(E,E) 1-Propenethiosulfinate | 120637-83-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硫代亚磺酸酯
• 英文名称: (E,E) 1-Propenethiosulfinate
• 英文别名: S-1-propenyl 1-propenethiosulfinate；S-1-(E)-propenyl 1-(E)-propenesulfinothioate；Thiosulfinate；(E)-1-[(E)-prop-1-enyl]sulfinylsulfanylprop-1-ene
• CAS: 120637-83-4
• 化学式: C₆H₁₀OS₂
• 分子量: 162.277
• InChiKey: GYJUUWJKEUIYPF-GGWOSOGESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E,E) 1-Propenethiosulfinate 生成 (+/-)(1α,2α,3β,4α,5β)-2,3-Dimethyl-5,6-dithiabicyclo[2.1.1]hexane 5-oxide
  参考文献：
  名称：

  Zwiebelanes: novel biologically active 2,3-dimethyl-5,6-dithiabicyclo[2.1.1]hexane 5-oxides from onion

  摘要：

  DOI：

  10.1021/ja00190a064
• 作为产物：
  描述：

  (E,E)-di-1-propenyl disulfide 在 sodium carbonate 、 间氯过氧苯甲酸 作用下， 以 氘代氯仿 为溶剂， 生成 (E,E) 1-Propenethiosulfinate
  参考文献：
  名称：

  Allium Chemistry:  Synthesis and Sigmatropic Rearrangements of Alk(en)yl 1-Propenyl Disulfide S-Oxides from Cut Onion and Garlic¹

  摘要：

  Reduction (LiAlH4) of propyl 1-propynyl sulfide (8) to (E)-1-propenyl propyl sulfide ((E)-10), C-S cleavage (Li/NH3) to lithium (E)-1-propenethiolate (Li(E)-11), and reaction with MeSO(2)Cl gives (E,E)-bis(1-propenyl) disulfide ((E,E)-2); i-Bu(2)AlH reduction of 8 to (Z)-10 and reaction with Li/NH3 and then MeSO(2)Cl gives (Z,Z)-2 via Li (Z)-11. Reaction of MeSO(2)SR (R = Me (12a), n-Pr (12b), CH2CH=CH2 (12c), CH=CHMe (12d)) with K (E)-11 gives (E,Z)-2 from (Z)-12d; Li (E,Z)-11 gives alkyl (E)- and (Z)-1-propenyl disulfides (MeCH=CHSSR, R = Me (3a), n-Pr (3b), CH2=CHCH2 (3c)) from 12a-c, respectively. Oxidation at -60 degrees C of (E,E)-, (Z,Z)-, and (E,Z)-2 gives (E)-1-propenesulfinothioic acid S-(E)-1-propenyl ester ((E,E)-13, (E,E)-MeCH=CHS(O)SCH=CHMe) from (E,E)-2, (Z,Z)-13 from (Z,Z)-2, and ca. 2:1 (E,Z)-13)/(Z,E)-13 from (E,Z)-2. Warming (Z,Z)-13 gives (+/-)-(1 alpha,2 alpha,3 beta,4 alpha,5 beta)-2,3-dimethyl-5,6-dithiabicyclo[2.1.1]hexane 5-oxide (1a), endo-5-methyl-exo-6-methyl-2-oxa-3,7-dithiabicyclo[2.2.1]heptane (14a), and exo-5-methyl-endo-6-methyl-2-oxa-3,7-dithiabicyclo[2.2. 1]heptane (14b). Warming (E,E)-13 gives 14a and 14b; (E,Z)-13/(Z,E)-13 gives (1 alpha,2 alpha,3 alpha,4 alpha,5 beta)-2,3-dimethyl-5,6-dithiabicyclo[2.1.1]hexane 5-oxide (1b), exo-5-methyl-exo-6-methyl-2-oxa-3,7-dithiabicyclo[2.2.1]heptane (14c), and endo-5-methyl-endo-6-methyl-2-oxa-3,7-dithiabicyclo[2.2.1]heptane (14d). Oxidation of 3a-c gives MeCH=CHSS(O)R (4) and MeCH=CHS(O)SR (5). At -60 degrees C, m-CPBA (2 equiv) converts (E,E)-2 into (Z,Z)-d,l-2,3-dimethyl-1,4-butanedithial 1,4-dioxide (26) while (Z,Z)-2 gives meso- and d,l-26. With NaIO4, 4/5 (R = Me) gives (E)- or (Z)-12a and MeCH=CHSO(2)SMe (6a); with m-CPBA (Z)-MeS(O)CHMeCH=S+-O- (25a) forms. At 85 degrees C 2 gives 1:1 cis- and trans-2-mercapto-3,4-dimethyl-2,3-dihydrothiophene (29).

