View source for Sinigrin

{{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 [[glucoside]]s found in some plants of the family [[Brassicaceae]] such as [[Brussels sprout]]s, [[broccoli]], and the seeds of black [[Mustard seed|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 |url-status=dead |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 |page=112100 |pmid=31771793 |bibcode=2020PChem.169k2100B |s2cid=208318505 }}</ref>{{rp|Section 2}} Sinigrin is now known to occur widely in other [[brassica|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==
[[File:Sinigrin.svg|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 [[pyranose|β-<small>D</small>-glucopyranose]] configuration. It was unclear whether the C=N bond was in the [[E–Z notation|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 [[allelopathy|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 [[wikt:epithionitrile|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:Nutrition]]
[[Category:Glucosinolates]]
[[Category:Allyl compounds]]
[[Category:Potassium compounds]]
[[Category:Sulfate esters]]