Sinigrin

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Sinigrin
Sinigrin structure.svg
Names
IUPAC name
(Z)-N-[1-(β-D-glucopyranosylsulfanyl)but-3-en-1-ylidene]hydroxylamine-O-sulfonic acid
Systematic IUPAC name
(Z)-N-(1-{[(2S,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]sulfanyl}but-3-en-1-ylidene)hydroxylamine-O-sulfonic acid
Other names
Allyl glucosinolate; 2-Propenyl glucosinolate; (1Z)-N-(Sulfooxy)but-3-enimidoyl 1-thio-β-D-glucopyranoside
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
PubChem CID
UNII
  • InChI=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 Yes check.svgY
    Key: PHZOWSSBXJXFOR-GLVDENFASA-N Yes check.svgY
  • K+ salt:InChI=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
    Key: QKFAFSGJTMHRRY-FVDOMRANSA-M
  • Sinigrin: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+ salt: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+]
Properties
C10H17NO9S2
Molar mass 359.36 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

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. [1] Seeds of white mustard, Sinapis alba, give a less pungent mustard because this species contains a different glucosinolate, sinalbin.

Contents

Occurrence

The compound was first reported in 1839, [2] after its isolation from black mustard Brassica nigra , also known as Sinapis nigra, after which it was named. [3] : Section 2  Sinigrin is now known to occur widely in other brassica families including Brassicaceae and Capparaceae. [4]

Structure

E isomer (shown as anion) Sinigrin.svg
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-D-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. [5] [6] It is now known that all natural glucosinolates are of Z form. [3]

Synthesis

Biosynthesis

Sinigrin is biosynthesised from the amino acid methionine in a multi-step pathway. [3]

Laboratory synthesis

The first laboratory syntheses of sinigrin was published in 1965. [2] Later work provided a more efficient route. [7] [3] : Section 3 

Function

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. [8] This effect has been called the mustard oil bomb. [9] Singrin is also known to be allelopathic. [10] At concentrations typically found in foods, the glucosinolates are not toxic to humans and can be useful flavor components. [11]

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. [3] : Fig. 22 

See also

Related Research Articles

<span class="mw-page-title-main">Brassicaceae</span> Family of flowering plants

Brassicaceae or Cruciferae is a medium-sized and economically important family of flowering plants commonly known as the mustards, the crucifers, or the cabbage family. Most are herbaceous plants, while some are shrubs. The leaves are simple, lack stipules, and appear alternately on stems or in rosettes. The inflorescences are terminal and lack bracts. The flowers have four free sepals, four free alternating petals, two shorter free stamens and four longer free stamens. The fruit has seeds in rows, divided by a thin wall.

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

Wasabi or Japanese horseradish is a plant of the family Brassicaceae, which also includes horseradish and mustard in other genera. The plant is native to Japan and the Russian Far East including Sakhalin, as well as the Korean Peninsula. It grows naturally along stream beds in mountain river valleys in Japan.

<span class="mw-page-title-main">Horseradish</span> Species of flowering plants in the cabbage family Brassicaceae

Horseradish is a perennial plant of the family Brassicaceae. It is a root vegetable, cultivated and used worldwide as a spice and as a condiment. The species is probably native to Southeastern Europe and Western Asia.

<span class="mw-page-title-main">Isothiocyanate</span> Chemical group (–N=C=S)

In organic chemistry, isothiocyanate is the functional group −N=C=S, formed by substituting the oxygen in the isocyanate group with a sulfur. Many natural isothiocyanates from plants are produced by enzymatic conversion of metabolites called glucosinolates. These natural isothiocyanates, such as allyl isothiocyanate, are also known as mustard oils. An artificial isothiocyanate, phenyl isothiocyanate, is used for amino acid sequencing in the Edman degradation.

<span class="mw-page-title-main">Mustard oil</span> Oil derived from mustard plants

Mustard oil can mean either the pressed oil used for cooking, or a pungent essential oil also known as volatile oil of mustard. The essential oil results from grinding mustard seed, mixing the grounds with water, and isolating the resulting volatile oil by distillation. It can also be produced by dry distillation of the seed. Pressed mustard oil is used as cooking oil in some cultures, but sale is restricted in some countries due to high levels of erucic acid. Varieties of mustard seed also exist that are low in erucic acid.

