黑芥子苷

黑芥子苷
	IUPAC名; (Z)-N-[1-(β-D-glucopyranosylsulfanyl)but-3-en-1-ylidene]hydroxylamine-O-sulfonic acid
	系统名; (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
别名	黑芥子硫苷、烯丙基硫代葡萄糖苷、2-烯丙基硫代葡萄糖苷
识别
CAS号	534-69-0 ; 3952-98-5
PubChem	5486549; 23684362
ChemSpider	4588961, 4576678
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;
ChEBI	79317
性质
化学式	C10H17NO9S2
摩尔质量	359.37 g·mol−1
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

黑芥子苷（英语：sinigrin），又称烯丙基硫代葡萄糖苷（英语：allyl glucosinolate）。是一种硫代葡萄糖苷，存在于在许多十字花科植物中，如抱子甘蓝、西兰花、黑芥末（学名：Brassica nigra）的种子等。当这类含有黑芥子苷植物的组织受到损坏时，黑芥子酶（英语：Myrosinase）会将黑芥子苷分解产生芥末油（异硫氰酸烯丙酯），产生和芥末和辣根一样的辛辣味^[1]。

白芥末（学名：Sinapis alba）籽辛辣味较小是因为其包含另一种硫代葡萄糖苷—白芥子苷。

分布

黑芥末籽首次被报导是在1839年,^[2]，科学家从黑芥末（学名： Sinapis nigra）中分离得到，由此命名为"sinigrin"^[3]^{:Section 2}。现在已知其在十字花科和山柑科等十字花目植物中广泛存在^[4]。

结构

黑芥子苷的结构域在1930年开始构建，发现其是一种β-D-吡喃葡萄糖衍生物。但不清楚C=N键为Z式构象（即S和O原子在双键同一侧）还是E式构象（S和O原子在双键两侧）。直到1963年通过X射线衍射研究其钾盐才查明为Z式构象^[5]^[6]^[3]。

合成

生物合成

黑芥子苷在生物体内由甲硫氨酸经多步反应得到^[3]。

实验室合成

在1965年首次发表了黑芥子苷的实验室合成方法^[2]。后续又不断优化其合成路线，使得合成效率更高^[7]^[3]^{:Section 3}。

作用

黑芥子苷作为硫代葡萄糖苷，在自然条件下是作为植物的防御物质。通过葡萄糖硫苷酶脱除黑芥子苷中葡萄糖基后，剩余部分经过重排得到芥末辛辣味物质异硫氰酸烯丙酯。当植物收到伤害时，就会引发该反应产生对许多虫子有毒的异硫氰酸烯丙酯.^[8]。这一过程也被称为“芥子油炸弹”^[9] 。黑芥子苷同时也是植物用于化感作用的物质^[10]。在这些植物作为食物的情况下，这些硫代葡萄糖苷的浓度不会对人体产生中毒，然而可以作为一种调味料使用^[11]。

