天然芥菜籽油 | 57-06-7

• 物质功能分类: 生物化工 - 提取物 - 植物基础油
• 分子结构分类: 有机化合物 - 有机硫化合物 - 异硫氰酸盐
• 中文名称: 天然芥菜籽油
• 中文别名: 芥末油；芥籽油；3-异硫氰基-1-丙烯；异硫氰酸烯丙酯；异硫氰酸丙烯酯；异硫代氰酸烯丙酯
• 英文名称: Allyl isothiocyanate
• 英文别名: N-allyl isothiocyanate；AITC；3-isothiocyanatoprop-1-ene
• CAS: 57-06-7；8007-40-7
• 化学式: C₄H₅NS
• mdl: MFCD00004822
• 分子量: 99.1564
• InChiKey: ZOJBYZNEUISWFT-UHFFFAOYSA-N

物化性质

• 物理描述：
  Allyl isothiocyanate, stabilized appears as a colorless to pale-yellow oily liquid with an irritating odor. Flash point 135°F. Boiling point 300°F. Poisonous by ingestion and skin absorption. Emits toxic fumes when heated to high temperature. Insoluble in water and slightly denser than water. Hence sinks in water. Used to make other chemicals and as a fumigant.
• 颜色/状态：
  Colorless to pale yellow, oily liquid
• 气味：
  Very pungent
• 味道：
  Acrid taste
• 沸点：
  152.0 °C
• 熔点：
  -80.0 °C
• 闪点：
  115 °F (46 °C) (Closed Cup)
• 溶解度：
  In water, 2,000 mg/L at 20 °C
• 密度：
  1.0126 g/cu cm at 20 °C
• 蒸汽密度：
  3.41 (NTP, 1992) (Relative to Air)
• 蒸汽压力：
  0.493 kPa at 20 °C (3.7 mm Hg at 30 °C)
• 稳定性/保质期：
  Tends to darken on aging.
• 分解：
  When heated to decomposition or on contact with acid or acid fumes it emits highly toxic fumes of /cyanides, oxides of sulfur, and oxides of nitrogen/.
• 气味阈值：
  8X10-3 PPM
• 折光率：
  Index of refraction = 1.5306 at 20 °C/D
• 保留指数：
  846;847;846;853;856;860;885;885

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  6
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  44.4
• 氢给体数：
  0
• 氢受体数：
  2

ADMET

代谢

四名成年志愿者（两男两女，年龄20-45岁）摄入了10克棕色芥末和面包，而对照组的四名参与者只吃了没有芥末的面包。在第二个实验中，20克棕色芥末被加入火鸡或鸡肉三明治中食用。在这两个实验中，在用餐后至48小时的不同时间间隔内收集尿液样本。尿液中的主要代谢物是N-乙酰-S-(N-烯丙基硫代碳酸基)-L-半胱氨酸，即烯丙基异硫氰酸酯的N-乙酰半胱氨酸结合物，但在12小时后未发现该代谢物。这种代谢物的排泄与剂量有关。

Four adult volunteers (two men, two women, aged 20-45) ingested 10 g brown mustard with bread, and a control group of four participants ate bread without mustard. In a second experiment, 20 g of brown mustard were eaten in turkey or chicken sandwiches. In both experiments, urine samples were collected at various intervals up to 48 hr following the meal. The major urinary metabolite was N-acetyl-S-(N-allylthiocarbamoyl)- L-cysteine, the N-acetylcysteine conjugate of allyl isothiocyanate, but none was found after 12 hr. Excretion of this metabolite was dose-dependent.

