allicin (2), which followed by reaction with L-cysteine hydrochloride to give S-allylthio-L-cysteine (3) in 90% yield for two steps. Compound 3 was then converted into 5P39 by transesterification reaction with tert-butyl acetate in the presence of HClO4 in 24% yield, and byproduct 4 was obtained meanwhile in yield of 12%. (0007) To a rapidly stirred solution of compound 1 (973mg, 6.65mmol) in acetic acid (4.0ml) was added dropwise a mixture of 30% hydrogen peroxide (1.0ml, 9.81mmol) in acetic acid (3.0ml) during 0.2hat 0°C. Then the mixture was continually stirred at 0°C for 2h and at r.t. for 4h, and poured into ice-water (50ml). The mixture was extracted with CH2Cl2 (4×50ml), and the combined organic solvent was washed with saturated aqueous Na2CO3 solution (3×50ml), dried over anhydrous Na2SO4, filtered and concentrated to give a residue (1.08g) of crude product 2. To a solution of the residue (450mg) in water (40ml) was added L-cysteine hydrochloride (2.0g, 12.7mmol) and enough sodium bicarbonate to adjust pH 6. White precipitate appeared immediately and was filtered after standing for 0.33h, and then washed with water and ether successively to give a white solid. The obtained white solid was dissolved in 9% HCl (aq.) and extracted with ether. To the aqueous layer was added NaHCO3 to adjust pH 6 and white solid precipitated out. The white solid was filtered, washed with water and ether, and dried to give compound 3 (480mg, 90% for two steps) as a white powder, mp: 187-190°C (Freeman et al., 1994. mp: 198-199°C). (0008) To a rapidly stirred solution of compound 3 (3.49g, 18.0mmol) in t-butyl acetate (36ml, 268mmol) at 0°C was slowly added HClO4 (1.53ml, 26.8mmol). The mixture was stirred at room temperature for 12h then adjusted to pH 9 by 10% Na2CO3 (aq.), and then extracted with CH2Cl2 (3×100ml). The combined organic solvent was dried over anhydrous Na2SO4, filtered and concentrated to give an oil. Silica gel flash column chromatography using CH2Cl2 as the eluent gave t-butyl S-allylthio-L-cysteinate (5P39, 1.10g, 24%) and t-butyl S-(t-butyl)-L-cysteinate (4, 0.50g, 12%) as pale yellow oil respectively. Compound 5P39: 1H NMR (400MHz, CDCl3) δ 5.80-5.95 (m, 1H), 5.23 (d, J = 16.9 Hz, 1H), 5.17 (d, J = 9.9 Hz, 1H), 3.67 (dd, J = 7.9, 4.5 Hz, 1H), 3.35 (d, J=7.3Hz, 2H), 3.10 (dd, J=13.4, 4.5Hz, 1H), 2.84 (dd, J=13.4, 8.0Hz, 1H), 1.70 (s, 2H), 1.48 (s, 9H). 13C NMR (CDCl3, 100MHz) δ 172.3, 132.7, 118.1, 81.1, 53.8, 43.7, 41.6, 27.4. ESI-MS m/z: 250.1 (M+H+). Compound 4: 1H NMR (400MHz, CDCl3) δ 3.54 (dd, J=7.4, 4.5Hz,1H), 2.90 (dd, J = 12.3, 4.5 Hz, 1H), 2.75 (dd, J = 12.3, 7.4 Hz, 1H), 1.71 (s, 2H), 1.48 (s, 9H), 1.33 (s, 9H); ESI-MS (m/z): 234.2 (M+H+).
  • 6
  • [ 539-86-6 ]
  • [ 67-03-8 ]
  • [ 554-44-9 ]
  • 7
  • [ 2179-57-9 ]
  • [ 539-86-6 ]
  • 2-(2',3'-dithia-5'-hexenyl)-3,4-dihydro-2H-thiopyran [ No CAS ]
  • 3-(2',3'-dithia-5'-hexenyl)-3,4-dihydro-2H-thiopyran [ No CAS ]
  • 9
  • [ 21593-77-1 ]
  • [ 2179-57-9 ]
  • [ 539-86-6 ]
  • [ 29418-05-1 ]
  • [ 113-24-6 ]
  • 10
  • [ 21593-77-1 ]
  • [ 2179-57-9 ]
  • [ 539-86-6 ]
  • [ 29418-05-1 ]
  • [ 127-17-3 ]
  • 11
  • [ 539-86-6 ]
  • [ 62488-53-3 ]
  • [ 2179-57-9 ]
  • [ 2050-87-5 ]
  • [ 80028-57-5 ]
  • 12
  • [ 539-86-6 ]
  • [ 62488-53-3 ]
  • [ 2179-57-9 ]
  • [ 2050-87-5 ]
  • [ 80028-57-5 ]
  • [ 92285-00-2 ]
  • [ 92284-99-6 ]
  • 13
  • [ 539-86-6 ]
  • [ 104228-61-7 ]
  • [ 92284-99-6 ]
YieldReaction ConditionsOperation in experiment
1: 0.024 g 2: 0.220 g With acetic acid at 25℃; for 120h;
  • 14
  • [ 539-86-6 ]
  • [ 92285-00-2 ]
  • [ 92284-99-6 ]
YieldReaction ConditionsOperation in experiment
In water; acetone at 63 - 64℃; for 4h; Heating; in water-benzene, 37 deg C, 48 h;
In water; benzene at 37℃; for 48h; Heating; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
In water; acetone for 4h; Heating; Yield given. Yields of byproduct given;
In water; acetone at 63 - 64℃; for 4h; Heating; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With acetic acid In water; acetone at 40℃; for 6.5h; 2 Example 2; The procedure described in Example 1 was used to produce 30 litres of a15,000 ppm allicin solution. The liquid was left to sediment for 48 hours then filtered through celite under vacuum. The clarified solution was then mixed with 1 1 Kg of sodium chloride in a 100 litres reactor. The reactor was cooled at -10QC for 24 hours. The liquid was then filtered through paper to remove protein, fibre and excess salt. The liquid was transferred to a 100 litres reactor. 30 litres of ice-cold acetone was added to the reactor, the liquids were stirred slowly with an impeller designed to ensure enough turbulence to allow transfer of the allicin from the aqueous layer to the organic layer without generating excess emulsion. The solution was allowed to stand for 12 hours and cooled to less than 10QC; this was sufficient time for the immiscible acetone layer to separate from the brine layer. Approximately 10 litres of emulsion was generated at the interface of the bi-layer. This emulsion was broken in a centrifuge at 3000 rpm for 5 minutes. The allicin concentration of the top acetone layer and the bottom brine layer was determined to be 2% (w/v) and 0.08% (w/v) respectively.The acetone layer was then mixed with a 25 litres solution of Acetone/water/acetic acid (65/34/1 ) in a 100 litres reactor. The solution was then heated at 40 degrees for 6.5 hours. The reaction was