  DOI：

  10.1021/ja953444h

文献信息

• First insights into the mode of action of a “lachrymatory factor synthase” – Implications for the mechanism of lachrymator formation in Petiveria alliacea, Allium cepa and Nectaroscordum species
  作者：Quan He、Roman Kubec、Abhijit P. Jadhav、Rabi A. Musah

  DOI：10.1016/j.phytochem.2011.07.013

  日期：2011.11

  alliacea L. (Phytolaccaceae) to yield the P. alliacea lachrymator (phenylmethanethial S-oxide) showed the protein to be a dehydrogenase. It functions by abstracting hydride from sulfenic acids of appropriate structure to form their corresponding sulfines. Successful hydride abstraction is dependent upon the presence of a benzyl group on the sulfur to stabilize the intermediate formed on abstraction of hydride

  一项酶与 Petiveria alliacea L.（Phytolaccaceae）中的蒜氨酸酶产生的次磺酸反应以产生 P. alliacea lachrymator（苯甲硫基 S-氧化物）的研究表明该蛋白质是一种脱氢酶。它的作用是从适当结构的次磺酸中提取氢化物以形成相应的亚磺酸。成功的氢化物提取取决于硫上苄基的存在，以稳定提取氢化物时形成的中间体。这种脱氢酶活性与在洋葱中发现的催泪因子合酶 (LFS) 的活性形成对比，后者催化 1-丙烯亚磺酸重排为 (Z)-丙硫醇 S-氧化物，即洋葱催泪剂。根据其催化的反应类型，洋葱 LFS 应归类为异构酶，并称为“
• Identification of Two Novel Pigment Precursors and a Reddish-Purple Pigment Involved in the Blue-Green Discoloration of Onion and Garlic
  作者：Shinsuke Imai、Kaori Akita、Muneaki Tomotake、Hiroshi Sawada

  DOI：10.1021/jf0519818

  日期：2006.2.1

  By using a model reaction system representing blue-green discoloration that occurs when purees of onion (Allium cepa L.) and garlic (Allium sativum L.) are mixed, we isolated two pigment precursors (PPs) and a reddish-purple pigment (PUR-1) and determined their chemical structures. PPs were isolated from a heat-treated solution containing color developer (CD) and either l-valine or l-alanine, and their

  通过使用表示洋葱（Allium cepa L.）和大蒜（Allium sativum L.）的浆液混合时发生的蓝绿色变色的模型反应系统，我们分离了两种颜料前体（PPs）和红紫色颜料（PUR -1）并确定其化学结构。从含有彩色显影剂（CD）和l-缬氨酸或l-丙氨酸的热处理溶液中分离PPs，并确定其结构为2-（3,4-二甲基吡咯基）-3-甲基丁酸（PP-Val）分别是2-（3,4-二甲基-1H-吡咯基）丙酸（PP-Ala）。接下来，从包含PP-Val和大蒜素的热处理溶液中分离出PUR-1，并确定其结构为（1E）-1-（1-（（（1S）-1-羧基-2-甲基丙基）-3） ，4-二甲基-1H-吡咯-2-基）-丙-1-烯-3-（1-（（（1S）-1-羧基-2-甲基丙基）-3,4-二甲基-1H-吡咯- 2-y）。PUR-1的结构表明，含有3,4-二甲基吡咯环的PP分子已被大蒜素的烯丙基交联形成共轭颜料。
• PROCESS OF PREPARING CONJUGATES OF ALLIUM ORGANOSULFUR COMPOUNDS WITH AMINO ACIDS, PEPTIDES, AND PROTEINS
  申请人：Parkin Kirk L.

  公开号：US20110082282A1

  公开（公告）日：2011-04-07

  Processes using Allium tissue homogenates and extracts in a simple and cost-effective manner to maximize the yields and recovery of thiosulfinates from Allium tissues and related organisms possessing alliinase, LF synthase and/or S-alk(en)yl-L-cysteine sulfoxides are disclosed.

  本发明揭示了使用Allium组织匀浆和提取物的过程，以简单且经济有效的方式最大化从Allium组织和相关生物中具有alliinase、LF合成酶和/或S-烷基-L-半胱氨酸亚砜的硫代磺酸盐的产量和回收率。
• US8481284B2
  申请人：——

  公开号：US8481284B2

  公开（公告）日：2013-07-09
• [EN] PROCESS OF PREPARING CONJUGATES OF ALLIUM ORGANOSULFUR COMPOUNDS WITH AMINO ACIDS, PEPTIDES, AND PROTEINS<br/>[FR] PROCÉDÉ DE PRÉPARATION DE CONJUGUÉS DE COMPOSÉS ORGANOSOUFRÉS D'ALLIUM AVEC DES ACIDES AMINÉS, DES PEPTIDES, ET DES PROTÉINES
  申请人：WISCONSIN ALUMNI RES FOUND

  公开号：WO2011044113A1

  公开（公告）日：2011-04-14

  Processes using Allium tissue homogenates and extracts in a simple and cost-effective manner to maximize the yields and recovery of thiosulfinates from Allium tissues and related organisms possessing alliinase, LF synthase and/or S-alk(en)yl-L-cysteine sulfoxides are disclosed.