来源:Hazardous Substances Data Bank (HSDB)

代谢

Fischer 344 大鼠（8-10周龄）和 B6C3F1 小鼠（6-8周龄）雄性和雌性被给予 (14)C-异硫氰酸烯丙基的乙醇溶液：Emulphor EL-620：水（1:1:8）的剂量为 25.2 或 252 微摩尔/千克（2.5 或 25 毫克/千克体重）通过灌胃给药... 在大鼠和小鼠尿液中检测到的主要代谢物是巯基酸，N-乙酰-S-(N-烯丙基硫代碳酸基)-L-半胱氨酸，而小鼠尿液中还含有另外三种主要代谢物和两种次要代谢物。雄性和雌性大鼠对异硫氰酸烯丙基的代谢相似，但雌性大鼠排出的尿液量是雄性的两倍多。

Male and female Fischer 344 rats (8-10 weeks old) and male and female B6C3F1 mice (6-8 weeks old) were given (14)C-allyl isothiocyanate in a solution of ethanol: Emulphor EL-620:water (1:1:8) at doses of 25.2 or 252 umol/kg (2.5 or 25 mg/kg bw) by gavage... The major metabolite detected in rat and mouse urine was the mercapturic acid, N-acetyl-S-(N-allylthiocarbamoyl)-L-cysteine, while mouse urine also contained three other major and two minor metabolites. The metabolism of allyl isothiocyanate by male and female rats was similar, but the females excreted more than twice as much urine as the males.

来源:Hazardous Substances Data Bank (HSDB)

代谢

... 活体吸收的烯丙基异硫氰酸酯主要通过巯基酸途径代谢并以尿液形式排出体外。...

... Allyl isothiocyanate absorbed in vivo is metabolized mainly through the mercapturic acid pathway and excreted in urine. ...

来源:Hazardous Substances Data Bank (HSDB)

代谢

大鼠在尿液中排泄出一种主要和四种次要的代谢物。通过核磁共振光谱学鉴定，大鼠尿液中的主要代谢物是巯基尿酸 N-乙酰-S-(N-丙烯基硫代甲酰基)-L-半胱氨酸。小鼠在尿液中排泄出与大鼠尿液中相同的主要代谢物，以及另外三种主要和两种次要的代谢物。观察到这些代谢物的相对量存在性别相关的差异。两个物种都在粪便中排泄出单一代谢物。雄性和雌性大鼠对 AITC 的代谢相似，但雌性大鼠的尿量是雄性大鼠的两倍多。目前的研究结果表明，尿液中的 AITC 代谢物（或代谢物）的更浓缩溶液的排泄可能是 AITC 对雄性大鼠膀胱产生毒性作用的原因。

...Rats excreted one major and four minor metabolites in urine. The major metabolite from rat urine was identified by NMR spectroscopy to be the mercapturic acid N-acetyl-S-(N-allylthiocarbamoyl)-L-cysteine. Mice excreted in urine the same major metabolite identified in rat urine as well as three other major and two minor metabolites. Sex-related variations were observed in the relative amounts of these metabolites. Both species excreted a single metabolite in feces. Metabolism of AITC by male and female rats was similar, but female rats excreted over twice the urine volume of male rats. Results of the present study indicate that excretion of a more concentrated solution of AITC metabolite(s) in urine may account for the toxic effects of AITC on the bladder of male rats.

来源:Hazardous Substances Data Bank (HSDB)

代谢

在小鼠尿液中发现了三种放射性成分，在大鼠尿液中发现了两种。小鼠体内的三种成分是无机硫氰酸盐、烯丙基硫代氨基甲酰巯基尿酸和烯丙基硫代氨基甲酰半胱氨酸，但在大鼠尿液中没有发现半胱氨酸结合物。在大鼠体内，大约80%的(14)C以硫氰酸根离子的形式存在于尿液中，而在小鼠中，大约75%以巯基尿酸的形式存在。这表明，在小鼠中，AITC的水解是主要的代谢途径，而在大鼠中，谷胱甘肽结合是主要的途径。

... Three radioactive components were found in the urine of mice and two in rats. The three components were inorganic thiocyanate, allylthiocarbamoylmercapturic acid and allylthiocarbamoylcysteine in mice, but no cysteine conjugate was found in rat urine. In the mouse, approximately 80% of the (14)C was present in the urine as the thiocyanate ion whereas in the rat some 75% was as the mercapturate. This indicates that in the mouse, hydrolysis of AITC was the major metabolic pathway whereas in the rat glutathione conjugation was the major route. ...