monitored by the HPLC ajoene method described above. The reaction mixture was then paper filtered through a 30 cm 1 13 Whatman paper filter. The liquid was then partitioned against 2 x 10 litres of pentane to remove non-polar allicin metabolites such as the polysulphides and vinyl dithiins. The filtrate was then reduced under vacuum at 50QC to remove solvent. The residue and the oil were homogenised with stirring. The residue acetic acid in the liquid was neutralised with the drop wise addition of a concentrated sodium hydroxide solution.The aqueous liquid was then extracted with 2 x 5 litres of methyl tert butyl ether. The methyl tert butyl ether extracts were combined then dried with magnesium sulphate. The dried methyl tert butyl ether was then reduced under vacuum at 50QC. A total of 21 O g of oil was obtained and the ajoene content was determined to be 50 % (w/v) and the E/Z ratio was determined to be 3.1
82 % de In water; benzene at 37℃; for 48h; 3 Example 3: Synthesis of compound (1), (E,Z)-aioene ΓΕ: Ζ = 10: 11A solution of compound (3), allicin (0.162 g, 1.0 mmol) in a 10 % aqueous benzene solution (1.6 ml_) was treated with AcOH (0.011 ml_, 0.2 mmol). The resulting mixture was heated to 37 °C for 48h. The cooled reaction mixture was diluted with 50% aqueous methanol (6 ml_) and extracted with pentane (5 x 10 ml_). The aqueous fraction was saturated with solid NH4S04 and the mixture was extracted with CH2CI2 (5 x 10 ml_). The combined organic extracts were dried (Na2S04) and concentrated in vacuo. The crude residue (0.15g) was further purified by column chromatography (eluting with 60-80% EtOAc in pentane) to yield compound (1) (E,Z)-ajoene (E: Z ratio 10: 1, 0.023g, 0.1 mmol, 30% yield) as a light yellow liquid.

YieldReaction ConditionsOperation in experiment
With ethanol durch Extraktion;
  • 16
  • [ 556-27-4 ]
  • [ 539-86-6 ]
YieldReaction ConditionsOperation in experiment
With immobilized alliinase
Immobilized alliinase column; Allicin was prepared by passing the synthetic substrate alliin [(+)S2-propenyl L-cysteine Soxide] through an immobilized alliinase column (Pinzon-Ortiz, C., et al. and Gonzalez-Ceron, L., et al.). The concentration of allicin was confirmed by HPLC (Krettli, A. U., et al.), and it was stored in a dark tightly closed tube at 4° C. for less than 3 months.
With alliinase In water at 25 - 35℃; for 0.5h; Enzymatic reaction; Inert atmosphere; 1 Embodiment 1 Figures 1-3 are schematic diagrams of embodiments according to this invention. The preparation method of allicin injection is as follows: (1) Add approximately 1000~2000 ml of deoxygenated pure water into a 5000 ml three-necked bottle A, add 35.4 g of alliinase, and stirr thoroughly (M, 60rpm) to completely dissolve the alliinase to obtain an alliinase solution Adjust the temperature of water bath I to 25-35 °C, check and confirm that the solution has a pH in the pH range of 6.5-8.5; (2) Add about 500~1000 ml of deoxygenated pure water into an enclosed type separatory funnel, add 35.4 g alliin, and then gently shake the enclosed type separatory funnel to dissolve the alliin, and fillthe three-necked bottle G with high purity nitrogen or argon simultaneously; (3) While stirring (M, 60rpm), dropwise add the alliin solution into the three-necked bottle A at speed of 50 ml/min through opening B of the enclosed type separatory funnel, after completion of the dropwise addition of the alliin solution, keep stirring the mixed solution for 10 minutes, and the total reaction is about 30min to obtain an enzymolysis reaction solution containing allicin and so on, and then replace the warm bath water with ice water immediately to lower down the temperature of the water bath to 0°C. The device is shown in Fig. 1. (0035) The enzymolysis reaction conditions are: temperature of the reactor is 25-35 °C, the pH of the aqueous solution is 6.5-8.5 and the reaction time is about 30 min. The key for successful preparation of the allicin is to keep the allicin stable chemically. The present invention uses inert gas protection to isolate from air and the temperature is lowered to a low temperature (0 °C) immediately at the end of the reaction (about 30min from the beginning of dropwise adding alliin). (0036) A low temperature stirring ultrafiltration device (Fig. 2) is installed in a bio-safety cabinet. The reaction solution W was taked out and transferred to a pressure flask with a ultrafiltration device by a pump. The refrigeration platform T was adjusted to a temperature of -2°C and sheathed with a heat preservation case C. The blender S was started and simultaneously a cylinder of high purity and high pressure nitrogen was connected to the gas inlet G. Alliinase and other macromolecules were removed from the solution using ultrafiltration membrane H of 1000~ 5000D at a predetermined pressure, to gain about 1500~3000 ml of allicin solution A with alliinase being removed. (0037) In a clean bio-safety cabinet, appropriate amount of allicin solution A was taked to determine the allicin content by High Performance Liquid Chromatography (HPLC). Then the solution A was diluted with precooled deoxygenated pure water (or deoxygenated pure water with addition of ethanol or propylene glycol cryoprotectant) to gain about 1500 ml of 10.0mg/ml or about 3000 ml of 5.0mg/ml allicin solution. The allicin content was again determined by HPLC, which conform to 98%-102% of the labelled amount.
