Diallyl disulfide

Diallyl disulfide
Names
Preferred IUPAC name
3-[(Prop-2-en-1-yl)disulfanyl]prop-1-ene
Other names
Diallyl disulfide
Garlicin
1,2-Diallyldisulfane (not recommended)
4,5-Dithia-1,7-octadiene
Identifiers
2179-57-9 YesY
3D model (Jmol) Interactive image
ChEBI CHEBI:4488 YesY
ChEMBL ChEMBL366603 YesY
ChemSpider 15730 YesY
ECHA InfoCard 100.016.862
KEGG C08369 YesY
PubChem 16590
Properties
C6H10S2
Molar mass 146.28 g/mol
Appearance yellowish clear liquid with an intense garlic smell[1]
Density 1.01 g/cm3[2]
Boiling point 180 °C (356 °F; 453 K)
soluble in ethanol and oils[1]
Hazards
R-phrases 22-36/37/38
S-phrases 22-36/37/38
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
YesY verify (what is YesYN ?)
Infobox references

Diallyl disulfide (DADS or 4,5-dithia-1,7-octadiene) is an organosulfur compound derived from garlic and a few other genus Allium plants.[3] Along with diallyl trisulfide and diallyl tetrasulfide, it is one of the principal components of the distilled oil of garlic. It is a yellowish liquid which is insoluble in water and has a strong garlic odor. It is produced during the decomposition of allicin, which is released upon crushing garlic and other plants of the Alliaceae family. Diallyl disulfide has many of the health benefits of garlic, but it is also an allergen causing garlic allergy. Highly diluted, it is used as a flavoring in food. It decomposes in the human body into other compounds such as allyl methyl sulfide.

History

In 1844, Theodor Wertheim separated by steam distillation a pungent-smelling substance from garlic and named it "allyl sulfur." However, only in 1892 could Friedrich Wilhelm Semmler identify diallyl disulfide as one of the components of distilled garlic oil. The natural precursor of diallyl disulfide, allicin, was discovered in 1944 by Chester J. Cavallito and John Hays Bailey. In 1947, A. Stoll and E. Seebeck found that allicin in turn can be produced from the cysteine derivative alliin using the enzyme alliinase.[3][4]

Occurrence

Diallyl disulfide and trisulfide are produced by decomposition of allicin, which is released upon breaking the cells of the Alliaceae plants, especially garlic. The diallyl disulfide yield is the highest for the steam distillation of garlic bulbs which contain about 2 wt.% of diallyl disulfide-rich oil. Diallyl disulfide can also be extracted from garlic leaves, but their oil content is significantly lower at 0.06 wt.%.[5][6]

Extraction and representation

On an industrial scale, diallyl disulfide is produced from sodium disulfide and allyl bromide or allyl chloride at temperatures of 40–60 °C in an inert gas atmosphere; sodium disulfide is generated in situ by reacting sodium sulfide with sulfur. The reaction is exothermic and its theoretical efficiency of 88% has been achieved in practice.[7]

Smaller quantities can be synthesized from the same starting materials, but in air and using tetrabutylammonium bromide as a catalyst. The corresponding yield is below 82%.[8] The major problem, both in the industrial synthesis and in the extraction from plants, is separation of diallyl disulfide from higher sulfides (diallyl trisulfide (DATS), etc.). They have very similar physical properties and therefore, a typical commercial product contains only 80% of diallyl disulfide. The conversion of allicin to diallyl disulfide and trisulfide takes place particularly rapidly above 37 °C.[9]

Properties

Physical characteristics

Diallyl disulfide has a strong garlic smell. It is a clear, yellowish liquid which boils at 138–139 °C (for the typical 80% purity) and has its flash point at 50 °C, a density of about 1.0 g/mL and a vapor pressure of 1 mmHg at 20 °C. It is non-polar; therefore, diallyl disulfide is insoluble in water and is soluble in fats, oils, lipids, and non-polar solvents such as hexane or toluene.[1][2]

