{{chembox | ImageFile = Sinigrin structure.svg | IUPACName = (''Z'')-''N''-[1-(β-<small>D</small>-glucopyranosylsulfanyl)but-3-en-1-ylidene]hydroxylamine-''O''-sulfonic acid | SystematicName = (''Z'')-''N''-(1-<nowiki/>{[(2''S'',3''R'',4''S'',5''S'',6''R'')-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]sulfanyl}but-3-en-1-ylidene)hydroxylamine-''O''-sulfonic acid | OtherNames = Allyl glucosinolate; 2-Propenyl glucosinolate; (1''Z'')-''N''-(Sulfooxy)but-3-enimidoyl 1-thio-β-<small>D</small>-glucopyranoside |Section1={{Chembox Identifiers | index_label = Sinigrin | index1_label = K<sup>+</sup> salt | CASNo_Ref = {{cascite|correct|CAS}} | CASNo = 534-69-0 <!-- CAS number for sinigrin has incorrect E geometry. Correct may be 223-545-8 not in CAS Common Chem --> | CASNo1_Ref = {{cascite|correct|CAS}} | CASNo1 = 3952-98-5 | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | ChemSpiderID = 4588961 | ChemSpiderID1_Ref = {{chemspidercite|correct|chemspider}} | ChemSpiderID1 = 4576678 | UNII1 = 50UM64RMBJ | PubChem = 5486549 | PubChem1 = 23684362 | ChEBI_Ref = {{ebicite|correct|EBI}} | ChEBI = 79317 | SMILES = C=CC/C(=N/OS(=O)(=O)O)/S[C@H]1[C@@H]([C@H]([C@@H]([C@H](O1)CO)O)O)O | SMILES1 = C=CC/C(=N/OS(=O)(=O)[O-])/S[C@H]1[C@@H]([C@H]([C@@H]([C@H](O1)CO)O)O)O.[K+] | StdInChI_Ref = {{stdinchicite|correct|chemspider}} | StdInChI = 1S/C10H17NO9S2/c1-2-3-6(11-20-22(16,17)18)21-10-9(15)8(14)7(13)5(4-12)19-10/h2,5,7-10,12-15H,1,3-4H2,(H,16,17,18)/b11-6-/t5-,7-,8+,9-,10+/m1/s1 | StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} | StdInChIKey = PHZOWSSBXJXFOR-GLVDENFASA-N | InChI1 = 1S/C10H17NO9S2.K/c1-2-3-6(11-20-22(16,17)18)21-10-9(15)8(14)7(13)5(4-12)19-10;/h2,5,7-10,12-15H,1,3-4H2,(H,16,17,18);/q;+1/p-1/b11-6-;/t5-,7-,8+,9-,10+;/m1./s1 | InChIKey1 = QKFAFSGJTMHRRY-FVDOMRANSA-M }} |Section2={{Chembox Properties | C=10 | H=17 | N=1 | O=9 | S=2 | Appearance = | Density = | MeltingPt = | BoilingPt = | Solubility = }} |Section3={{Chembox Hazards | MainHazards= | FlashPt= | AutoignitionPt = }} }}
'''Sinigrin''' or '''allyl glucosinolate''' is a glucosinolate that belongs to the family of glucosides found in some plants of the family Brassicaceae such as Brussels sprouts, broccoli, and the seeds of black mustard (''Brassica nigra''). Whenever sinigrin-containing plant tissue is crushed or otherwise damaged, the enzyme myrosinase degrades sinigrin to a mustard oil (allyl isothiocyanate), which is responsible for the pungent taste of mustard and horseradish.<ref>{{cite web |last=Richard |first=H. |title=Arômes alimentaires |url=http://www.cnrs.fr/chimie/communication/images/images-chimietous/minidossiers/cours%20aromes_hubert%20richard.pdf |language=fr |archive-url=https://web.archive.org/web/20070214074448/http://www.cnrs.fr/chimie/communication/images/images-chimietous/minidossiers/cours%20aromes_hubert%20richard.pdf |archive-date=2007-02-14 }}</ref> Seeds of white mustard, ''Sinapis alba'', give a less pungent mustard because this species contains a different glucosinolate, sinalbin.