  • 17
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  • [ 2179-57-9 ]
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YieldReaction ConditionsOperation in experiment
With dihydrogen peroxide; for 0.25h;Product distribution / selectivity; 7.2.2 Reactions of Allyl Mercaptan with Hydrogen Peroxide; Thiols are known to have various antioxidant properties, including the ability to scavenge hydrogen peroxide (H2O2). Several studies of the reaction between various low molecular weight thiols (e.g. cysteine, N-acetylcysteine, glutathione) and H2O2 have been reported, but there does not appear to be a consensus as to the reaction products formed under various conditions or the mechanism(s) by which the products form. An extensive analysis of the reaction of cysteine with H2O2, including both a review of the literature and new experimental results, is presented in JOPS94:304. The specific ability of allyl mercaptan in this regard was deemed worthy of being experimentally investigated because further experiments were planned that would rely on this ability. Unfortunately, the real-time probe for H2O2 measurement was found to drift significantly with time. A literature search revealed that probes (like this one) that use platinum in the probe tip react with thiols and lose sensitivity. Therefore, HPLC alone was used to measure the other reactants and products. Starting with 0.85 mM of AllylSH and 10 mM of H2O2 the formation of diallyl disulfide was found to be essentially linear with time over the 15 minute duration of the experiment (see FIG. 7). The results confirm that allyl mercaptan (AllylSH) can serve as an antioxidant in the presence of hydrogen peroxide, reducing the H2O2 to H2O and oxidizing the AllylSH to diallyl disulfide (DADS, DAS2 in the figure) in the process. In FIG. 7, the concentrations are reported as ?uM allyl? to take into account the fact that each DADS molecule contains two allyl groups, while each AllylSH molecule has only one. The initial drop in ?all 3 compounds? was later determined to be due to the hydrophobic compounds (DADS and to a lesser extent AllylSH) sticking to the glasswork. Tests at other AllylSH and H2O2 concentrations confirmed that the amount of product was proportional to the AllylSH concentration, and to the H2O2 concentration (but the effect of the initial drop was more significant at lower concentrations). Surprisingly, some allicin was found among the reaction products. Another test with a significantly higher initial concentration of H2O2 (40 mM) provided a much higher allicin yield (32%, 143 uM allyl) (FIG. 8). For convenience, the relevant molecular formulas are repeated below: While not meaning to be bound to a particular theory, the following reaction mechanism is proposed for the production of allicin from AllylSH in the presence of H2O2 without DADS as an intermediary: AllylSH+H2O2->AllylSOH+H2O AllylSOH+AllylSOH->allicin+H2O (Alternatively, AllylS- could be involved in either reaction step, yielding OH- instead of H2O, without affecting the following conclusions.) According to this theory, because the formation of allicin is doubly dependent on the concentration of AllylSOH (a sulfenic acid), which in turn is dependent on the concentration of H2O2, the resulting allicin concentration is a strong function of the H2O2 concentration. Later, I found a paper describing the formation of thiosulfinates from cysteine and H2O2 that validates and extends these results. The analysis (and experimental data) presented in JOPS94:304 shows that at low to moderate concentrations of H2O2, the direct formation of the disulfide predominates (illustrated as Scheme I in the JOPS94:304 reference), but at high concentrations there are competing paths for the sulfenic acid (illustrated as Scheme II in the JOPS94:304 reference), including as one alternative the reaction with another molecule of the sulfenic acid, yielding a thiosulfinate. But even at high H2O2 concentrations, their experimental data shows that the formation of the disulfide dominates (FIG. 7 of the JOPS94:304 reference), leading them to conclude that the alternative paths tend to also ultimately yield the disulfide (in other words, their Scheme II actually yields a higher disulfide concentration than Scheme I alone would produce). The analysis (and experimental data) presented in JOPS94:304 shows that the direct formation of cysteine disulfide is likely to involve the following two steps (their Scheme I): CyS-+H2O2->CySOH+OH- CySOH+CyS-->CySSCy+OH- It is reasonable to assume that the direct formation of DADS from AllylSH in the presence of H2O2 can proceed via analogous reaction steps, with the net equation: 2 AllylS-+H2O2->DADS+2OH- While not meaning to be bound to a particular theory, the following reaction mechanism is proposed as an alternative final step for the production of allicin from AllylSH in the presence of H2O2 with DADS as an intermediary: DADS+H2O2->allicin+H2O In practice, both reaction mechanisms can proceed in parallel, with any individual AllylSOH molecule reacting with either an AllylSH, an AllylSOH, or a DADS, depending on which it encounters first. According to this theory, because both the formation of DADS and the subsequent formati...
  • 18
  • [ 539-86-6 ]
  • [ 2179-57-9 ]
  • [ 592-88-1 ]
  • [ 2050-87-5 ]
  • [ 2444-49-7 ]
  • [ 118686-45-6 ]
YieldReaction ConditionsOperation in experiment
With sulfur; dibutylamine; at 60 - 70℃; for 1h;Product distribution / selectivity; Phase 1 ExperimentsSamples of allicin-enriched garlic extract ("standard solution") were obtained from Neem Biotech Ltd, Cardiff, CF 14 6HR, United Kingdom. The allicin concentration in the sample material was around 10,000 ppm (w/w).Such allicin-enriched samples were used for analytical simplicity, but the examples described below, and the methods described herein may equally be used with non- enriched allicin-containing plant extracts. Suitable starting material may be produced by the mechanical treatment of bulbs of the genus Allium, and especially from garlic, Allium sativum L.Two sub-samples of the allicin-enriched material were used, one of which was used in studies at 600C and one used in studies at 7O0C.At each temperature the following reaction conditions were generated and maintained for one hour: -(1) Standard solution (5g) heated.(2) Standard solution (5g) with 50 mg of added elemental sulphur, then heated (3) Standard solution (5g) with 5 mg of added elemental sulphur, then heated.(4) Standard solution (5g) with 5 mg of added elemental sulphur and 20 mg of dibutyl amine, then heated.The sulphur used was in the form of commercial, powdered sulphur ("Flowers of Sulphur"). <n="7"/>Both temperature studies were controlled against a sample maintained in a refrigerator for the same one-hour period that the test solutions were being heated.Following completion of the heating phase, the solutions were rapidly cooled and then analysed by HPLC a few hours later.Table 1 details the concentration of polysulfides found in the control samples (refrigerated for 1 hour).Table 1Area under HPLC peak: milli-Absorbance Units.s The molecules analysed were as follows: DAS: Diallyl sulfide DAS2: Diallyl disulfide DAS3 : Diallyl trisulfideDAS4: Diallyl tetrasulfide DAS5: Diallyl pentasulfide DAS6: Diallyl hexasulfide; Reaction condition (4): This sample was treated by the addition of 5mg elemental sulphur to the 5g of sample, giving a total concentration of 0.1%(w/w) sulphur and also by the addition of 20mg dibutyl amine (giving a concentration of 0.4%w/v). The sample was mixed by vigorous shaking, and held at either 6O0C or 7O0C. The results of analysis of products results from this treatment are presented in Table 5 (nomenclature as before):Table 5