Chemical reactions

Diallyl disulfide can be readily oxidized to allicin with hydrogen peroxide or peracetic acid. Allicin in turn can hydrolyze giving diallyl disulfide and trisulfide. Reaction of diallyl disulfide with liquid sulfur gives a mixture containing diallyl polysulfides with as many as 22 sulfur atoms in a continuous chain.[3][10] When diallyl disulfide is heated it decomposes giving a complex mixture. The carbon-sulfur bond of diallyl disulfide is 16 kcal mol−1 weaker than the sulfur-sulfur bond (46 kcal mol−1 versus 62 kcal mol−1, respectively), with the consequence that on heating diallyl disulfide gives the allyldithio radical (AllSS•), which through addition to the double bonds in diallyl disulfide followed by fragmentation and subsequent reactions generates numerous organosulfur compounds, many of which are found in trace amounts in distilled garlic oil.[3][11] In the presence of a catalyst, diallyl disulfide can combine with alkyl halides forming 1-alkylthio-3-allylthio-1-propene and 1,3-di(alkylthio)propene.[12]

Applications

In the presence of iron chloride or copper chloride catalyst, or of liquid sulfur at 120 °C[3][13] Diallyl disulfide can be used as a precursor for the synthesis of higher diallyl polysulfides (polysulfanes). In agriculture, diallyl disulfide and related diallyl polysulfides show useful activity as environmentally-benign nematicides.[3] Diallyl disulfide is also a starting material for the synthesis of allicin. In the food industry, diallyl disulfide is used to improve the taste of meat, vegetables and fruits.[1][14]

Biological importance

Smell and taste

The unpleasant smell of diallyl disulfide is perceived through the transient receptor potential cation channel, member A1 (TRPA1). This ion channel had long been present not only in humans and animals, but even in fungi. Thus, Alliaceae plants have likely developed the diallyl disulfide-TRPA1 protection mechanism against predators at the early stages of the evolution.[15][16]

Poisoning and detoxification

Diallyl disulfide is an efficient agent for detoxication of the cells. It significantly increases the production of the enzyme glutathione S-transferase (GST), which binds electrophilic toxins in the cell. Garlic therefore supports, for example, the detoxification function of liver cells in vitro and protects nerve cells from oxidative stress, also in vitro.[17][18][19][20][21][22][23][24] The detoxification effect may prevent symptoms of inflammation. This was confirmed a study on rats where prolonged administration of diallyl disulfide protected poisoning of their intestinal cells. This study also showed that certain side effects of high doses of garlic oil are not attributable to the diallyl disulfide.[25] By supporting the detoxification activity in the liver, diallyl disulfide might offer liver protection during the chemotherapy, e.g. against cyanide detoxification.[26][27]

Antimicrobial effect

The release of organosulfur compounds upon destruction of Alliaceae plant cells has great importance, because of the antimicrobial, insecticidal and larvicidal properties of those compounds.[28] In particular, diallyl disulfide is the main reason for inhibiting the growth of molds and bacteria by garlic oil. It is also acts against the stomach ulcer germ Helicobacter pylori, however not as efficiently as allicin.[29][30] Because of its antimicrobial effects, diallyl disulfide, together with tobramycin, is included in preparations which are used for selective decontamination of the organs (e.g. gut) before surgical operations. A clinical study showed that such preparations prevent endotoxemia in heart valve operations.[31]

Protection against colon cancer

Garlic can prevent the colorectal cancer,[32] and several studies revealed that diallyl disulfide is a major component responsible for this action. The effect is dose dependent as demonstrated on mice.[33][34] Diallyl disulfide affects cancer cells much stronger than normal cells.[35] It also results in a strong and dose-dependent accumulation of several agents, such as reactive oxygen species, which activate enzyme and lead to destruction of cancer cells.[36]

Protection against cardiovascular disease

There is evidence that garlic may prevent the development of cardiovascular diseases. A possible reason for some of these diseases, such as atherosclerosis or coronary heart disease is oxidative stress. The latter is reduced by diallyl disulfide by assisting in the detoxification of the cell, as well as some other mechanisms.[4] By activating the TRPA1 ion channel, diallyl disulfide leads to a short-term lowering of blood pressure.[15]

