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二烯丙基二硫

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二烯丙基二硫
IUPAC名
4,5-dithia-1,7-octadiene
Diallyldisulfide
英文名 Diallyl disulfide
別名 4,5-二硫雜-1,7-辛二烯
二烯丙基二硫醚
二(2-丙烯基)二硫
二硫化二丙烯
烯丙基二硫
烯丙基二硫醚
二硫(2-丙烯)
二烯丙基二硫(大蒜素)
二烯丙基二硫化物
識別
CAS號 2179-57-9  checkY
PubChem 16590
ChemSpider 15730
SMILES
 
  • S(SC\C=C)C\C=C
InChI
 
  • 1/C6H10S2/c1-3-5-7-8-6-4-2/h3-4H,1-2,5-6H2
InChIKey PFRGXCVKLLPLIP-UHFFFAOYAX
KEGG C08369
性質
化學式 C6H10S2
摩爾質量 146.28 g·mol⁻¹
外觀 淡黃清澈液體,強烈蒜臭味[1]
密度 1.01 g/cm3[2]
沸點 180℃
折光度n
D
1.541[3]
危險性
歐盟危險性符號
有害有害 Xn
刺激性刺激性 Xi
[3]
警示術語 R:R10, R22, R36/37/38
安全術語 S:S16, S22, S26, S36, S36/37/39, S37/39
閃點 144 °F(62 °C)[3]
若非註明,所有數據均出自標準狀態(25 ℃,100 kPa)下。

二烯丙基二硫(英語:diallyl disulfide,縮寫DADS)又叫4,5-二硫雜-1,7-辛二烯4,5-dithia-1,7-octadiene),是一種有機硫化合物,常見於蔥屬植物中,如洋蔥大蒜。二烯丙基二硫、二烯丙基三硫和二烯丙基四硫是大蒜油的主要成分。DADS是一種淡黃液體,不溶於水,含有強烈蒜臭味。大蒜或者其他蔥科植物切開後就會釋放蒜素,蒜素分解後可得到DADS,它對大蒜健康生長有很多好處,但它也是一種抗敏原,會導致大蒜過敏。通過高度稀釋後的DADS也可以用作食物調味料

歷史

1844年奧地利化學家西奧多·韋爾特海姆(Theodor Wertheim)用水蒸氣蒸餾法蒸餾大蒜得到有刺激性氣味物質,並將它命名為「烯丙基」,然而在1892年,德國化學家弗里德里希·威廉·塞姆萊爾(Friedrich Wilhelm Semmler)發現產物中的一部分物質為二烯丙基二硫。1944年切斯特·卡瓦里托(Chester J. Cavallito)和約翰·海斯·貝利(John Hays Bailey)共同發現了DADS的前體——蒜素。1947年,A.斯托爾和E.澤貝克發現半胱氨酸的衍生物(如蒜氨酸)可通過蒜氨酸酶催化生成二烯丙基二硫和蒜素。[4]

含量

蔥科植物(特別是大蒜洋蔥韭蔥)的細胞破損後釋放蒜素,蒜素分解後可得到DADS。每100克蒜頭中含有2克富含DADS的蒜油(2 wt%),通過水蒸汽蒸餾蒜頭得到DADS的產量最高;DADS也可以從大蒜葉中提取,但是含量要明顯低得多,每100克大蒜葉只含有0.06克蒜油(0.06 wt%)。[5][6]

性質

物理性質

DADS是淡黃色清澈液體,有強烈的蒜臭味,在典型的80%純度下沸點為138–139°C,閃點為50°C;在20°C下,密度約為1.0 g/mL,蒸汽壓約為1 mmHg。DADS是一種非極性的分子,因此它不溶於水,而溶於脂肪、 油、 油脂和非極性溶劑,如正己烷甲苯[1][3][2]

化學性質

  • 催化劑作用下,二烯丙基二硫與鹵代烷反應,生成1-烷硫基-3-1-丙烯和1,3-二(烷硫基)丙烯[7]。(圖左方)
  • 間氯過氧苯甲酸會氧化二烯丙基二硫,生成外消旋大蒜素[8]。(圖右上方)
  • 系催化劑作用下,DADS可反應生成含硫的雜原子多環化合物[9]。(圖右下方)

製備

工業製備DADS的方法是在惰性氣體環境下,將二硫化鈉烯丙基氯(或烯丙基溴)加熱至40–60°C反應生成DADS。該反應為放熱反應,實際上可得到理論的88%的收率[10]