  • 19
  • [ 539-86-6 ]
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  • [ 2050-87-5 ]
  • [ 2444-49-7 ]
YieldReaction ConditionsOperation in experiment
at 60 - 70℃; for 1h;Product distribution / selectivity; Phase 1 Experiments; Samples of allicin-enriched garlic extract ("standard solution") were obtained from Neem Biotech Ltd, Cardiff, CF 14 6HR, United Kingdom. The allicin concentration in the sample material was around 10,000 ppm (w/w).Such allicin-enriched samples were used for analytical simplicity, but the examples described below, and the methods described herein may equally be used with non- enriched allicin-containing plant extracts. Suitable starting material may be produced by the mechanical treatment of bulbs of the genus Allium, and especially from garlic, Allium sativum L.Two sub-samples of the allicin-enriched material were used, one of which was used in studies at 600C and one used in studies at 7O0C.At each temperature the following reaction conditions were generated and maintained for one hour: -(1) Standard solution (5g) heated.(2) Standard solution (5g) with 50 mg of added elemental sulphur, then heated (3) Standard solution (5g) with 5 mg of added elemental sulphur, then heated.(4) Standard solution (5g) with 5 mg of added elemental sulphur and 20 mg of dibutyl amine, then heated.The sulphur used was in the form of commercial, powdered sulphur ("Flowers of Sulphur"). <n="7"/>Both temperature studies were controlled against a sample maintained in a refrigerator for the same one-hour period that the test solutions were being heated.Following completion of the heating phase, the solutions were rapidly cooled and then analysed by HPLC a few hours later.Table 1 details the concentration of polysulfides found in the control samples (refrigerated for 1 hour).Table 1Area under HPLC peak: milli-Absorbance Units.s The molecules analysed were as follows: DAS: Diallyl sulfide DAS2: Diallyl disulfide DAS3 : Diallyl trisulfideDAS4: Diallyl tetrasulfide DAS5: Diallyl pentasulfide DAS6: Diallyl hexasulfide Reaction condition (1): This sample was heated to either 6O0C or 70C, and held at that temperature for 1 hour. The results of analysis of products results from this treatment are presented in Table 2 (nomenclature as before): <n="8"/>Table 2; Phase 2 Experiments; In a further series of experiments, manipulation of the polysulfide composition of garlic extracts was carried out on freshly-prepared extracts, and also extracts that had been stored in a frozen state for approximately three months, to demonstrate the applicability of the technique on samples having variation in their background matrix, that might be a result from typical biological variation often observed with such natural products. The samples had different appearances (a different colour) this being indicative of differences between the plant-derived matrix in which the allicin is found.The samples, again sourced from Neem Biotech Ltd, containing approximately 10,000ppm of allicin were stored in a frozen state. Sub-samples were defrosted and weighed in to 1O g aliquots followed by various amendments with elemental sulphur.All samples were then heated at 7O0C for 1 hour with periodic vigorous shaking, prior to rapid cooling in iced water.After cooling, lOOmg samples of the reacted supernatants were added to 10 ml of pure ethanol, the resulting solutions were then mixed and sub-samples filtered prior to analysis by HPLC.The samples were coded as "Nov 06" for the aged samples, which was a light orange in colour. The un-aged sample was coded as "Mar 07 ", and was distinctly green in colour; both had a similar smell of freshly-crushed garlic.The reactions with sulphur were controlled against a sub-sample heated with no sulphur addition and a sub-sample with no sulphur addition placed in a refrigerator. After one hour all experimental solutions were processed and analysed by HPLC as a group. <n="12"/>The following results were obtained: <n="13"/>Table 6
  • 20
  • [ 539-86-6 ]
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  • [ 2444-49-7 ]
  • [ 118686-45-6 ]
YieldReaction ConditionsOperation in experiment
at 70℃; for 1h;Product distribution / selectivity; Phase 1 Experiments; Samples of allicin-enriched garlic extract ("standard solution") were obtained from Neem Biotech Ltd, Cardiff, CF 14 6HR, United Kingdom. The allicin concentration in the sample material was around 10,000 ppm (w/w).Such allicin-enriched samples were used for analytical simplicity, but the examples described below, and the methods described herein may equally be used with non- enriched allicin-containing plant extracts. Suitable starting material may be produced by the mechanical treatment of bulbs of the genus Allium, and especially from garlic, Allium sativum L.Two sub-samples of the allicin-enriched material were used, one of which was used in studies at 600C and one used in studies at 7O0C.At each temperature the following reaction conditions were generated and maintained for one hour: -(1) Standard solution (5g) heated.(2) Standard solution (5g) with 50 mg of added elemental sulphur, then heated (3) Standard solution (5g) with 5 mg of added elemental sulphur, then heated.(4) Standard solution (5g) with 5 mg of added elemental sulphur and 20 mg of dibutyl amine, then heated.The sulphur used was in the form of commercial, powdered sulphur ("Flowers of Sulphur"). <n="7"/>Both temperature studies were controlled against a sample maintained in a refrigerator for the same one-hour period that the test solutions were being heated.Following completion of the heating phase, the solutions were rapidly cooled and then analysed by HPLC a few hours later.Table 1 details the concentration of polysulfides found in the control samples (refrigerated for 1 hour).Table 1Area under HPLC peak: milli-Absorbance Units.s The molecules analysed were as follows: DAS: Diallyl sulfide DAS2: Diallyl disulfide DAS3 : Diallyl trisulfideDAS4: Diallyl tetrasulfide DAS5: Diallyl pentasulfide DAS6: Diallyl hexasulfide Reaction condition (1): This sample was heated to either 6O0C or 70C, and held at that temperature for 1 hour. The results of analysis of products results from this treatment are presented in Table 2 (nomenclature as before): <n="8"/>Table 2
