Alliin

Last updated
Alliin
L-alliin-2D-skeletal.png
L-alliin-3D-balls.png
Names
Systematic IUPAC name
(2R)-2-Amino-3-[(S)-(prop-2-ene-1-sulfinyl)]propanoic acid
Other names
3-(2-Propenylsulfinyl)alanine
(S)-3-(2-Propenylsulfinyl)-L-alanine
3-[(S)-Allylsulfinyl]-L-alanine
S-Allyl-L-cysteine sulfoxide
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.008.291 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 209-118-9
KEGG
PubChem CID
UNII
  • InChI=1S/C6H11NO3S/c1-2-3-11(10)4-5(7)6(8)9/h2,5H,1,3-4,7H2,(H,8,9)/t5-,11-/m0/s1 Yes check.svgY
    Key: XUHLIQGRKRUKPH-DYEAUMGKSA-N Yes check.svgY
  • C=CCS(=O)CC(C(=O)O)N
  • N[C@H](C(=O)O)C[S@@](=O)CC=C
Properties
C6H11NO3S
Molar mass 177.22 g·mol−1
AppearanceWhite to off white crystalline powder
Melting point 163–165 °C (325–329 °F)
Soluble
Hazards
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H315, H319, H335
P261, P264, P271, P280, P302+P352, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
1
1
0
Safety data sheet (SDS) External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Alliin /ˈæli.ɪn/ is a sulfoxide that is a natural constituent of fresh garlic. [1] It is a derivative of the amino acid cysteine. When fresh garlic is chopped or crushed, the enzyme alliinase converts alliin into allicin, which is responsible for the aroma of fresh garlic. Allicin and other thiosulfinates in garlic are unstable and form a number of other compounds, such as diallyl sulfide (DAS), diallyl disulfide (DADS) and diallyl trisulfide (DAT), dithiins and ajoene. [2] Garlic powder is not a source of alliin, nor is fresh garlic upon maceration, since the enzymatic conversion to allicin takes place in the order of seconds.

Contents

Alliin was the first natural product found to have both carbon- and sulfur-centered stereochemistry. [3]

Chemical synthesis

The first reported synthesis, by Stoll and Seebeck in 1951, [4] begins the alkylation of L-cysteine with allyl bromide to form deoxyalliin. Oxidation of this sulfide with hydrogen peroxide gives both diastereomers of L-alliin, differing in the orientation of the oxygen atom on the sulfur stereocenter.

H2O2toAlliin.png

A newer route, reported by Koch and Keusgen in 1998, [5] allows stereospecific oxidation using conditions similar to the Sharpless asymmetric epoxidation. The chiral catalyst is produced from diethyl tartrate and titanium isopropoxide.

Medical exploration

Garlic has been used since antiquity for conditions now associated with oxidative stress (production and accumulation of reactive oxygen species (ROS)).[ citation needed ] In an in vitro test, garlic powder showed antioxidant properties, and alliin showed good hydroxyl radical-scavenging effect. [6] Alliin has also been found to affect immune responses in blood cells in vitro. [7]

Related Research Articles

<span class="mw-page-title-main">Sulfur</span> Chemical element with atomic number 16 (S)

Sulfur (also spelled sulphur in British English) is a chemical element; it has symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with the chemical formula S8. Elemental sulfur is a bright yellow, crystalline solid at room temperature.

<span class="mw-page-title-main">Garlic</span> Species of edible plant

Garlic is a species of bulbous flowering plant in the genus Allium. Its close relatives include the onion, shallot, leek, chive, Welsh onion, and Chinese onion. It is native to South Asia, Central Asia and northeastern Iran and has long been used as a seasoning worldwide, with a history of several thousand years of human consumption and use. It was known to ancient Egyptians and has been used as both a food flavoring and a traditional medicine. China produced 73% of the world's supply of garlic in 2021.

<span class="mw-page-title-main">Thiol</span> Any organic compound having a sulfanyl group (–SH)

In organic chemistry, a thiol, or thiol derivative, is any organosulfur compound of the form R−SH, where R represents an alkyl or other organic substituent. The −SH functional group itself is referred to as either a thiol group or a sulfhydryl group, or a sulfanyl group. Thiols are the sulfur analogue of alcohols, and the word is a blend of "thio-" with "alcohol".