Safety

Diallyl disulfide is a skin irritant and an allergen. In particular, it is the main cause of garlic allergy (allergic contact dermatitis to garlic). The allergy usually starts at the fingertips and cannot be prevented by wearing gloves because diallyl disulfide penetrates through most commercial glove types.[37][38][39][40]

The median lethal dose (LD50) for oral intake in rats is 260 mg per kg of body weight and it is 3.6 g/kg for dermal intake. High doses of 5 g/kg placed on the skin of cats cause death through hemolytic anemia.[1][41]

Diallyl disulfide can be easily detected in the air or in the blood with gas chromatography.[42][43]

See also

References

  1. 1 2 3 4 5 allyl disulfide
  2. 1 2 Diallyl disulfide at Sigma Aldrich
  3. 1 2 3 4 5 6 Block, E (2010). Garlic and Other Alliums: The Lore and the Science. Royal Society of Chemistry. ISBN 0-85404-190-7.
  4. 1 2 Omar, SH (2007). "Historical, chemical and cardiovascular perspectives on garlic: A review". Pharmacognosy Reviews. 1 (1): 80.
  5. ↑ Lawson, L; Wang, Z; Hughes, B (2007). "Identification and HPLC Quantitation of the Sulfides and Dialk(en)yl Thiosulfinates in Commercial Garlic Products". Planta Medica. 57 (4): 363–370. doi:10.1055/s-2006-960119. PMID 1775579.
  6. ↑ Edris, A; Fadel, H (2002). "Investigation of the volatile aroma components of garlic leaves essential oil. Possibility of utilization to enrich garlic bulb oil". European Food Research and Technology. 214 (2): 105–107. doi:10.1007/s00217-001-0429-2.
  7. ↑ WIPO Patent WO/2006/16881
  8. ↑ Yuan, X; Chen, X; Jiang, X; Nie, Y (2006). "Synthesis, characterization and bioactivity evaluation of diallyl disulfide". Journal of Central South University of Technology. 13 (5): 515–518. doi:10.1007/s11771-006-0079-4.
  9. ↑ Freeman, F; Kodera, Y (1995). "Garlic Chemistry: Stability of S-(2-Propenyl)-2-Propene-1-sulfinothioate (Allicin) in Blood, Solvents, and Simulated Physiological Fluids". Journal of Agricultural and Food Chemistry. 43 (9): 2332–2338. doi:10.1021/jf00057a004.
  10. ↑ Wang, K; Groom, M; Sheridan, R; Zhang, S; Block, E (2013). “Liquid Sulfur as a Reagent: Synthesis of Families of Polysulfanes with Twenty or More Sulfur Atoms with Characterization by Ultra Performance Liquid Chromatography–(Ag+)Coordination Ion Spray–Mass Spectrometry” J. Sulfur Chem. 34:55-66. doi: 10.1080/17415993.2012.721368
  11. ↑ Block, E; Iyer, R; Grisoni, S; Saha, C; Belman, S; Lossing, FP (1988). "Lipoxygenase Inhibitors from the Essential Oil of Garlic. Markownikoff Addition of the Allyldithio Radical to Olefins". Journal of the American Chemical Society. 110 (23): 7813–7827. doi:10.1021/ja00231a037.
  12. ↑ Amosova SV et al. (1986) "Synthesis of 1-alkylthio-3-allylthio-1-propene by the reaction of allyl halides with dialllyl disulfide in the alkali-metal hydroxide-DMSO superbasic system" J. Org. Chem USSR (Engl Transl.) 22(5): 957–963. Abstract
  13. ↑ U.S. Patent 8,101,802
  14. ↑ U.S. Patent 5,231,114
  15. 1 2 Bautista, DM; Movahed, P; Hinman, A; Axelsson, HE; Sterner, O; Högestätt, ED; Julius, D; Jordt, SE; Zygmunt, PM (2005). "Pungent products from garlic activate the sensory ion channel TRPA1". Proceedings of the National Academy of Sciences. 102 (34): 12248–12252. doi:10.1073/pnas.0505356102. PMC 1189336Freely accessible. PMID 16103371.
