methyl N-isopropyl-2-methoxy-2,3-butadienimidothioate | 918135-78-1

• 分子结构分类: 有机化合物 - 有机硫化合物 - 亚氨硫酯类
• 英文名称: methyl N-isopropyl-2-methoxy-2,3-butadienimidothioate
• 英文别名: methyl N-isopropyl-2-methoxybuta-2,3-dienimidothioate；methyl-N-isopropyl-2-methoxybuta-2,3-dienimidothioate
• CAS: 918135-78-1
• 化学式: C₉H₁₅NOS
• 分子量: 185.29
• InChiKey: LNRBLDGJOGBYEC-UHFFFAOYSA-N

物化性质

• 沸点：
  246.9±23.0 °C(Predicted)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  46.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl N-isopropyl-2-methoxy-2,3-butadienimidothioate 反应 0.05h， 生成 1-(methylsulfanyl)-N-(1-methylethylidene)-2-methoxybuta-1,3-dien-1-amine
  参考文献：
  名称：

  Reactions of heterocumulenes with organometallic reagents: XVII. One-pot synthesis of alkoxy and (alkylsulfanyl)-substituted pyrroles and 2,3-dihydropyridines from aliphatic isothiocyanates and lithiated alkoxyallenes

  摘要：

  A fundamentally new approach was developed to designing pyrrole and dihydropyridine rings from available allenes and isothiocyanates involving a single preparative stage. Applying the reaction of lithiated alkoxyallenes with aliphatic isothiocyanates we have synthesized previously unknown 1-alkyl(cycloalkyl) pyrroles and 2,3-dihydropyridines with rare alkoxy- and alkylsulfanyl substituents. It was proved that the five- and six-membered azaheterocycles formed as a result of competing reactions of direct intramolecular cyclization of S-alkylated adducts of lithiated alkoxyallenes with isothiocyanates (1-aza-1,3,4-trienes) into pyrroles and of [1,5]-sigmatropic rearrangement into conjugated 2-aza-1,3,5-trienes with subsequent closure into dihydropyridine ring (through 6 pi-electrocyclization).

  DOI：

  10.1134/s1070428011050034
• 作为产物：
  描述：

  异硫氰酸异丙酯 、 1-甲氧基-1,2-丙二烯 在 正丁基锂 、 碘甲烷 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 methyl N-isopropyl-2-methoxy-2,3-butadienimidothioate
  参考文献：
  名称：

  2-Aza-1,3,5-三烯与超碱的反应的进一步发展：通过串联去质子化-环化竞争性形成新的4,5-二氢-1,3-噻唑，二氢氮杂环庚烷和氮杂环庚烷

  摘要：

  摘要 烯丙基-和苄基硫烷基取代的2-氮杂-1,3,5-三烯很容易转化为多官能化的4,5-二氢-1,3-噻唑（ 2-噻唑啉），方法是用超碱处理使活化的SCH 2基团去质子化，然后进行分子内[1,5]环闭合。同一分子的酮亚胺功能的甲基或亚甲基片段竞争性去质子化，然后进行[1,7]电环化，形成七元氮杂杂环，二氢氮杂和/或氮杂。 烯丙基-和苄基硫烷基取代的2-氮杂-1,3,5-三烯很容易转化为多官能化的4,5-二氢-1,3-噻唑（ 2-噻唑啉），方法是用超碱处理使活化的SCH 2基团去质子化，然后进行分子内[1,5]环闭合。同一分子的酮亚胺功能的甲基或亚甲基片段竞争性去质子化，然后进行[1,7]电环化，形成七元氮杂杂环，二氢氮杂和/或氮杂。

  DOI：

  10.1055/s-0034-1378805

文献信息

• Mass spectra of new heterocycles: X. Fragmentation of the molecular ions of 1-alkyl(cycloalkyl, aryl)-3-alkoxy(aryl)-2-methylsulfanyl-1H-pyrroles
  作者：L. V. Klyba、N. A. Nedolya、O. A. Tarasova、E. R. Zhanchipova、O. G. Volostnykh

  DOI：10.1134/s1070428010070134

  日期：2010.7

  The mass spectra of previously unknown 1-alkyl(cycloalkyl, aryl)-3-alkoxy(aryl)-2-methylsulfanyl-1H-pyrroles were studied. Fragmentation of all 3-alkoxy-substituted pyrroles under electron impact (70 eV) follow both ether and sulfide decomposition paths; In particular, 1-R-substituted 3-methoxy-2-methylsulfanyl-1H-pyrroles (R = Me, Et, i-Pr, s-Bu, cyclo-C5H9, cyclo-C6H11, Ph) lose methyl radical group