在空氣環境、催化劑四丁銨作用下,相同原材料可合成少量的DADS,對應的收率為低於82%[11]。工業合成或直接從植物中提取DADS的主要問題是DADS與其他更高的硫化物(如二烯丙基三硫)分離,他們有着相似的物理性質,所以典型的工業製品中DADS含量只有80%。當溫度超過37°C的時候,蒜素能特別快地還原成DADS[12]

另外也可以利用烯丙基硫醇乙醇吡啶存在下氧化生成DADS[3]

應用

氯化鐵或者氯化銅的催化作用下,DADS可以作為合成聚合度更高的二烯丙基聚硫的前體物,而且它也是合成蒜素的原材料之一。在食品工業里,DADS可用來提升肉類、蔬菜和水果的口感。[1][13][3]

生物學重要性

氣味和口味

生物感知DADS的難聞氣味要通過瞬態電壓感受器陽離子通道,子類A,成員1(TRPA1),這種離子通道一早就已存在於人類和動物體內,就連在真菌中也可以找到。因此,蔥科植物很可能在早期進化時就已經形成DADS-TRPA1的保護機制,以對抗捕食者。[14][15]

中毒和解毒作用

DADS是細胞解毒過程中一種高效物質,他能顯著增加穀胱甘肽S-轉移酶(GST)的產量,而GST能在細胞中與親電子有害化合物結合。所以蒜頭能夠促進諸如參與體外肝細胞的解毒作用和保護體外神經細胞以免進入氧化應激狀態的活動[16][17][18][19][20][21][22][23]。通過一個對老鼠的研究證實這種解毒的效果可以預防炎症的發生,其中老鼠長期服用的DADS保護腸細胞免於中毒。這項研究也顯示服用高劑量的蒜油可產生某種副作用,但這並非是由DADS引起的[24]。在化療過程中,DADS可通過參與肝的解毒作用為肝提供保護,例如阻止氰化物的解毒作用。[25][26]

抗菌效果

因為有機硫化合物具有抗菌和殺(幼)蟲的特性,所以蔥科植物細胞在遭遇破壞後釋放這類化合物變得極為重要[27]。蒜油中的DADS能抑制黴菌和細菌的生長,而且它也扮演着對抗引起胃潰瘍的細菌——幽門螺桿菌Helicobacter pylori)的角色,但就沒有如蒜素一樣高效[28][29]。手術前進行的內臟(如消化道)選擇性去污染服用的製劑中就包含妥布黴素和具抗菌效果的DADS。一項臨床研究顯示,在心臟瓣膜手術中這樣的製劑可以預防內毒素血症的出現[30]

抵禦結腸癌

大蒜可以預防結腸直腸癌(大腸癌)[31],而且多項研究表明DADS是負責預防過程中的主要成分,和在老鼠身上表現出來的一樣,其效果具有劑量依賴性[32][33]。也有研究表明DADS對癌細胞的影響比正常細胞更加強烈[34]。它導致多種物質的大量累積,如能激活酶並且導致癌細胞凋亡的活性氧,這種累積同樣具有劑量依賴性[35]

抵禦心血管疾病

有證據顯示大蒜能阻止多種心血管疾病的發展。其中一些心血管疾病的產生原因可能跟氧化應激有關,如動脈硬化冠心病,其中後者的病情可通過DADS協助細胞解毒和其他機制而得到減輕[4]。DADS通過激活TRPA1離子通道能短暫降低血壓[14]

安全性

DADS是一種皮膚刺激劑、過敏原。這是大蒜過敏(對大蒜的變應性接觸性皮炎)的主要原因,對廚師和家庭主婦影響較大。過敏症狀通常始於指尖而且不能通過戴手套預防過敏發生,因為DADS能滲透大部分在市面上出售的手套到達皮膚[36][37][38][39]

老鼠口服DADS的半數致死量(LD50)是每千克體重260毫克,而皮膚攝入DADS的半數致死量是每千克體重3.6克。每千克體重5克的高劑量DADS放在貓的皮膚上足可以溶血性貧血而致死[1][40]。因此不可讓貓狗等寵物食用含有蔥科植物成份的食物。

通過氣相色譜法,DADS可在空氣和血液中容易被檢測出來[41][42][43]

參見

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外部連結