黑芥子苷在硫代葡萄糖苷中并不常见，因为它也是其他挥发性化合物的天然前体，包括环氧硫腈、烯丙基腈和烯丙基硫氰酸酯等^[3]^{:Fig. 22}。

参考文献

^ Richard, H. Arômes alimentaires (PDF). （原始内容 (PDF)存档于2007-02-14）（法语）.
^ ^2.0 ^2.1 Benn, M. H.; Ettlinger, M. G. The synthesis of sinigrin. Chemical Communications. 1965, (19): 445. doi:10.1039/C19650000445.
^ ^3.0 ^3.1 ^3.2 ^3.3 ^3.4 Blažević, Ivica; Montaut, Sabine; Burčul, Franko; Olsen, Carl Erik; Burow, Meike; Rollin, Patrick; Agerbirk, Niels. Glucosinolate structural diversity, identification, chemical synthesis and metabolism in plants. Phytochemistry. 2020, 169: 112100. Bibcode:2020PChem.169k2100B. PMID 31771793. S2CID 208318505. doi:10.1016/j.phytochem.2019.112100 .
^ Fahey, Jed W.; Zalcmann, Amy T.; Talalay, Paul. The chemical diversity and distribution of glucosinolates and isothiocyanates among plants. Phytochemistry. 2001, 56 (1): 5–51. Bibcode:2001PChem..56....5F. PMID 11198818. doi:10.1016/S0031-9422(00)00316-2.
^ Waser, Jürg; Watson, William H. Crystal Structure of Sinigrin. Nature. 1963, 198 (4887): 1297–1298. Bibcode:1963Natur.198.1297W. S2CID 4187013. doi:10.1038/1981297b0.
^ Marsh, R. E.; Waser, J. Refinement of the crystal structure of sinigrin. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 1970, 26 (7): 1030–1037. Bibcode:1970AcCrB..26.1030M. doi:10.1107/S0567740870003539.
^ Abramski, Wojciech; Chmielewski, Marek. Practical Synthesis of Sinigrin. Journal of Carbohydrate Chemistry. 1996, 15: 109–113. doi:10.1080/07328309608005429.
^ Morant, Anne Vinther; Jørgensen, Kirsten; Jørgensen, Charlotte; Paquette, Suzanne Michelle; Sánchez-Pérez, Raquel; Møller, Birger Lindberg; Bak, Søren. β-Glucosidases as detonators of plant chemical defense. Phytochemistry. 2008, 69 (9): 1795–1813. Bibcode:2008PChem..69.1795M. PMID 18472115. doi:10.1016/j.phytochem.2008.03.006.
^ Matile, Ph. "Die Senfolbombe": Zur Kompartimentierung des Myrosinasesystems. Biochemie und Physiologie der Pflanzen. 1980, 175 (8–9): 722–731. doi:10.1016/S0015-3796(80)80059-X （德语）.
^ Lankau, Richard. A Chemical Trait Creates a Genetic Trade-Off Between Intra- and Interspecific Competitive Ability. Ecology. 2008, 89 (5): 1181–1187. PMID 18543611. doi:10.1890/07-1541.1.
^ Fenwick, G. Roger; Heaney, Robert K.; Mullin, W. John; Vanetten, Cecil H. Glucosinolates and their breakdown products in food and food plants. C R C Critical Reviews in Food Science and Nutrition. 1983, 18 (2): 123–201. PMID 6337782. doi:10.1080/10408398209527361.

[1] Richard, H. Arômes alimentaires (PDF). （原始内容 (PDF)存档于2007-02-14）（法语）.

[Benn-2] 2.0 ^2.1 Benn, M. H.; Ettlinger, M. G. The synthesis of sinigrin. Chemical Communications. 1965, (19): 445. doi:10.1039/C19650000445.

[pmid31771793-3] 3.0 ^3.1 ^3.2 ^3.3 ^3.4 Blažević, Ivica; Montaut, Sabine; Burčul, Franko; Olsen, Carl Erik; Burow, Meike; Rollin, Patrick; Agerbirk, Niels. Glucosinolate structural diversity, identification, chemical synthesis and metabolism in plants. Phytochemistry. 2020, 169: 112100. Bibcode:2020PChem.169k2100B. PMID 31771793. S2CID 208318505. doi:10.1016/j.phytochem.2019.112100 .

[4] Fahey, Jed W.; Zalcmann, Amy T.; Talalay, Paul. The chemical diversity and distribution of glucosinolates and isothiocyanates among plants. Phytochemistry. 2001, 56 (1): 5–51. Bibcode:2001PChem..56....5F. PMID 11198818. doi:10.1016/S0031-9422(00)00316-2.

[5] Waser, Jürg; Watson, William H. Crystal Structure of Sinigrin. Nature. 1963, 198 (4887): 1297–1298. Bibcode:1963Natur.198.1297W. S2CID 4187013. doi:10.1038/1981297b0.

[6] Marsh, R. E.; Waser, J. Refinement of the crystal structure of sinigrin. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 1970, 26 (7): 1030–1037. Bibcode:1970AcCrB..26.1030M. doi:10.1107/S0567740870003539.

[7] Abramski, Wojciech; Chmielewski, Marek. Practical Synthesis of Sinigrin. Journal of Carbohydrate Chemistry. 1996, 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. β-Glucosidases as detonators of plant chemical defense. Phytochemistry. 2008, 69 (9): 1795–1813. Bibcode:2008PChem..69.1795M. PMID 18472115. doi:10.1016/j.phytochem.2008.03.006.

[9] Matile, Ph. "Die Senfolbombe": Zur Kompartimentierung des Myrosinasesystems. Biochemie und Physiologie der Pflanzen. 1980, 175 (8–9): 722–731. doi:10.1016/S0015-3796(80)80059-X （德语）.

[10] Lankau, Richard. A Chemical Trait Creates a Genetic Trade-Off Between Intra- and Interspecific Competitive Ability. Ecology. 2008, 89 (5): 1181–1187. PMID 18543611. doi:10.1890/07-1541.1.

[11] Fenwick, G. Roger; Heaney, Robert K.; Mullin, W. John; Vanetten, Cecil H. Glucosinolates and their breakdown products in food and food plants. C R C Critical Reviews in Food Science and Nutrition. 1983, 18 (2): 123–201. PMID 6337782. doi:10.1080/10408398209527361.

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