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

氰化物是电子传递链第四个复合体中细胞色素c氧化酶的抑制剂（存在于真核细胞线粒体膜中）。它与这种酶中的铁原子形成复合物。氰化物与这种细胞色素的结合阻止了电子从细胞色素c氧化酶传递到氧气。因此，电子传递链被中断，细胞无法再通过有氧呼吸产生ATP能量。主要依赖有氧呼吸的组织，如中枢神经系统和心脏，受到的影响尤为严重。氰化物也通过结合过氧化氢酶、谷胱甘肽过氧化物酶、变性血红蛋白、羟钴胺素、磷酸酶、酪氨酸酶、抗坏血酸氧化酶、黄嘌呤氧化酶、琥珀酸脱氢酶和Cu/Zn超氧化物歧化酶产生一些毒性效应。氰化物与变性血红蛋白中的铁离子结合，形成无活性的氰变性血红蛋白。

Cyanide is an inhibitor of cytochrome c oxidase in the fourth complex of the electron transport chain (found in the membrane of the mitochondria of eukaryotic cells). It complexes with the ferric iron atom in this enzyme. The binding of cyanide to this cytochrome prevents transport of electrons from cytochrome c oxidase to oxygen. As a result, the electron transport chain is disrupted and the cell can no longer aerobically produce ATP for energy. Tissues that mainly depend on aerobic respiration, such as the central nervous system and the heart, are particularly affected. Cyanide is also known produce some of its toxic effects by binding to catalase, glutathione peroxidase, methemoglobin, hydroxocobalamin, phosphatase, tyrosinase, ascorbic acid oxidase, xanthine oxidase, succinic dehydrogenase, and Cu/Zn superoxide dismutase. Cyanide binds to the ferric ion of methemoglobin to form inactive cyanmethemoglobin. (L97)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌性证据

评估：对于丙烯基异硫氰酸酯在人类中的致癌性，证据不足。在实验动物中，丙烯基异硫氰酸酯的致癌性证据有限。总体评估：丙烯基异硫氰酸酯的致癌性无法归类为对人类有影响（第3组）。

Evaluation: There is inadequate evidence in humans for the carcinogenicity of allyl isothiocyanate. There is limited evidence in experimental animals for the carcinogenicity of allyl isothiocyanate. Overall evaluation: Allyl isothiocyanate is not classifiable as to its carcinogenicity to humans (Group 3).

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌物分类

国际癌症研究机构致癌物：烯丙基异硫氰酸酯

IARC Carcinogenic Agent:Allyl isothiocyanate

来源:International Agency for Research on Cancer (IARC)

毒理性

• 致癌物分类

国际癌症研究机构（IARC）致癌物分类：第3组：无法归类其对人类致癌性

IARC Carcinogenic Classes:Group 3: Not classifiable as to its carcinogenicity to humans

来源:International Agency for Research on Cancer (IARC)

毒理性

• 致癌物分类

国际癌症研究机构专论：第73卷：（1999年）某些在啮齿动物中引起肾或膀胱肿瘤的化学物质以及其他一些物质

IARC Monographs:Volume 73: (1999) Some Chemicals that Cause Tumours of the Kidney or Urinary Bladder in Rodents and Some Other Substances

来源:International Agency for Research on Cancer (IARC)

吸收、分配和排泄

烯丙基异硫氰酸酯的生物利用度极高，几乎90%口服给药的烯丙基异硫氰酸酯被吸收。

... Bioavailability of allyl isothiocyanate is extremely high, as nearly 90% of orally administered AITC is absorbed. ...