With sulfur; at 60 - 70℃; for 1h;Product distribution / selectivity; Phase 1 ExperimentsSamples of allicin-enriched garlic extract ("standard solution") were obtained from Neem Biotech Ltd, Cardiff, CF 14 6HR, United Kingdom. The allicin concentration in the sample material was around 10,000 ppm (w/w).Such allicin-enriched samples were used for analytical simplicity, but the examples described below, and the methods described herein may equally be used with non- enriched allicin-containing plant extracts. Suitable starting material may be produced by the mechanical treatment of bulbs of the genus Allium, and especially from garlic, Allium sativum L.Two sub-samples of the allicin-enriched material were used, one of which was used in studies at 600C and one used in studies at 7O0C.At each temperature the following reaction conditions were generated and maintained for one hour: -(1) Standard solution (5g) heated.(2) Standard solution (5g) with 50 mg of added elemental sulphur, then heated (3) Standard solution (5g) with 5 mg of added elemental sulphur, then heated.(4) Standard solution (5g) with 5 mg of added elemental sulphur and 20 mg of dibutyl amine, then heated.The sulphur used was in the form of commercial, powdered sulphur ("Flowers of Sulphur"). <n="7"/>Both temperature studies were controlled against a sample maintained in a refrigerator for the same one-hour period that the test solutions were being heated.Following completion of the heating phase, the solutions were rapidly cooled and then analysed by HPLC a few hours later.Table 1 details the concentration of polysulfides found in the control samples (refrigerated for 1 hour).Table 1Area under HPLC peak: milli-Absorbance Units.s The molecules analysed were as follows: DAS: Diallyl sulfide DAS2: Diallyl disulfide DAS3 : Diallyl trisulfideDAS4: Diallyl tetrasulfide DAS5: Diallyl pentasulfide DAS6: Diallyl hexasulfide; Reaction condition (3): This sample was treated by the addition of 5mg elemental sulphur to the 5g of sample, giving a total concentration of 0.1%(w/w). The sample was mixed by vigorous shaking, and held at either 6O0C or 7O0C. The results of analysis of products results from this treatment are presented in Table 4 (nomenclature as before): <n="9"/>Table 4
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  • [ 118686-45-6 ]
  • [ 137443-18-6 ]
YieldReaction ConditionsOperation in experiment
With sulfur; at 60 - 70℃; for 1h;Product distribution / selectivity; Phase 1 ExperimentsSamples of allicin-enriched garlic extract ("standard solution") were obtained from Neem Biotech Ltd, Cardiff, CF 14 6HR, United Kingdom. The allicin concentration in the sample material was around 10,000 ppm (w/w).Such allicin-enriched samples were used for analytical simplicity, but the examples described below, and the methods described herein may equally be used with non- enriched allicin-containing plant extracts. Suitable starting material may be produced by the mechanical treatment of bulbs of the genus Allium, and especially from garlic, Allium sativum L.Two sub-samples of the allicin-enriched material were used, one of which was used in studies at 600C and one used in studies at 7O0C.At each temperature the following reaction conditions were generated and maintained for one hour: -(1) Standard solution (5g) heated.(2) Standard solution (5g) with 50 mg of added elemental sulphur, then heated (3) Standard solution (5g) with 5 mg of added elemental sulphur, then heated.(4) Standard solution (5g) with 5 mg of added elemental sulphur and 20 mg of dibutyl amine, then heated.The sulphur used was in the form of commercial, powdered sulphur ("Flowers of Sulphur"). <n="7"/>Both temperature studies were controlled against a sample maintained in a refrigerator for the same one-hour period that the test solutions were being heated.Following completion of the heating phase, the solutions were rapidly cooled and then analysed by HPLC a few hours later.Table 1 details the concentration of polysulfides found in the control samples (refrigerated for 1 hour).Table 1Area under HPLC peak: milli-Absorbance Units.s The molecules analysed were as follows: DAS: Diallyl sulfide DAS2: Diallyl disulfide DAS3 : Diallyl trisulfideDAS4: Diallyl tetrasulfide DAS5: Diallyl pentasulfide DAS6: Diallyl hexasulfide; Reaction condition (2): This sample was treated by the addition of 50mg elemental sulphur to the 5g of sample, giving a total concentration of l%(w/w). The sample was mixed by vigorous shaking, and held at either 6O0C or 7O0C. The results of analysis of products results from this treatment are presented in Table 3 (nomenclature as before):
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  • [ 137443-18-6 ]
  • [ 139693-24-6 ]
YieldReaction ConditionsOperation in experiment
With sulfur; at 70℃; for 1h;Product distribution / selectivity; Phase 2 Experiments; In a further series of experiments, manipulation of the polysulfide composition of garlic extracts was carried out on freshly-prepared extracts, and also extracts that had been stored in a frozen state for approximately three months, to demonstrate the applicability of the technique on samples having variation in their background matrix, that might be a result from typical biological variation often observed with such natural products. The samples had different appearances (a different colour) this being indicative of differences between the plant-derived matrix in which the allicin is found.The samples, again sourced from Neem Biotech Ltd, containing approximately 10,000ppm of allicin were stored in a frozen state. Sub-samples were defrosted and weighed in to 1O g aliquots followed by various amendments with elemental sulphur.All samples were then heated at 7O0C for 1 hour with periodic vigorous shaking, prior to rapid cooling in iced water.After cooling, lOOmg samples of the reacted supernatants were added to 10 ml of pure ethanol, the resulting solutions were then mixed and sub-samples filtered prior to analysis by HPLC.The samples were coded as "Nov 06" for the aged samples, which was a light orange in colour. The un-aged sample was coded as "Mar 07 ", and was distinctly green in colour; both had a similar smell of freshly-crushed garlic.The reactions with sulphur were controlled against a sub-sample heated with no sulphur addition and a sub-sample with no sulphur addition placed in a refrigerator. After one hour all experimental solutions were processed and analysed by HPLC as a group. <n="12"/>The following results were obtained: <n="13"/>Table 6
  • 23
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  • [ 50-44-2 ]
  • [ 1146104-41-7 ]
YieldReaction ConditionsOperation in experiment
80% With sodium hydrogencarbonate In ethanol; water