  16. ↑ Hile, AG; Shan, Z; Zhang, SZ; Block, E (2004). "Aversion of European starlings (Sturnus vulgaris) to garlic oil treated granules: garlic oil as an avian repellent. Garlic oil analysis by nuclear magnetic resonance spectroscopy". Journal of Agricultural and Food Chemistry. 52 (8): 2192–6. doi:10.1021/jf035181d. PMID 15080619.
  17. ↑ Germain, E; Chevalier, J; Siess, MH; Teyssier, C (2003). "Hepatic metabolism of diallyl disulphide in rat and man". Xenobiotica. 33 (12): 1185–99. doi:10.1080/00498250310001636840. PMID 14742141.
  18. ↑ Tsai, CW; Yang, JJ; Chen, HW; Sheen, LY; Lii, CK (2005). "Garlic organosulfur compounds upregulate the expression of the pi class of glutathione S-transferase in rat primary hepatocytes". The Journal of Nutrition. 135 (11): 2560–5. PMID 16251611.
  19. ↑ Wu, CC; Sheen, LY; Chen, HW; Kuo, WW; Tsai, SJ; Lii, CK (2002). "Differential effects of garlic oil and its three major organosulfur components on the hepatic detoxification system in rats". Journal of Agricultural and Food Chemistry. 50 (2): 378–83. doi:10.1021/jf010937z. PMID 11782211.
  20. ↑ Fukao, T; Hosono, T; Misawa, S; Seki, T; Ariga, T (2004). "The effects of allyl sulfides on the induction of phase II detoxification enzymes and liver injury by carbon tetrachloride". Food and chemical toxicology. 42 (5): 743–9. doi:10.1016/j.fct.2003.12.010. PMID 15046820.
  21. ↑ Lemar, KM; Aon, MA; Cortassa, S; O'Rourke, B; Müller, CT; Lloyd, D (2007). "Diallyl disulphide depletes glutathione in Candida albicans: oxidative stress-mediated cell death studied by two-photon microscopy". Yeast. 24 (8): 695–706. doi:10.1002/yea.1503. PMC 2292485Freely accessible. PMID 17534841.
  22. ↑ Hu, Y; Urig, S; Koncarevic, S; Wu, X; Fischer, M; Rahlfs, S; Mersch-Sundermann, V; Becker, K (2007). "Glutathione- and thioredoxin-related enzymes are modulated by sulfur-containing chemopreventive agents". Biological Chemistry. 388 (10): 1069–81. doi:10.1515/BC.2007.135. PMID 17937621.
  23. ↑ Koh, SH; Kwon, H; Park, KH; Ko, JK; Kim, JH; Hwang, MS; Yum, YN; Kim, OH; et al. (2005). "Protective effect of diallyl disulfide on oxidative stress-injured neuronally differentiated PC12 cells". Brain Research. Molecular Brain Research. 133 (2): 176–86. doi:10.1016/j.molbrainres.2004.10.006. PMID 15710234.
  24. ↑ Kim, JG; Koh, SH; Lee, YJ; Lee, KY; Kim, Y; Kim, S; Lee, MK; Kim, SH (2005). "Differential effects of diallyl disulfide on neuronal cells depend on its concentration". Toxicology. 211 (1–2): 86–96. doi:10.1016/j.tox.2005.02.011. PMID 15863251.
  25. ↑ Chiang, YH; Jen, LN; Su, HY; Lii, CK; Sheen, LY; Liu, CT (2006). "Effects of garlic oil and two of its major organosulfur compounds, diallyl disulfide and diallyl trisulfide, on intestinal damage in rats injected with endotoxin". Toxicology and Applied Pharmacology. 213 (1): 46–54. doi:10.1016/j.taap.2005.08.008. PMID 16274720.
  26. ↑ Iciek, M; Marcinek, J; Mleczko, U; Włodek, L (2007). "Selective effects of diallyl disulfide, a sulfane sulfur precursor, in the liver and Ehrlich ascites tumor cells". European Journal of Pharmacology. 569 (1–2): 1–7. doi:10.1016/j.ejphar.2007.04.055. PMID 17560567.