  研究了以前未知的1-烷基（环烷基，芳基）-3-烷氧基（芳基）-2-甲基硫基-1 H-吡咯的质谱。所有3-烷氧基取代的吡咯在电子轰击（70 eV）下的裂解均遵循醚和硫化物的分解路径。特别是1-R-取代的3-甲氧基-2-甲基硫烷基-1 H-吡咯（R ＝ Me，Et，i- Pr，s- Bu，环-C 5 H 9，环-C 6 H 11，Ph ）从甲氧基和甲基硫烷基基团失去甲基基团。1秒的质谱丁基和1环烷基吡咯也有一个强峰（10-49％），该峰来自通过同步氢转移裂解NR键形成的奇电子[ M C n H 2 n ] +·离子。3-烷氧基-1-异丙基-2-甲基硫烷基-1 H-吡咯（Alk = Et，i -Pr，t -Bu）断裂中的O-Alk键断裂伴随重排过程，导致相应的烯烃和1-电子的1-异丙基-2-甲基硫烷基-1 H-吡咯-3-醇离子。1-烷基-2-甲基硫烷基-3-苯基-1 H-吡咯的主要裂解途径（Alk
• Simultaneous synthesis of 4,5-dihydro-3H-azepines and 3H-azepines, bearing alkoxy and alkylsulfanyl substituents, through metallation of 2-aza-1,3,5-trienes by t-BuOK
  作者：Nina A. Nedolya、Ol’ga A. Tarasova、Ol’ga G. Volostnykh、Alexander I. Albanov、Boris A. Trofimov

  DOI：10.1016/j.jorganchem.2011.07.016

  日期：2011.10

  and 3H-azepines have simultaneously been obtained from conjugated 2-aza-1,3,5-trienes by treatment with t-BuOK under mild reaction conditions (THF/DMSO, ∼−30 °C, 30 min). One-pot synthesis of 1-aza-1,3,4-trienes from α-lithiated alkoxyallenes, isopropyl isothiocyanate and alkyl iodides, followed by the thermally induced sigmatropic [1,5]-H shift, easily leads to starting 2-aza-1,3,5-trienes. The reaction

  通过在温和的条件下用t -BuOK处理，同时从共轭2-氮杂-1,3,5-三烯中同时获得了一系列新的烷氧基和烷基硫烷基取代的4,5-二氢-3 H-氮杂环庚烷和3 H-氮杂环庚烷。反应条件（THF / DMSO，〜-30°C，30分钟）。由α-锂化的烷氧基丙二烯，异硫氰酸异丙酯和烷基碘化物一锅合成1-氮杂-1,3,4-三烯，然后热诱导σ[1,5] -H转变，很容易导致2-氮杂-1,3,5-三烯。该反应通过氮杂三烯基阴离子的产生和[1,7]-电环化而进行，并且代表了一种新颖的简单方法来同时处理氮杂环庚二烯和氮杂环庚烯。
• Application of copper catalysis in a one-pot procedure for 1-alkyl-3-methoxy-2-methylthiopyrroles starting from methoxyallene and alkyl isothiocyanates
  作者：Nina A. Nedolya、Lambert Brandsma、Olga A. Tarasova、Hermann D. Verkruijsse、Boris A. Trofimov

  DOI：10.1016/s0040-4039(98)00211-1

  日期：1998.4

  1-Alkyl-3-methoxy-2-methylthiopyrroles are obtained with high purities and in high yields by Cu(I)halide-catalyzed cyclization of the products from addition of 1-lithiomethoxyallene to alkyl isothiocyanates and subsequent methylation. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Structural reorganization of (allyl-, benzyl-, and propargylsulfanyl)-substituted 2-aza-1,3,5-trienes in t-BuOK/THF/DMSO: access to rare functionalized 2-thiazolines
  作者：Nina A. Nedolya、Ol’ga A. Tarasova、Alexander I. Albanov、Boris A. Trofimov

  DOI：10.1016/j.tetlet.2014.03.015

  日期：2014.4

  Treatment of (allyl-, benzyl-, and propargylsulfanyl)-substituted 2-aza-1,3,5-trienes, which are readily accessible from lithiated methoxyallene, isopropyl isothiocyanate, and allyl, benzyl, or propargyl bromide, respectively, with t-BuOK in THF/DMSO resulted in the unexpected formation of 2-thiazoline derivatives along with seven-membered azaheterocycles [in the case of (allyl- and benzylsulfanyl)-substituted 2-aza-1,3,5-trienes]. An unprecedented structural reorganization of the azatrienes into 2-thiazolines presumably occurs via alpha-deprotonation of the substituents at the sulfur atom followed by intramolecular [1,5]-cyclization. Deprotonation of the ketimine fragment of the same molecule followed by [1,71-electrocyclization resulted in azepine ring formation. (C) 2014 Elsevier Ltd. All rights reserved.
• Reactions of lithiated allenes with isothiocyanates: First example of deprotonation of 2-aza-1,3,5-trienes. Synthesis of 6-methoxy-2-methyl-3H-azepine and 3-methoxy-7-methyl-2-methylsulfanyl-4,5-dihydro-3H-azepine
  作者：N. A. Nedolya、L. L. Dmitrieva、A. I. Albanov、L. V. Klyba、O. A. Tarasova、I. A. Ushakov

  DOI：10.1134/s1070428006030250

  日期：2006.3