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

口服给予Fischer 344大鼠和B6C3F1小鼠2.5和25毫克/千克体重的烯丙基(14)C-异硫氰酸酯(AITC)后，放射性物质主要通过尿液排出(占剂量的50-80%)。粪便中发现了较小的量(6-12%)，以及呼出气体中也有(3-7%)。两种物种之间的主要区别在于，与小鼠相比(占剂量的2-5%)，大鼠在4天后保留了更多的放射性物质(占剂量的18-24%)。在大鼠和小鼠的血液中，(14)C-AITC衍生的放射性物质的量存在物种差异；与小鼠相比(96小时)，在大鼠血液中可测量到的放射性物质的水平持续了更长的时间(长达240小时)。对口服(14)C-AITC后雄性和雌性大鼠的膀胱进行检查，发现性别差异，雄性大鼠膀胱组织中(14)C-AITC及其代谢产物的量更多。

The urine was the major route of excretion of radioactivity (50-80% of dose) following the oral administration (2.5 and 25 mg/kg body weight) of allyl(14)C-isothiocyanate (AITC) to male and female Fischer 344 rats and B6C3F1 mice. Smaller amounts were found in the feces (6-12%) and expired air (3-7%). The major difference between the two species was the greater retention of radioactivity after 4 days within rats (18-24% of dose) when compared with mice (2-5% of dose). ... A species difference was seen in the amount of (14)C-AITC-derived radioactivity present in the whole blood of rats and mice; measurable levels of radioactivity remained within rat blood for a longer time period (up to 240 hr) when compared with mice (96 hr). Examination of the urinary bladders of male and female rats following oral dosing with (14)C-AITC showed a sex difference with greater amounts of (14)C-AITC and/or its metabolites within the bladder tissue of male rats. ...

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

雄性和雌性Fischer 344大鼠（8-10周龄）以及雄性和雌性B6C3F1小鼠（6-8周龄）被给予乙醇：Emulphor EL-620：水（1:1:8）溶液中的(14)C-丙烯基异硫氰酸酯，剂量为25.2或252微摩尔/千克（2.5或25毫克/千克体重）通过灌胃给药，25毫克/千克体重通过尾静脉注射进行分布研究...放射性标记物主要在尿液中清除（70-80%），在呼出空气中（13-15%），在粪便中较少（3-5%），两种物种均如此。...丙烯基异硫氰酸酯在组织分布上的主要性别和物种差异局限于膀胱。因此，在早期时间点，雄性大鼠的膀胱中丙烯基异硫氰酸酯衍生的放射性标记物浓度是雄性小鼠的五倍，但在24小时内，所有丙烯基异硫氰酸酯衍生的放射性标记物都从雄性大鼠膀胱中清除。

Male and female Fischer 344 rats (8-10 weeks old) and male and female B6C3F1 mice (6-8 weeks old) were given (14)C-allyl isothiocyanate in a solution of ethanol: Emulphor EL-620:water (1:1:8) at doses of 25.2 or 252 umol/kg (2.5 or 25 mg/kg bw) by gavage, 25 mg/kg bw by injection into a tail vein for studies of distribution ...The radiolabel was cleared primarily in urine (70-80%) and exhaled air (13-15%), with lesser amounts in feces (3-5%) in both species. ... Major sex- and species-related differences in the tissue distribution of allyl isothiocyanate were restricted to the urinary bladder. Thus, the urinary bladder of male rats contained five times higher concentrations of allyl isothiocyanate-derived radiolabel that that of male mice at early time points, but all of the allyl isothiocyanate-derived radiolabel was cleared from male rat bladder by 24 hr.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 安全说明：
  S16,S23,S24,S26,S28B,S36/37,S36/37/39,S45,S60,S61
• 危险品运输编号：
  UN 1545 6.1/PG 2
• WGK Germany：
  3
• 海关编码：
  29309070
• 危险类别：
  6.1
• 危险品标志：
  T
• 危险类别码：
  R36/37/38,R43,R10,R50/53,R23/24/25
• RTECS号：
  NX8225000
• 包装等级：
  II
• 危险标志：
  GHS06,GHS08,GHS09
• 危险性描述：
  H301 + H331,H310,H315,H317,H319,H334,H410
• 危险性防范说明：
  P261,P273,P280,P301 + P310,P302 + P350,P305 + P351 + P338