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

Allyl isothiocyanate (AITC) is a naturally occurring unsaturated isothiocyanate. The colorless oil is responsible for the pungent taste of Cruciferous vegetables such as mustard, radish, horseradish, and wasabi. This pungency and the lachrymatory effect of AITC are mediated through the TRPA1 and TRPV1 ion channels. It is slightly soluble in water, but more soluble in most organic solvents.

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

Glucoraphanin is a glucosinolate found in broccoli, mustard and other cruciferous vegetables.

<span class="mw-page-title-main">Glucosinolate</span> Class of chemical compounds

Glucosinolates are natural components of many pungent plants such as mustard, cabbage, and horseradish. The pungency of those plants is due to mustard oils produced from glucosinolates when the plant material is chewed, cut, or otherwise damaged. These natural chemicals most likely contribute to plant defence against pests and diseases, and impart a characteristic bitter flavor property to cruciferous vegetables.

<span class="mw-page-title-main">Cruciferous vegetables</span> Vegetables of the family Brassicaceae

Cruciferous vegetables are vegetables of the family Brassicaceae with many genera, species, and cultivars being raised for food production such as cauliflower, cabbage, kale, garden cress, bok choy, broccoli, Brussels sprouts, mustard plant and similar green leaf vegetables. The family takes its alternative name from the shape of their flowers, whose four petals resemble a cross.

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

Glucobrassicin is a type of glucosinolate that can be found in almost all cruciferous plants, such as cabbages, broccoli, mustards, and woad. As for other glucosinolates, degradation by the enzyme myrosinase is expected to produce an isothiocyanate, indol-3-ylmethylisothiocyanate. However, this specific isothiocyanate is expected to be highly unstable, and has indeed never been detected. The observed hydrolysis products when isolated glucobrassicin is degraded by myrosinase are indole-3-carbinol and thiocyanate ion, which are envisioned to result from a rapid reaction of the unstable isothiocyanate with water. However, a large number of other reaction products are known, and indole-3-carbinol is not the dominant degradation product when glucosinolate degradation takes place in crushed plant tissue or in intact plants.

<i>Rhamphospermum arvense</i> Species of plant

Rhamphospermum arvense, the charlock mustard, field mustard, wild mustard, or just charlock, is an annual or winter annual plant in the family Brassicaceae. It is found in the fields of North Africa, Asia, Europe, and some other areas where it has been transported and naturalized. Pieris rapae, the small white butterfly, and Pieris napi, the green veined white butterfly, are significant consumers of charlock during their larval stages.

<span class="mw-page-title-main">Myrosinase</span>

Myrosinase is a family of enzymes involved in plant defense against herbivores, specifically the mustard oil bomb. The three-dimensional structure has been elucidated and is available in the PDB.

<i>Erysimum cheiranthoides</i> Species of flowering plant

Erysimum cheiranthoides, the treacle-mustard,wormseed wallflower, or wormseed mustard is a species of Erysimum native to most of central and northern Europe and northern and central Asia. Like other Erysimum species, E. cheiranthoides accumulates two major classes of defensive chemicals: glucosinolates and cardiac glycosides.

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

Sinalbin is a glucosinolate found in the seeds of white mustard, Sinapis alba, and in many wild plant species. In contrast to mustard from black mustard seeds which contain sinigrin, mustard from white mustard seeds has only a weakly pungent taste.

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

Gluconasturtiin or phenethyl glucosinolate is one of the most widely distributed glucosinolates in the cruciferous vegetables, mainly in the roots, and is probably one of the plant compounds responsible for the natural pest-inhibiting properties of growing crucifers, such as cabbage, mustard or rape, in rotation with other crops. This effect of gluconasturtiin is due to its degradation by the plant enzyme myrosinase into phenethyl isothiocyanate, which is toxic to many organisms.

<i>Brevicoryne brassicae</i> Species of true bug

Brevicoryne brassicae, commonly known as the cabbage aphid or cabbage aphis, is a destructive aphid native to Europe that is now found in many other areas of the world. The aphids feed on many varieties of produce, including cabbage, broccoli (especially), Brussels sprouts, cauliflower and many other members of the genus Brassica, but do not feed on plants outside of the family Brassicaceae. The insects entirely avoid plants other than those of Brassicaceae; even though thousands may be eating broccoli near strawberries, the strawberries will be left untouched.

