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
	系統名; (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
別名	黑芥子硫苷、烯丙基硫代葡萄糖苷、2-烯丙基硫代葡萄糖苷
識別
CAS號	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
性質
化學式	C10H17NO9S2
摩爾質量	359.37 g·mol−1
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

黑芥子苷（英語：sinigrin），又稱烯丙基硫代葡萄糖苷（英語：allyl glucosinolate）。是一種硫代葡萄糖苷，存在於在許多十字花科植物中，如抱子甘藍、西蘭花、黑芥末（學名：Brassica nigra）的種子等。當這類含有黑芥子苷植物的組織受到損壞時，黑芥子酶（英語：Myrosinase）會將黑芥子苷分解產生芥末油（異硫氰酸烯丙酯），產生和芥末和辣根一樣的辛辣味^[1]。

白芥末（學名：Sinapis alba）籽辛辣味較小是因為其包含另一種硫代葡萄糖苷—白芥子苷。

分佈

黑芥末籽首次被報導是在1839年,^[2]，科學家從黑芥末（學名： Sinapis nigra）中分離得到，由此命名為"sinigrin"^[3]^{:Section 2}。現在已知其在十字花科和山柑科等十字花目植物中廣泛存在^[4]。

結構

黑芥子苷的結構域在1930年開始構建，發現其是一種β-D-吡喃葡萄糖衍生物。但不清楚C=N鍵為Z式構象（即S和O原子在雙鍵同一側）還是E式構象（S和O原子在雙鍵兩側）。直到1963年通過X射線繞射研究其鉀鹽才查明為Z式構象^[5]^[6]^[3]。

合成

生物合成

黑芥子苷在生物體內由甲硫氨酸經多步反應得到^[3]。

實驗室合成

在1965年首次發表了黑芥子苷的實驗室合成方法^[2]。後續又不斷優化其合成路線，使得合成效率更高^[7]^[3]^{:Section 3}。

作用

黑芥子苷作為硫代葡萄糖苷，在自然條件下是作為植物的防禦物質。通過葡萄糖硫苷酶脫除黑芥子苷中葡萄糖基後，剩餘部分經過重排得到芥末辛辣味物質異硫氰酸烯丙酯。當植物收到傷害時，就會引發該反應產生對許多蟲子有毒的異硫氰酸烯丙酯.^[8]。這一過程也被稱為「芥子油炸彈」^[9] 。黑芥子苷同時也是植物用於化感作用的物質^[10]。在這些植物作為食物的情況下，這些硫代葡萄糖苷的濃度不會對人體產生中毒，然而可以作為一種調味料使用^[11]。

黑芥子苷在硫代葡萄糖苷中並不常見，因為它也是其他揮發性化合物的天然前體，包括環氧硫腈、烯丙基腈和烯丙基硫氰酸酯等^[3]^{:Fig. 22}。

參考文獻

^ Richard, H. Arômes alimentaires (PDF). （原始內容 (PDF)存檔於2007-02-14）（法語）.
^ ^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 （德語）.
^ 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). （原始內容 (PDF)存檔於2007-02-14）（法語）.

[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 （德語）.

[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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