制备方法与用途

芥子油简介

鱼生火肉生痰，萝卜白菜保平安。坐立不安腹胀气，求仙问神心难安，灵丹妙药钱儿不贵，仔细发现在身边。今天就为大家介绍一种排气的灵丹妙药——芥子油。芥子油实际上是多种异硫氰酸酯化合物的总称，不仅具有防癌作用，还能解决胀气问题。其主要成分是硫化物，通常带有辛辣气味，在生吃萝卜时可以感受到这种味道。

主要成分

芥子油是由多种芥子油苷组成的混合物。根据芥子油苷分子中侧链的不同，可分为脂肪族芥子油苷（如烯丙基芥子油苷）、吲哚族芥子油苷（如吲哚-3-甲基芥子油苷）和芳香族芥子油苷（苯基芥子油苷或苄基芥子油苷）。

来源

绿芥末来源于十字花科家族中的山嵛菜属植物——山葵。其中的异硫氰酸酯化合物在遇水后会产生强烈的辛辣味，用于制作各种调味品和泡菜。黑芥子含有挥发性精油0.25%～1.25%，主要成分是黑芥子糖苷或黑芥子硫苷酸钾；白芥子则不含挥发油，其主要成分为白芥子硫苷。

用途 香辛料

广泛用于各种调味剂，如配制芥末粉、芥末酱。整粒者可用于腌渍或与蔬菜同煮。

香料

供泡菜、罐头、沙司、调味料等之用。

生产方法

从十字花科一年生草本芥菜（黑芥Brassica nigra或白芥B．Alba）的种子中提取。粉碎后加入温水中搅拌，放置一昼夜，经水蒸馏而得。也可通过冷榨法压榨种子后再用水和蒸汽蒸馏。

毒性与使用限量 GRAS（FEMA；FDA，§182.10, 2000）

GRAS认证意味着芥子油是安全的，可以在食品中使用。

使用限量

• 黑芥：调味料5200mg/kg；肉类制品2300mg/kg。
• 白芥：软饮料350mg/kg；焙烤食品20mg/kg；调味料8200mg/kg；肉类制品1400mg/kg；腌渍品2500～3800mg/kg。

化学性质

芥子油为球形，体积甚小。白芥千粒重约6.5g；黑芥千粒重仅1.3g，约为白芥的一半。它们都带有强烈的辛辣刺激味。含脂肪25%～35%，可压榨除去。白芥籽中不含挥发性油，其主要成分为白芥子硫苷；黑芥子则含有0.25%～1.25%的挥发性精油。

安全与储存 性质

• 可燃。
• 火场排出辛辣刺激烟雾。

储运特性

库房低温、通风、干燥环境存放。

灭火剂

水、二氧化碳、干粉或砂土。

反应信息

• 作为反应物：
  描述：

  天然芥菜籽油 在 硫酸 作用下， 生成 羰基硫
  参考文献：
  名称：

  Hofmann,A.W., Chemische Berichte, 1868, vol. 1, p. 181

  摘要：

  DOI：
• 作为产物：
  描述：

  diethyl 1-[(prop-2-en-1-ylcarbamothioyl)sulfanyl]hydrazine-1,2-dicarboxylate 以85%的产率得到天然芥菜籽油
  参考文献：
  名称：

  使用偶氮二羧酸二烷基酯合成新型二硫代氨基甲酸酯和黄原酸酯：SN键的形成

  摘要：

  通过在温和且无催化剂的条件下原位生成的二硫代氨基甲酸或黄原酸酯与偶氮二羧酸二烷基酯的反应，开发了一种用于合成一类新型二硫代氨基甲酸酯或黄原酸酯的单锅三组分途径。该反应的特点是范围广，效率高和直接的分离方案。在制备对称和不对称的硫脲，异硫氰酸酯和硫代氨基甲酸酯时，证明了二硫代氨基甲酸酯和黄原酸酯的合成效用。