  27. ↑ Iciek, M; Bilska, A; Ksiazek, L; Srebro, Z; Włodek, L (2005). "Allyl disulfide as donor and cyanide as acceptor of sulfane sulfur in the mouse tissues". Pharmacological Reports. 57 (2): 212–8. PMID 15886420.
  28. ↑ Amonkar, SV; Banerji, A (1971). "Isolation and characterization of larvicidal principle of garlic". Science. 174 (16): 1343–4. doi:10.1126/science.174.4016.1343. PMID 5135721.
  29. ↑ Avato, P; Tursil, E; Vitali, C; Miccolis, V; Candido, V (2000). "Allylsulfide constituents of garlic volatile oil as antimicrobial agents". Phytomedicine. 7 (3): 239–43. doi:10.1016/s0944-7113(00)80010-0. PMID 11185736.
  30. ↑ O'Gara, EA; Hill, DJ; Maslin, DJ (2000). "Activities of garlic oil, garlic powder, and their diallyl constituents against Helicobacter pylori". Applied and Environmental Microbiology. 66 (5): 2269–73. doi:10.1128/AEM.66.5.2269-2273.2000. PMC 101489Freely accessible. PMID 10788416.
  31. ↑ Yu, J; Xiao, YB; Wang, XY (2007). "Effects of preoperatively selected gut decontamination on cardiopulmonary bypass-induced endotoxemia". Chinese Journal of Traumatology. 10 (3): 131–7. PMID 17535634.
  32. ↑ World Cancer Research Fund/American Institute for Cancer Research: Food, Nutrition, Physical Activity and the Prevention of Cancer. 2nd Edition, 2007 (ISBN 0-97225222-3) S. pp.93–94 (PDF, 12 MB)
  33. ↑ Milner, JA (2006). "Preclinical perspectives on garlic and cancer". The Journal of Nutrition. 136 (3 Suppl): 827S–831S. PMID 16484574.
  34. ↑ Yang, JS; Kok, LF; Lin, YH; Kuo, TC; Yang, JL; Lin, CC; Chen, GW; Huang, WW; et al. (2006). "Diallyl disulfide inhibits WEHI-3 leukemia cells in vivo". Anticancer Research. 26 (1A): 219–25. PMID 16475702.
  35. ↑ Huang, Z; Lei, X; Zhong, M; Zhu, B; Tang, S; Liao, D (2007). "Bcl-2 small interfering RNA sensitizes cisplatin-resistant human lung adenocarcinoma A549/DDP cell to cisplatin and diallyl disulfide". Acta Biochimica et Biophysica Sinica. 39 (11): 835–43. doi:10.1111/j.1745-7270.2007.00356.x. PMID 17989874.
  36. ↑ Jo, HJ; Song, JD; Kim, KM; Cho, YH; Kim, KH; Park, YC (2008). "Diallyl disulfide induces reversible G2/M phase arrest on a p53-independent mechanism in human colon cancer HCT-116 cells". Oncology Reports. 19 (1): 275–80. doi:10.3892/or.19.1.275. PMID 18097607.
  37. ↑ Block, E (2009). Garlic and other alliums: the lore and the science. Royal Society of Chemistry. p. 228. ISBN 0-85404-190-7.
  38. ↑ Horn, TD (2003). Dermatology, Volume 2. Elsevier Health Sciences. p. 305. ISBN 0-323-02578-1.
  39. ↑ Garlic
  40. ↑ Moyle, M; Frowen, K; Nixon, R (2004). "Use of gloves in protection from diallyl disulphide allergy". The Australasian Journal of Dermatology. 45 (4): 223–5. doi:10.1111/j.1440-0960.2004.00102.x. PMID 15527433.
  41. ↑ EPA documents
  42. ↑ documents of the U.S. Department of Labor Occupational Safety & Health
  43. ↑ Sun, X; Guo, T; He, J; Zhao, M; Yan, M; Cui, F; Deng, Y (2006). "Simultaneous determination of diallyl trisulfide and diallyl disulfide in rat blood by gas chromatography with electron-capture detection". Die Pharmazie. 61 (12): 985–8. PMID 17283653.
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