80% With sodium hydrogencarbonate In ethanol; water at 20℃; for 10h; 1 Example 1. Synthesis of S-allylthio-6-mercaptopurine (SA-6MP) and S- aHylthio-6-mercaptopurine 9-riboside (SA-6MPR)S-allylthio-6-mercaρtopurine (SA-6MP) was prepared by reacting 6- mercaptopurine (6-MP) and allicin, as depicted in Scheme 1 above. A solution of 6- MP (1 mmole) in ethanol (100 ml) was added at room temperature to allicin (0.55 mmole) in aqueous solution (55 ml). The pH was adjusted to 8.0-8.4 using solid NaHCO3 to 0.025M (final concentration). The reaction rate was monitored by HPLC analysis until 6-MP was no longer detected (about 10 hours). Ethanol was partially removed by rotaevaporation and the slightly turbid solution was stored at 40C. The product, SA-6MP, which crystallized, was collected by filtration, washed with cold water and dried. A second harvest was done after removal of ethanol from the filtrate and storage at 40C for precipitation. The overall yield was 80%. Re- crystallization was done after re-dissolving the precipitate in ethanol and adding water.S-allylthio-6-mercaptopurine 9-riboside (SA-6MPR) was prepared by reacting 6-mercaptopurine riboside (6-MPR) and allicin, as depicted in Scheme 1 above. A solution of 6-MPR (0.6 mmole), in 0.04 M phosphate buffer, pH 7.2 (40 ml), was added at room temperature to a solution of allicin (0.35 mmole), in 50% ethanol (10 ml). The reaction proceeded for 4 hours and was stored at 40C. The reaction rate was monitored by HPLC analysis. The product, a white precipitate, was harvested by filtration. A second harvest was done after removal of ethanol and storage at 40C. The overall yield was 85%. Re-crystallization was done as described above.The synthesis of both SA-6MP and SA-6MPR were confirmed by mass spectroscopy analysis (electrospray ionization, ESI) and NMR. SA-6MP (molecular weight 224) is an off white crystal, showing a maximum absorbance in ethanol at 283 run, EM283 was 13,780 M-1Cm'1. ESI-MS: m/z (%)=[M+H]+=225.2 (40); DMSO=79 (100). SA-6MPR appeared as white crystals (ESI-MS: molecular weight 356), its maximum absorbance in ethanol at 284 run EM284 was 14,240 M-1Cm"1. HPLC retention times for SA-6MP and SA-6MPR were 8.7 and 7.3 min, respectively, as shown in Figs. IA- IB. NMR analysis is shown in Table 1 hereinbelow. The ClogP values (hydrophobicity partition coefficient) were: 6-MP: 0.823; SA-6MP: 1.344; 6-MPR: -1.191; SA-6MPR 0.90.Table 1: 1H and 13C NMR chemical shifts of SA-6MP and SA-6MPR in CDCl3
In ethanol at 20℃; aq. phosphate buffer;
  • 24
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  • [ 15639-75-5 ]
  • [ 1191918-40-7 ]
YieldReaction ConditionsOperation in experiment
85% In ethanol for 4h; aq. phosphate buffer;
85% In ethanol; water at 4℃; for 4h; Phosphate buffer; 1 Example 1. Synthesis of S-allylthio-6-mercaptopurine (SA-6MP) and S- aHylthio-6-mercaptopurine 9-riboside (SA-6MPR)S-allylthio-6-mercaρtopurine (SA-6MP) was prepared by reacting 6- mercaptopurine (6-MP) and allicin, as depicted in Scheme 1 above. A solution of 6- MP (1 mmole) in ethanol (100 ml) was added at room temperature to allicin (0.55 mmole) in aqueous solution (55 ml). The pH was adjusted to 8.0-8.4 using solid NaHCO3 to 0.025M (final concentration). The reaction rate was monitored by HPLC analysis until 6-MP was no longer detected (about 10 hours). Ethanol was partially removed by rotaevaporation and the slightly turbid solution was stored at 40C. The product, SA-6MP, which crystallized, was collected by filtration, washed with cold water and dried. A second harvest was done after removal of ethanol from the filtrate and storage at 40C for precipitation. The overall yield was 80%. Re- crystallization was done after re-dissolving the precipitate in ethanol and adding water.S-allylthio-6-mercaptopurine 9-riboside (SA-6MPR) was prepared by reacting 6-mercaptopurine riboside (6-MPR) and allicin, as depicted in Scheme 1 above. A solution of 6-MPR (0.6 mmole), in 0.04 M phosphate buffer, pH 7.2 (40 ml), was added at room temperature to a solution of allicin (0.35 mmole), in 50% ethanol (10 ml). The reaction proceeded for 4 hours and was stored at 40C. The reaction rate was monitored by HPLC analysis. The product, a white precipitate, was harvested by filtration. A second harvest was done after removal of ethanol and storage at 40C. The overall yield was 85%. Re-crystallization was done as described above.The synthesis of both SA-6MP and SA-6MPR were confirmed by mass spectroscopy analysis (electrospray ionization, ESI) and NMR. SA-6MP (molecular weight 224) is an off white crystal, showing a maximum absorbance in ethanol at 283 run, EM283 was 13,780 M-1Cm'1. ESI-MS: m/z (%)=[M+H]+=225.2 (40); DMSO=79 (100). SA-6MPR appeared as white crystals (ESI-MS: molecular weight 356), its maximum absorbance in ethanol at 284 run EM284 was 14,240 M-1Cm"1. HPLC retention times for SA-6MP and SA-6MPR were 8.7 and 7.3 min, respectively, as shown in Figs. IA- IB. NMR analysis is shown in Table 1 hereinbelow. The ClogP values (hydrophobicity partition coefficient) were: 6-MP: 0.823; SA-6MP: 1.344; 6-MPR: -1.191; SA-6MPR 0.90.Table 1: 1H and 13C NMR chemical shifts of SA-6MP and SA-6MPR in CDCl3
  • 25
  • [ 52-90-4 ]
  • [ 539-86-6 ]
  • [ 2165586-23-0 ]
YieldReaction ConditionsOperation in experiment
In water at 20℃; for 0.666667h; 19 Example 19Synthesis of S-allylmercapto-L-cysteine (SAMC)Allicin (5 g) is added to the solution of L-cysteine (2.5 g, 0.207 mol) in H2O (80 ml) in small portions under vigorous stirring at room temperature. After stirring the mixture at room temperature for 40 min, it is kept at 0 degree C. overnight for reaction. Then the mixture is filtered. The solid product (SAMC) is washed successively with H2O, C2H5OH, and ethyl acetate until white crystal SAMC is produced.
  • 26
  • [ 539-86-6 ]
  • [ 62571-86-2 ]
  • S-allylthio-captopril [ No CAS ]
  • 27
  • [ 539-86-6 ]
  • [ 574-25-4 ]
  • [ 1146104-45-1 ]
  • 28
  • [ 539-86-6 ]
  • [ 92285-01-3 ]
YieldReaction ConditionsOperation in experiment
In tetrahydrofuran at 64℃; for 4h; 2 Example 2: Synthesis of compound (1), (E,Z)-aioene using acetone solventA solution of compound (3), allicin (0.162 g, 1.0 mmol) in a 40 % aqueous acetone solution (1.6 mL) was treated with AcOH (0.011 mL, 0.2 mmol). The resulting mixture was heated to 64 °C for 4h. The cooled reaction mixture was diluted with 50% aqueous methanol (6 ml_) and extracted with pentane (5 x 10 ml_). The aqueous fraction was saturated with solid NH4S04 and the mixture was extracted with CH2CI2 (5 x 10 ml_). The combined organic extracts were dried (Na2S04) and concentrated in vacuo. The crude residue (0.16 g) was further purified by column chromatography (eluting with 60-80% EtOAc in pentane) to yield compound (1), (E,Z)-ajoene (E: Z ratio = 1 :4, 0.025g, 0.1 mmol, 32% yield) as a light yellow liquid.The above reaction was repeated using a variety of acids. Remaining parameters were kept the same as above. Exchange of acid had impact on both yields and E: Z ratios of ajoene as seen in table 2 below:Entry Acid Conditions Yield (E:Z)1 TsOH 40% aq. acetone, 64°C, 4h 24 (1:4) 2 CSA 40% aq. acetone, 64°C, 4h 20 (1:5) 3 MsOH 40% aq. acetone, 64°C, 4h 22 (1:4) 4 TFA 40% aq. acetone, 64°C, 4h 12 (1:1) Table 2: conversion of allicin (3) to (E,Z) ajoene (1) using different acids.Importantly, it was found that when using less than highly pure allicin (3) the yields in the above reactions were drastically reduced, if not zero. It was also found that when using the methods of the prior art to obtain allicin (3), some impurities stemming from either garlic extract or the reactants or the products used in the block synthesis of allicin resulted in yields of ajoene no higher than 6- 12%. This applied regardless of which solvent and acid was used for the ajoene synthesis.