<span class="mw-page-title-main">Allicin</span> Chemical compound

Allicin is an organosulfur compound obtained from garlic. When fresh garlic is chopped or crushed, the enzyme alliinase converts alliin into allicin, which is responsible for the aroma of fresh garlic. Allicin is unstable and quickly changes into a series of other sulfur-containing compounds such as diallyl disulfide. Allicin is an antifeedant, i.e. the defense mechanism against attacks by pests on the garlic plant.

Organosulfur chemistry is the study of the properties and synthesis of organosulfur compounds, which are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur derivatives, e.g., saccharin. Nature is abound with organosulfur compounds—sulfur is vital for life. Of the 20 common amino acids, two are organosulfur compounds, and the antibiotics penicillin and sulfa drugs both contain sulfur. While sulfur-containing antibiotics save many lives, sulfur mustard is a deadly chemical warfare agent. Fossil fuels, coal, petroleum, and natural gas, which are derived from ancient organisms, necessarily contain organosulfur compounds, the removal of which is a major focus of oil refineries.

<span class="mw-page-title-main">Sulfoxide</span> Organic compound containing a sulfinyl group (>SO)

In organic chemistry, a sulfoxide, also called a sulphoxide, is an organosulfur compound containing a sulfinyl functional group attached to two carbon atoms. It is a polar functional group. Sulfoxides are oxidized derivatives of sulfides. Examples of important sulfoxides are alliin, a precursor to the compound that gives freshly crushed garlic its aroma, and dimethyl sulfoxide (DMSO), a common solvent.

<span class="mw-page-title-main">Allyl alcohol</span> Organic compound (CH2=CHCH2OH)

Allyl alcohol is an organic compound with the structural formula CH2=CHCH2OH. Like many alcohols, it is a water-soluble, colourless liquid. It is more toxic than typical small alcohols. Allyl alcohol is used as a precursor to many specialized compounds such as flame-resistant materials, drying oils, and plasticizers. Allyl alcohol is the smallest representative of the allylic alcohols.

Organoselenium chemistry is the science exploring the properties and reactivity of organoselenium compounds, chemical compounds containing carbon-to-selenium chemical bonds. Selenium belongs with oxygen and sulfur to the group 16 elements or chalcogens, and similarities in chemistry are to be expected. Organoselenium compounds are found at trace levels in ambient waters, soils and sediments.

<span class="mw-page-title-main">Thial</span> Chemical group (–CH=S)

In organic chemistry, a thial or thioaldehyde is a functional group which is similar to an aldehyde, RC(O)H, in which a sulfur (S) atom replaces the oxygen (O) atom of the aldehyde. Thioaldehydes are even more reactive than thioketones. Unhindered thioaldehydes are generally too reactive to be isolated — for example, thioformaldehyde, H2C=S, condenses to the cyclic trimer 1,3,5-trithiane. Thioacrolein, H2C=CHCH=S, formed by decomposition of allicin from garlic, undergoes a self Diels-Alder reaction giving isomeric vinyldithiins. While thioformaldehyde is highly reactive, it is found in interstellar space along with its mono- and di-deuterated isotopologues. With sufficient steric bulk, however, stable thioaldehydes can be isolated.

<span class="mw-page-title-main">Diallyl disulfide</span> Chemical compound

Diallyl disulfide is an organosulfur compound derived from garlic and a few other genus Allium plants. 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 odour. It is produced during the decomposition of allicin, which is released upon crushing garlic and other plants of the family Alliaceae. 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.

<span class="mw-page-title-main">Stainless steel soap</span> Piece of stainless steel

Stainless steel soap is a piece of stainless steel, in the form of a soap bar or other hand-held shape. Its purported purpose is to neutralize or reduce strong odors such as those from handling garlic, onion, durian, guava, salami, or fish.

<span class="mw-page-title-main">Sulfur assimilation</span> Incorporation of sulfur into living organisms

Sulfur assimilation is the process by which living organisms incorporate sulfur into their biological molecules. In plants, sulfate is absorbed by the roots and then transported to the chloroplasts by the transipration stream where the sulfur are reduced to sulfide with the help of a series of enzymatic reactions. Furthermore, the reduced sulfur is incorporated into cysteine, an amino acid that is a precursor to many other sulfur-containing compounds. In animals, sulfur assimilation occurs primarily through the diet, as animals cannot produce sulfur-containing compounds directly. Sulfur is incorporated into amino acids such as cysteine and methionine, which are used to build proteins and other important molecules.