  DOI：

  10.1016/j.tet.2018.02.049
• 作为试剂：
  描述：

  L-胱氨酸 在 天然芥菜籽油 作用下， 以 水 为溶剂， 生成 1,3-二烯丙基-2-硫脲 、 2-allylamino-2-thiazoline-4-carboxylic acid 、 3(3H)-allyl-5,6-dihydro-5-amino-2(2H)-thioxo-1,3-thiazin-4-one 、 2-氨基-2-噻唑啉-4-羧酸
  参考文献：
  名称：

  Kawakishi, Shunro; Goto, Tamami; Namiki, Mitsuo, Agricultural and Biological Chemistry, 1983, vol. 47, # 9, p. 2071 - 2076

  摘要：

  DOI：

文献信息

• Studying Products of Hydrazine Interaction with Isothiocyanates by Means of Chromatography and Mass Spectrometry
  作者：A. V. Ul’yanov、K. E. Polunin、I. A. Polunina、A. K. Buryak

  DOI：10.1134/s0036024421050290

  日期：2021.5

  compounds in real-time and delayed modes are optimized. The physicochemical characteristics of the sorption of thiosemicarbazides are determined. The decomposition and fragmentation of their metastable protonated molecules are studied. Schemes are proposed for the formation of fragmented and characteristic thiosemicarbazide ions in different modes of ionization.

  摘要 使用质谱在电子碰撞电离和基质辅助激光解吸/电离模式下结合气相色谱和液相色谱研究烷基肼与乙基-、烯丙基-和苯基异硫氰酸酯之间的相互作用产物。优化了反应混合物的色谱分离条件以及实时和延迟模式下目标化合物的质谱鉴定。测定氨基硫脲吸附的物理化学特性。研究了它们的亚稳态质子化分子的分解和碎裂。提出了在不同电离模式下形成碎片化和特征氨基硫脲离子的方案。
• Mechanism of the zinc-catalyzed addition of azide ion to unsaturated compounds: Synthesis of 5-substituted 1Н-tetrazoles from nitriles and of 1-substituted 1Н-tetrazole-5-thiols from isothiocyanates
  作者：L. V. Myznikov、S. V. Vorona、T. V. Artamonova、Yu. E. Zevatskii

  DOI：10.1134/s1070363217040119

  日期：2017.4

  The mechanism of the formation of 5-substituted 1H-tetrazoles from organic nitriles and thiocyanates in the presence of NaN3 and ZnCl2 in aliphatic alcohols was studied. The results of this study allowed efficient methods of synthesis of substituted tetrazoles from nitriles, thiocyanates, and isothiocyanates to be proposed.

  研究了NaN 3和ZnCl 2在脂肪醇中由有机腈和硫氰酸盐形成5-取代的1 H-四唑的机理。这项研究的结果允许提出从腈，硫氰酸盐和异硫氰酸盐合成取代四唑的有效方法。
• Antimicrobial and Anti-biofilm Activity of Thiourea Derivatives Bearing 3-amino-1H-1,2,4-triazole Scaffold
  作者：Joanna Stefanska、Karolina Stepien、Anna Bielenica、Daniel Szulczyk、Barbara Miroslaw、Anna E Koziol、Giuseppina Sanna、Filippo Iuliano、Silvia Madeddu、Michal Jozwiak、Marta Struga

  DOI：10.2174/1573406412666151204003146

  日期：2016.6.23

  3-amino-1H-1,2,4-triazole with the commercial aliphatic and aromatic isothiocyanates. The aliphatic isothiocyanate was used as reagent leading to substitution on NH atom of 3-aminotriazole ring, whereas the triazole amino group was substituted when isothiocyanate group was bonded to the Csp2 hybridized atom, e.g. an aryl or C=O fragment. All compounds were evaluated in vitro for the antimicrobial activity