  • 29
  • [ 539-86-6 ]
  • [ 118590-71-9 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: trifluoroacetic acid / tetrahydrofuran / 4 h / 64 °C 2: potassium permanganate / acetone / 2 h / -20 °C
  • 30
  • [ 1195577-61-7 ]
  • [ 539-86-6 ]
  • [ 127-17-3 ]
YieldReaction ConditionsOperation in experiment
With alliinase In water at 25 - 35℃; for 0.5h; Enzymatic reaction; Inert atmosphere; (1) Add approximately 1000∼2000 ml of deoxygenated pure water into a 5000 ml three-necked bottle A, add 35.4 g of alliinase, and stirr thoroughly (M, 60rpm) to completely dissolve the alliinase to obtain an alliinase solution Adjust the temperature of water bath I to 25-35 °C, check and confirm that the solution has a pH in the pH range of 6.5-8.5; [0063] (2) Add about 500∼1000 ml of deoxygenated pure water into an enclosed type separatory funnel, add 35.4 g alliin, and then gently shake the enclosed type separatory funnel to dissolve the alliin, and fill the three-necked bottle G with high purity nitrogen or argon simultaneously; [0064] (3) While stirring (M, 60rpm), dropwise add the alliin solution into the three-necked bottle A at speed of 50 ml/min through opening B of the enclosed type separatory funnel, after completion of the dropwise addition of the alliin solution, keep stirring the mixed solution for 10 minutes, and the total reaction is about 30min to obtain an enzymolysis reaction solution containing allicin and so on, and then replace the warm bath water with ice water immediately to lower down the temperature of the water bath to 0°C. The device is shown in Fig. 1. [0065] The enzymolysis reaction conditions are: temperature of the reactor is 25-35 °C, the pH of the aqueous solution is 6.5-8.5 and the reaction time is about 30 min. The key for successful preparation of the allicin is to keep the allicin stable chemically. The present invention uses inert gas protection to isolate from air and the temperature is lowered to a low temperature (0 °C) immediately at the end of the reaction (about 30min from the beginning of dropwise adding alliin). [0066] A low temperature stirring ultrafiltration device (Fig. 2) is installed in a bio-safety cabinet. The reaction solution W was taked out and transferred to a pressure flask with a ultrafiltration device by a pump. The refrigeration platform T was adjusted to a temperature of -2°C and sheathed with a heat preservation case C. The blender S was started and simultaneously a cylinder of high purity and high pressure nitrogen was connected to the gas inlet G. Alliinase and other macromolecules were removed from the solution using ultrafiltration membrane H of 1000∼ 5000D at a predetermined pressure, to gain about 1500∼3000 ml of allicin solution A with alliinase being removed. [0067] In a clean bio-safety cabinet, appropriate amount of allicin solution A was taked to determine the allicin content by High Performance Liquid Chromatography (HPLC). Then the solution A was diluted with precooled deoxygenated pure water (or deoxygenated pure water with addition of ethanol or propylene glycol cryoprotectant) to gain about 1500 ml of 10.0mg/ml or about 3000 ml of 5.0mg/ml allicin solution. The allicin content was again determined by HPLC, which conform to 98%-102% of the labelled amount.
  • 31
  • [ 539-86-6 ]
  • [ 184826-39-9 ]
  • [ 1554393-05-3 ]
YieldReaction ConditionsOperation in experiment
49% With sodium hydrogencarbonate In ethanol; water at 60℃; for 10h;
  • 32
  • [ 17795-27-6 ]
  • [ 539-86-6 ]
YieldReaction ConditionsOperation in experiment
99% With water extract of garlic In water at 20℃; Enzymatic reaction;
  • 33
  • [ 2268-79-3 ]
  • [ 539-86-6 ]
  • 2-(allyldisulfanyl)-6-methylbenzo[d]thiazole [ No CAS ]
  • 35
  • [ 539-86-6 ]
  • [ 51618-29-2 ]
  • 2-(allyldisulfanyl)-6-chlorobenzo[d]thiazole [ No CAS ]
  • 36
  • [ 539-86-6 ]
  • [ 49559-83-3 ]
  • 2-(allyldisulfanyl)-5-methoxybenzoxazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
31% In methanol at 20℃;
  • 37
  • [ 539-86-6 ]
  • [ 22876-20-6 ]
  • 2-(allyldisulfanyl)-6-chlorobenzoxazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
40% In methanol at 20℃;
  • 40
  • [ 2642186-59-0 ]
  • [ 539-86-6 ]
YieldReaction ConditionsOperation in experiment
29% With 3-chloro-benzenecarboperoxoic acid In dichloromethane at -78℃; for 3h;
  • 41
  • [ 2642186-60-3 ]
  • [ 539-86-6 ]
YieldReaction ConditionsOperation in experiment
64% With 3-chloro-benzenecarboperoxoic acid In dichloromethane at -78℃; for 3h;
  • 42
  • [ 2642186-61-4 ]
  • [ 539-86-6 ]
YieldReaction ConditionsOperation in experiment
71% With 3-chloro-benzenecarboperoxoic acid In dichloromethane at -78℃; for 3h;
  • 43
  • [ 17795-27-6 ]
  • [ 539-86-6 ]
  • [ CAS Unavailable ]
  • [ 127-17-3 ]
YieldReaction ConditionsOperation in experiment
With 4-hydroxybutanoic acid In methanol; water at 20℃;
  • 44
  • [ 539-86-6 ]
  • [ 18741-24-7 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
20 % In 1,4-dioxane; <i>tert</i>-butyl alcohol at 25℃; General procedure C for the synthesis of compounds (11a-11d). General procedure: Into a solution of 2-mercapto-quinazolinone (0.5mmol) in 4mL tBuOH:Dioxane (1:1) was added allicin (1.0mmol) dropwise at room temperature. The reaction mixture was stirred at room temperature for 4-24h and reaction progress was monitored by TLC. The solvent was removed in vacuo. The desired product was isolated using silica gel flash column chromatography (20-30% EtOAc:Hex) as a white solid. 2-(Allyldisulfanyl)-3-phenylquinazolin-4(3H)-one (11a). Following the general procedure C, the title product was obtained as an off-white solid (32mg, 20% yield); mp 119-121°C; 1H NMR (400MHz, DMSO) δ 8.11 (dd, 1H), 7.93 - 7.84 (m, 1H), 7.73 (d, 1H), 7.60 - 7.56 (m, 3H), 7.56 - 7.47 (m, 3H), 5.92 - 5.65 (m, 1H), 5.22 - 5.08 (m, 2H), 3.58 (d, J=7.4Hz, 2H). 13C NMR (101MHz, DMSO) δ 160.8, 155.36, 147.2, 135.5, 135.0, 132.4, 130.2, 129.6, 129.53, 126.7, 126.6, 126.6, 119.9, 119.5, 40.0; IR (ATR) νmax 3242, 3069, 2915, 2309, 2109, 1843, 1685, 1547, 1466, 1299, 1255, 1198, 1117, 917, 766; ESI-HRMS m/z: calcd for C11H10N2OS2 [M+H]+: 327.0620; found 327.0617.