<span class="mw-page-title-main">Sulfenic acid</span> Organosulfur compound of the form R–SOH

In chemistry, a sulfenic acid is an organosulfur compound and oxoacid with the general formula R−S−OH. It is the first member of the family of organosulfur oxoacids, which also include sulfinic acids and sulfonic acids, respectively. The base member of the sulfenic acid series with R = H is hydrogen thioperoxide.

<span class="mw-page-title-main">Alliinase</span> Class of enzyme

In enzymology, an alliin lyase is an enzyme that catalyzes the chemical reaction

<span class="mw-page-title-main">Thiosulfinate</span> Functional group

In organosulfur chemistry, thiosulfinate is a functional group consisting of the linkage R-S(O)-S-R. Thiolsulfinates are also named as alkanethiosulfinic acid esters.

<span class="mw-page-title-main">Garlic allergy</span> Type of skin allergy caused by garlic

Garlic allergy or allergic contact dermatitis to garlic is a common inflammatory skin condition caused by contact with garlic oil or dust. It mostly affects people who cut and handle fresh garlic, such as chefs, and presents on the tips of the thumb, index and middle fingers of the non-dominant hand. The affected fingertips show an asymmetrical pattern of fissure as well as thickening and shedding of the outer skin layers, which may progress to second- or third-degree burn of injured skin.

Vinyldithiins, more precisely named 3-vinyl-4H-1,2-dithiin and 2-vinyl-4H-1,3-dithiin, are organosulfur phytochemicals formed in the breakdown of allicin from crushed garlic (Allium sativum). Vinyldithiins are Diels-Alder dimers of thioacrolein, H2C=CHCH=S, formed in turn by decomposition of allicin. In garlic supplements, vinyldithiins are only found in garlic oil macerates that are made by incubation of crushed garlic in oil.

<span class="mw-page-title-main">Garlic breath</span> Bad breath induced by the consumption of garlic

Garlic breath is halitosis resulting from the consumption of garlic.

Diallyl trisulfide (DATS), also known as Allitridin, is an organosulfur compound with the formula S(SCH2CH=CH2)2. It is one of several compounds produced by hydrolysis of allicin, including diallyl disulfide and diallyl tetrasulfide; DATS is one of the most potent.

<span class="mw-page-title-main">Selenosulfide</span> Class of chemical compounds, both organic and inorganic, containing sulfur as well as selenium

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References

  1. Iberl, B; Winkler, G; Müller, B; Knobloch, K (1990). "Quantitative Determination of Allicin and Alliin from Garlic by HPLC". Planta Med. 56 (3): 320–326. doi:10.1055/s-2006-960969. PMID   17221429. S2CID   30268881.
  2. Amagase, Harunobu; Petesch, Brenda L.; Matsuura, Hiromichi; Kasuga, Shigeo; Itakura, Yoichi (2001). "Intake of Garlic and Its Bioactive Components". The Journal of Nutrition. 131 (3). Oxford University Press (OUP): 955S–962S. doi: 10.1093/jn/131.3.955s . ISSN   0022-3166. PMID   11238796.
  3. Block, E (2009). Garlic and Other Alliums: The lore and the science. Royal Society of Chemistry. pp. 100–106.
  4. Stoll, A; Seeback, E (1951). Chemical investigations on alliin, the specific principle of garlic. Advances in Enzymology and Related Subjects of Biochemistry. Vol. 11. pp. 377–400. doi:10.1002/9780470122563.ch8. ISBN   9780470122563. PMID   24540596.
  5. Koch; Keusgen (1998). "Diastereoselective synthesis of alliin by an asymmetric sulfur oxidation". Pharmazie. 53 (668–671). doi:10.1002/chin.199904184.
  6. Kourounakis, PN; Rekka, EA (November 1991). "Effect on active oxygen species of alliin and Allium sativum (garlic) powder". Res. Commun. Chem. Pathol. Pharmacol. 74 (2): 249–252. PMID   1667340.
  7. Salman, H; Bergman, M; Bessler, H; Punsky, I; Djaldetti, M (September 1999). "Effect of a garlic derivative (alliin) on peripheral blood cell immune responses". Int. J. Immunopharmacol. 21 (9): 589–597. doi:10.1016/S0192-0561(99)00038-7. PMID   10501628.