<span class="mw-page-title-main">Mustard (condiment)</span> Condiment made from mustard seeds

Mustard is a condiment made from the seeds of a mustard plant.

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

Allyl cyanide is an organic compound with the formula CH2CHCH2CN. Like other small alkyl nitriles, allyl cyanide is colorless and soluble in organic solvents. Allyl cyanide occurs naturally as an antifeedant and is used as a cross-linking agent in some polymers.

Phenylalanine N-monooxygenase (EC 1.14.14.40, phenylalanine N-hydroxylase, CYP79A2) is an enzyme with systematic name L-phenylalanine,NADPH:oxygen oxidoreductase (N-hydroxylating). This enzyme catalyses the following chemical reaction

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

Glucotropaeolin or benzyl glucosinolate is a glucosinolate found in cruciferous vegetables, particularly garden cress. Upon enzymatic activity, it is transformed into benzyl isothiocyanate, which contributes to the characteristic flavor of these brassicas.

References

  1. ↑ Richard, H. "Arômes alimentaires" (PDF) (in French). Archived from the original (PDF) on 2007-02-14.
  2. 1 2 Benn, M. H.; Ettlinger, M. G. (1965). "The synthesis of sinigrin". Chemical Communications (19): 445. doi:10.1039/C19650000445.
  3. 1 2 3 4 5 Blažević, Ivica; Montaut, Sabine; Burčul, Franko; Olsen, Carl Erik; Burow, Meike; Rollin, Patrick; Agerbirk, Niels (2020). "Glucosinolate structural diversity, identification, chemical synthesis and metabolism in plants". Phytochemistry. 169: 112100. Bibcode:2020PChem.169k2100B. doi: 10.1016/j.phytochem.2019.112100 . PMID   31771793. S2CID   208318505.
  4. ↑ Fahey, Jed W.; Zalcmann, Amy T.; Talalay, Paul (2001). "The chemical diversity and distribution of glucosinolates and isothiocyanates among plants". Phytochemistry. 56 (1): 5–51. Bibcode:2001PChem..56....5F. doi:10.1016/S0031-9422(00)00316-2. PMID   11198818.
  5. ↑ Waser, Jürg; Watson, William H. (1963). "Crystal Structure of Sinigrin". Nature. 198 (4887): 1297–1298. Bibcode:1963Natur.198.1297W. doi:10.1038/1981297b0. S2CID   4187013.
  6. ↑ Marsh, R. E.; Waser, J. (1970). "Refinement of the crystal structure of sinigrin". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 26 (7): 1030–1037. Bibcode:1970AcCrB..26.1030M. doi:10.1107/S0567740870003539.
  7. ↑ Abramski, Wojciech; Chmielewski, Marek (1996). "Practical Synthesis of Sinigrin". Journal of Carbohydrate Chemistry. 15: 109–113. doi:10.1080/07328309608005429.
  8. ↑ Morant, Anne Vinther; Jørgensen, Kirsten; Jørgensen, Charlotte; Paquette, Suzanne Michelle; Sánchez-Pérez, Raquel; Møller, Birger Lindberg; Bak, Søren (2008). "β-Glucosidases as detonators of plant chemical defense". Phytochemistry. 69 (9): 1795–1813. Bibcode:2008PChem..69.1795M. doi:10.1016/j.phytochem.2008.03.006. PMID   18472115.
  9. ↑ Matile, Ph. (1980). ""Die Senfolbombe": Zur Kompartimentierung des Myrosinasesystems". Biochemie und Physiologie der Pflanzen (in German). 175 (8–9): 722–731. doi:10.1016/S0015-3796(80)80059-X.
  10. ↑ Lankau, Richard (2008). "A Chemical Trait Creates a Genetic Trade-Off Between Intra- and Interspecific Competitive Ability". Ecology. 89 (5): 1181–1187. doi:10.1890/07-1541.1. PMID   18543611.
  11. ↑ Fenwick, G. Roger; Heaney, Robert K.; Mullin, W. John; Vanetten, Cecil H. (1983). "Glucosinolates and their breakdown products in food and food plants". C R C Critical Reviews in Food Science and Nutrition. 18 (2): 123–201. doi:10.1080/10408398209527361. PMID   6337782.
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