20 % In 1,4-dioxane; <i>tert</i>-butyl alcohol at 25℃; General procedure C for the synthesis of compounds (11a-11d). General procedure: Into a solution of 2-mercapto-quinazolinone (0.5mmol) in 4mL tBuOH:Dioxane (1:1) was added allicin (1.0mmol) dropwise at room temperature. The reaction mixture was stirred at room temperature for 4-24h and reaction progress was monitored by TLC. The solvent was removed in vacuo. The desired product was isolated using silica gel flash column chromatography (20-30% EtOAc:Hex) as a white solid. 2-(Allyldisulfanyl)-3-phenylquinazolin-4(3H)-one (11a). Following the general procedure C, the title product was obtained as an off-white solid (32mg, 20% yield); mp 119-121°C; 1H NMR (400MHz, DMSO) δ 8.11 (dd, 1H), 7.93 - 7.84 (m, 1H), 7.73 (d, 1H), 7.60 - 7.56 (m, 3H), 7.56 - 7.47 (m, 3H), 5.92 - 5.65 (m, 1H), 5.22 - 5.08 (m, 2H), 3.58 (d, J=7.4Hz, 2H). 13C NMR (101MHz, DMSO) δ 160.8, 155.36, 147.2, 135.5, 135.0, 132.4, 130.2, 129.6, 129.53, 126.7, 126.6, 126.6, 119.9, 119.5, 40.0; IR (ATR) νmax 3242, 3069, 2915, 2309, 2109, 1843, 1685, 1547, 1466, 1299, 1255, 1198, 1117, 917, 766; ESI-HRMS m/z: calcd for C11H10N2OS2 [M+H]+: 327.0620; found 327.0617.
  • 45
  • [ 539-86-6 ]
  • [ 924869-18-1 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
19 % In 1,4-dioxane; <i>tert</i>-butyl alcohol at 25℃; General procedure C for the synthesis of compounds (11a-11d). General procedure: Into a solution of 2-mercapto-quinazolinone (0.5mmol) in 4mL tBuOH:Dioxane (1:1) was added allicin (1.0mmol) dropwise at room temperature. The reaction mixture was stirred at room temperature for 4-24h and reaction progress was monitored by TLC. The solvent was removed in vacuo. The desired product was isolated using silica gel flash column chromatography (20-30% EtOAc:Hex) as a white solid.
19 % In 1,4-dioxane; <i>tert</i>-butyl alcohol at 25℃; General procedure C for the synthesis of compounds (11a-11d). General procedure: Into a solution of 2-mercapto-quinazolinone (0.5mmol) in 4mL tBuOH:Dioxane (1:1) was added allicin (1.0mmol) dropwise at room temperature. The reaction mixture was stirred at room temperature for 4-24h and reaction progress was monitored by TLC. The solvent was removed in vacuo. The desired product was isolated using silica gel flash column chromatography (20-30% EtOAc:Hex) as a white solid.
  • 46
  • [ 539-86-6 ]
  • [ 1239758-42-9 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
47 % In 1,4-dioxane; <i>tert</i>-butyl alcohol at 25℃; General procedure C for the synthesis of compounds (11a-11d). General procedure: Into a solution of 2-mercapto-quinazolinone (0.5mmol) in 4mL tBuOH:Dioxane (1:1) was added allicin (1.0mmol) dropwise at room temperature. The reaction mixture was stirred at room temperature for 4-24h and reaction progress was monitored by TLC. The solvent was removed in vacuo. The desired product was isolated using silica gel flash column chromatography (20-30% EtOAc:Hex) as a white solid.
47 % In 1,4-dioxane; <i>tert</i>-butyl alcohol at 25℃; General procedure C for the synthesis of compounds (11a-11d). General procedure: Into a solution of 2-mercapto-quinazolinone (0.5mmol) in 4mL tBuOH:Dioxane (1:1) was added allicin (1.0mmol) dropwise at room temperature. The reaction mixture was stirred at room temperature for 4-24h and reaction progress was monitored by TLC. The solvent was removed in vacuo. The desired product was isolated using silica gel flash column chromatography (20-30% EtOAc:Hex) as a white solid.
  • 47
  • [ 539-86-6 ]
  • [ 13906-09-7 ]
  • [ CAS Unavailable ]
YieldReaction ConditionsOperation in experiment
30 % In 1,4-dioxane; <i>tert</i>-butyl alcohol at 25℃; General procedure C for the synthesis of compounds (11a-11d). General procedure: Into a solution of 2-mercapto-quinazolinone (0.5mmol) in 4mL tBuOH:Dioxane (1:1) was added allicin (1.0mmol) dropwise at room temperature. The reaction mixture was stirred at room temperature for 4-24h and reaction progress was monitored by TLC. The solvent was removed in vacuo. The desired product was isolated using silica gel flash column chromatography (20-30% EtOAc:Hex) as a white solid.
30 % In 1,4-dioxane; <i>tert</i>-butyl alcohol at 25℃; General procedure C for the synthesis of compounds (11a-11d). General procedure: Into a solution of 2-mercapto-quinazolinone (0.5mmol) in 4mL tBuOH:Dioxane (1:1) was added allicin (1.0mmol) dropwise at room temperature. The reaction mixture was stirred at room temperature for 4-24h and reaction progress was monitored by TLC. The solvent was removed in vacuo. The desired product was isolated using silica gel flash column chromatography (20-30% EtOAc:Hex) as a white solid.
Same Skeleton Products
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