==Occurrence== The compound was first reported in 1839,<ref name=Benn>{{cite journal |doi=10.1039/C19650000445 |title=The synthesis of sinigrin |year=1965 |last1=Benn |first1=M. H. |last2=Ettlinger |first2=M. G. |journal=Chemical Communications |issue=19 |page=445 }}</ref> after its isolation from black mustard ''Brassica nigra'', also known as ''<u>Sin</u>apis <u>nigr</u>a'', after which it was named.<ref name=pmid31771793>{{cite journal |doi=10.1016/j.phytochem.2019.112100 |doi-access=free |title=Glucosinolate structural diversity, identification, chemical synthesis and metabolism in plants |year=2020 |last1=Blažević |first1=Ivica |last2=Montaut |first2=Sabine |last3=Burčul |first3=Franko |last4=Olsen |first4=Carl Erik |last5=Burow |first5=Meike |last6=Rollin |first6=Patrick |last7=Agerbirk |first7=Niels |journal=Phytochemistry |volume=169 |article-number=112100 |pmid=31771793 |bibcode=2020PChem.169k2100B |s2cid=208318505 }}</ref>{{rp|Section 2}} Sinigrin is now known to occur widely in other brassica families including Brassicaceae and Capparaceae.<ref>{{cite journal |doi=10.1016/S0031-9422(00)00316-2 |title=The chemical diversity and distribution of glucosinolates and isothiocyanates among plants |year=2001 |last1=Fahey |first1=Jed W. |last2=Zalcmann |first2=Amy T. |last3=Talalay |first3=Paul |journal=Phytochemistry |volume=56 |issue=1 |pages=5–51 |pmid=11198818 |bibcode=2001PChem..56....5F }}</ref>
==Structure== thumb|left|E isomer (shown as anion) The chemical structure of sinigrin had been established by 1930. This showed that it is a glucose derivative with β-<small>D</small>-glucopyranose configuration. It was unclear whether the C=N bond was in the Z (or ''syn'') form, with sulfur and oxygen substituents on the same side of the double bond, or the alternative E form in which they are on opposite sides. The matter was settled by X-ray crystallography of its potassium salt in 1963.<ref>{{cite journal |doi=10.1038/1981297b0 |title=Crystal Structure of Sinigrin |year=1963 |last1=Waser |first1=Jürg |last2=Watson |first2=William H. |journal=Nature |volume=198 |issue=4887 |pages=1297–1298 |bibcode=1963Natur.198.1297W |s2cid=4187013 }}</ref><ref>{{cite journal |doi=10.1107/S0567740870003539 |title=Refinement of the crystal structure of sinigrin |year=1970 |last1=Marsh |first1=R. E. |last2=Waser |first2=J. |journal=Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry |volume=26 |issue=7 |pages=1030–1037 |bibcode=1970AcCrB..26.1030M |url=https://authors.library.caltech.edu/70930/ }}</ref> It is now known that all natural glucosinolates are of Z form.<ref name=pmid31771793/>
==Synthesis== ===Biosynthesis=== Sinigrin is biosynthesised from the amino acid methionine in a multi-step pathway.<ref name=pmid31771793/>
===Laboratory synthesis=== The first laboratory syntheses of sinigrin was published in 1965.<ref name=Benn/> Later work provided a more efficient route.<ref>{{cite journal |doi=10.1080/07328309608005429 |title=Practical Synthesis of Sinigrin |year=1996 |last1=Abramski |first1=Wojciech |last2=Chmielewski |first2=Marek |journal=Journal of Carbohydrate Chemistry |volume=15 |pages=109–113 }}</ref><ref name=pmid31771793/>{{rp|Section 3}}
==Function== {{Main|Glucosinolate}} The natural role of glucosinolates are as plant defense compounds. The enzyme myrosinase removes the glucose group in sinigrin to give an intermediate which spontaneously rearranges to allyl isothiocyanate, the compound responsible for the pungent taste of Dijon mustard. This is a reactive material which is toxic to many insect predators and its production is triggered when the plant is damaged.<ref>{{cite journal |doi=10.1016/j.phytochem.2008.03.006 |title=β-Glucosidases as detonators of plant chemical defense |year=2008 |last1=Morant |first1=Anne Vinther |last2=Jørgensen |first2=Kirsten |last3=Jørgensen |first3=Charlotte |last4=Paquette |first4=Suzanne Michelle |last5=Sánchez-Pérez |first5=Raquel |last6=Møller |first6=Birger Lindberg |last7=Bak |first7=Søren |journal=Phytochemistry |volume=69 |issue=9 |pages=1795–1813 |pmid=18472115 |bibcode=2008PChem..69.1795M }}</ref> This effect has been called the mustard oil bomb.<ref>{{cite journal |doi=10.1016/S0015-3796(80)80059-X |title="Die Senfolbombe": Zur Kompartimentierung des Myrosinasesystems |year=1980 |last1=Matile |first1=Ph. |journal=Biochemie und Physiologie der Pflanzen |volume=175 |issue=8–9 |pages=722–731 |language=de }}</ref> Singrin is also known to be allelopathic.<ref>{{cite journal |doi=10.1890/07-1541.1 |title=A Chemical Trait Creates a Genetic Trade-Off Between Intra- and Interspecific Competitive Ability |year=2008 |last1=Lankau |first1=Richard |journal=Ecology |volume=89 |issue=5 |pages=1181–1187 |pmid=18543611 |bibcode=2008Ecol...89.1181L }}</ref> At concentrations typically found in foods, the glucosinolates are not toxic to humans and can be useful flavor components.<ref>{{cite journal |doi=10.1080/10408398209527361 |title=Glucosinolates and their breakdown products in food and food plants |year=1983 |last1=Fenwick |first1=G. Roger |last2=Heaney |first2=Robert K. |last3=Mullin |first3=W. John |last4=Vanetten |first4=Cecil H. |journal=C R C Critical Reviews in Food Science and Nutrition |volume=18 |issue=2 |pages=123–201 |pmid=6337782 }}</ref>
Sinigrin is unusual among the glucosinolates because it is also known to be the natural precursor for other volatile compounds including epithionitrile, allyl cyanide and allyl thiocyanate.<ref name=pmid31771793/>{{rp|Fig. 22}}
== See also == * List of phytochemicals in food
== References == {{Reflist}}
{{Glycosides}}
Category:Pungent flavors Category:Glucosinolates Category:Allyl compounds Category:Potassium compounds Category:Organosulfates