  通过使3-氨基-1H-1,2,4-三唑与市售的脂族和芳族异硫氰酸酯反应，制得了21种硫脲衍生物。脂族异硫氰酸酯用作导致3-氨基三唑环的NH原子上取代的试剂，而当异硫氰酸酯基团键合至Csp2杂化原子，例如芳基或C ＝ O片段时，三唑氨基被取代。在体外评估所有化合物的抗微生物活性。衍生物1、2、4、8、9、10和12对革兰氏阳性球菌（金黄色葡萄球菌和表皮葡萄球菌）显示出最高的抑制作用。观察到的MIC值在4–32μg/ mL范围内。还测试了化合物对医院中耐金霉素的金黄色葡萄球菌菌株的体外抗菌活性。观察到的MIC值从4到64μg/ mL不等。产物4和10有效地抑制了耐甲氧西林和表皮葡萄球菌标准菌株的生物膜的形成。与对照相比，发现化合物10的IC50值为2–6μg/ mL更有希望。此外，评估了所有研究的硫脲对MT-4细胞的细胞毒性。化合物18具有明显的细胞毒性（CC50 = 8μM）。
• 2-Thioxo-1,3-thiazepan-4-ones, a novel class of cyclic dithiourethanes with a 7-membered ring system
  作者：Wolfgang Hanefeld、Harald Schütz

  DOI：10.1002/jhet.5570360509

  日期：1999.9

  Reaction of isothiocyanates 1 with γ-thiobutyrolactone (2) in alkaline medium yielded 4-thiocarbamoylthiobutyric acids 3 after acidification, which could be cyclized to the 2-thioxo-1,3-thiazepan-4-ones 6. Additional reactions were observed with the formation of 6t from p-phenylenediisothiocyanate (1s) and with the formation of 6w from benzyl isothiocyanate (1t). 3-Acetylamino-γ-thiobutyrolactone (7)

  异硫氰酸酯1与γ-硫代丁内酯（2）在碱性介质中的反应在酸化后产生4-硫代氨基甲酰基硫代丁酸3，可将其环化为2-thioxo-1,3-thiazepan-4-ones 6。观察到另外的反应，由对苯二异硫氰酸酯形成6t（1s），由异硫氰酸苄酯形成6w（1t）。3-乙酰氨基-γ-硫代丁内酯（7）也可用于该反应，生成丁酸衍生物3u-3w。环化产生1,3-硫氮杂derivatives衍生物6x，y其在环收缩下重排至1，3-噻嗪酮8a，b。
• Stereoselective Lewis Acid Mediated (3+2) Cycloadditions of<i>N</i>-H- and<i>N</i>-Sulfonylaziridines with Heterocumulenes
  作者：Robert A. Craig、Nicholas R. O'Connor、Alexander F. G. Goldberg、Brian M. Stoltz

  DOI：10.1002/chem.201303699

  日期：2014.4.14

  Alkyl and aryl isothiocyanates and carbodiimides are effective substrates in (3+2) cycloadditions with N‐sulfonyl‐2‐substituted aziridines and 2‐phenylaziridine for the synthesis of iminothiazolidines and iminoimidazolidines. Additionally, the stereoselective (3+2) cycloaddition of N‐H‐ and N‐sulfonylaziridines with isothiocyanates can be accomplished, allowing for the synthesis of highly enantioenriched

  烷基和芳基异硫氰酸酯和碳二亚胺是与N-磺酰基-2-取代的氮丙啶和 2-苯基氮丙啶进行 (3+2) 环加成反应以合成亚氨基噻唑烷和亚氨基咪唑烷的有效底物。此外，可以完成N -H-和N-磺酰基氮丙啶与异硫氰酸酯的立体选择性（3+2）环加成，从而合成高度对映体富集的亚氨基噻唑烷。本文在这些化学、区域和非对映选择性转化的背景下提出了紧密离子对机制的证据。所证明的从杂环产物中除去磺酰基的能力显示了这些化合物对于进一步衍生化和应用的效用。

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