methyl N-benzamido-N-methylcarbamodithioate | 51592-30-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl N-benzamido-N-methylcarbamodithioate
• CAS: 51592-30-4
• 化学式: C₁₀H₁₂N₂OS₂
• 分子量: 240.35
• InChiKey: NEFRPUNGHGNBEZ-UHFFFAOYSA-N

物化性质

• 密度：
  1.271±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  89.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl N-benzamido-N-methylcarbamodithioate 在 高氯酸 、 乙酸酐 作用下， 以 乙醚 为溶剂， 反应 5.0h， 以96%的产率得到3-methyl-2-methylsulfanyl-5-phenyl-[1,3,4]thiadiazolium; perchlorate
  参考文献：
  名称：

  Alkyl 2-Methyldithiocarbazates in Heterocyclic Synthesis: Preparation of 2-Alkylthio-1,3,4-thiadiazolium Cations and 2-Thioxo-2,3-dihydro-1,3,4-Oxadiazole Derivatives

  摘要：

  烷基 3-酰基-2-甲基二硫代卡巴肼 2 可由烷基 2-甲基二硫代卡巴肼和酰基氯化物制得，在高氯酸/乙酸酐的作用下发生闭环反应，生成 2-烷硫基 3-甲基-1,3,4-噻二唑鎓盐 4。化合物 2 还会在碱催化下发生环化反应，生成 4-甲基-2-硫酮-2,3-二氢-1,3,4-恶二唑 3，再与四氟硼酸三甲基锍反应，生成 3-甲基-2-甲硫基-1,3,4-恶二唑阳离子 5。1-Aroyl-2-ethoxyoxalyl-1-phenylhydrazines 6 在三氟甲磺酸/乙酸酐的作用下发生环化反应，生成 2-芳基-5-乙氧羰基-3-苯基-1,3,4-恶二唑鎓盐 7。

  DOI：

  10.1055/s-1988-27672
• 作为产物：
  描述：

  1-甲基肼-1-二硫代羧酸甲酯 、 苯甲酰氯 以 甲苯 为溶剂， 反应 4.0h， 以99%的产率得到methyl N-benzamido-N-methylcarbamodithioate
  参考文献：
  名称：

  Alkyl 2-Methyldithiocarbazates in Heterocyclic Synthesis: Preparation of 2-Alkylthio-1,3,4-thiadiazolium Cations and 2-Thioxo-2,3-dihydro-1,3,4-Oxadiazole Derivatives

  摘要：

  烷基 3-酰基-2-甲基二硫代卡巴肼 2 可由烷基 2-甲基二硫代卡巴肼和酰基氯化物制得，在高氯酸/乙酸酐的作用下发生闭环反应，生成 2-烷硫基 3-甲基-1,3,4-噻二唑鎓盐 4。化合物 2 还会在碱催化下发生环化反应，生成 4-甲基-2-硫酮-2,3-二氢-1,3,4-恶二唑 3，再与四氟硼酸三甲基锍反应，生成 3-甲基-2-甲硫基-1,3,4-恶二唑阳离子 5。1-Aroyl-2-ethoxyoxalyl-1-phenylhydrazines 6 在三氟甲磺酸/乙酸酐的作用下发生环化反应，生成 2-芳基-5-乙氧羰基-3-苯基-1,3,4-恶二唑鎓盐 7。

  DOI：

  10.1055/s-1988-27672

文献信息

• Platinum assisted cyclization of S-methyl 3-acyl-2-methyldithiocarbazates under mild conditions. Crystal structure of [Pt2(μ-SMe)(terpy)2][ClO4]3 †
  作者：Giuliano Annibale、Paola Bergamini、Valerio Bertolasi、Michela Cattabriga、Antonio Lazzaro、Andrea Marchi、Gianni Vertuani

  DOI：10.1039/a904859f

  日期：——

  The reaction of the newly synthesized aqua complex [Pt(terpy)(OH2)][BF4]2 with S-methyl 3-acyl-2-methyldithiocarbazates under a variety of experimental conditions has been studied. Using a 2∶1 metal to ligand ratio in methanol, a platinum assisted cyclization was observed. The reaction products were Δ2-1,3,4-oxadiazoline-5-thione derivatives and the binuclear tricationic complex [Pt2(µ-SMe)(terpy)2]3+ whose molecular structure has been determined by X-ray crystallography. This platinum assisted transformation is proposed as a new synthetic route to Δ2-1,3,4-oxadiazoline-5-thiones under mild conditions. In the presence of an excess of a non-co-ordinating acid (HClO4, CH3SO3H or CF3SO3H) the cyclization is completely quenched and complexes with co-ordinated S-methyl 3-acyl-2-methyldithiocarbazates have been isolated. A general mechanism which accounts for the observed transformations is proposed on the basis of 1H NMR and UV/Vis evidence.

  研究了新合成的含水配合物 [Pt(terpy)(OH2)][BF4]2与 S-甲基 3-酰基-2-甲基二硫代咔嗪盐在各种实验条件下的反应。在甲醇中，金属与配体的比例为 2∥1，观察到了铂辅助环化反应。反应产物是δ2-1,3,4-噁二唑啉-5-硫酮衍生物和双核三阳离子配合物[Pt2(µ-SMe)(terpy)2]3+，其分子结构已通过 X 射线晶体学确定。这种铂辅助转化被认为是在温和条件下合成δ2-1,3,4-噁二唑啉-5-硫酮的新途径。在过量的非配位酸（HClO4、CH3SO3H 或 CF3SO3H）存在下，环化反应被完全淬灭，并分离出配位的 S-甲基 3-酰基-2-甲基二硫代氨基甲酸酯络合物。根据 1H NMR 和 UV/Vis 证据，提出了解释所观察到的转化的一般机制。
• Alkylierung der 3-Acyl-thio- und -dithio-carbazinester-Gruppierung CONHNHCSYR
  作者：Kurt Rüfenacht

  DOI：10.1002/hlca.19740570105

  日期：——

  Abstract3‐Benzoyl‐thiocarbazic acid O‐methyl ester 7a and 3‐benzoyl‐dithiocarbazic acid methyl ester 7b are methylated, in presence of alkali, at the SH group of 1a, the ene‐thiol tautomer of 1, to give the 3‐benzoyl‐isothiocarbazic acid O, S‐dimethyl ester 8a and the 3‐benzoyl‐isodithiocarbazic acid dimethyl ester 8b resp., which clearly differ from the N‐methylated compounds 11a and 12a or 11b and 12b prepared from the two N‐methyl benzohydrazides 9 and 10 resp. (melting points, thin‐layer chromatography and NMR. spectra).The previously reported [1] ring closure of 3‐(ω‐chloroalkanoyl)‐thiocarbazic acid O‐alkyl esters and ‐dithiocarbazic acid alkyl esters can be interpretated as an intramolecular auto‐alkylation of CONHNHCSYR: the 3‐(chloroacetyl)‐compounds 2 are S‐alkylated (enethiol form) to the six‐membered thiadiazinones 4, but the 3‐(3‐chloropropionyl)‐compounds 3 are N‐alkylated to the pyrazolidinones 6, the five‐membered ring being preferred in the latter case to the seven‐membered ring 5 which would be formed by S‐alkylation. Hence the position of alkylating attack depends on the size of the ring to be formed.As a consequence, starting from 3‐(4‐chlorobutyryl) compounds 13, an alternative between the two N‐alkylation products 14 (five‐membered ring) and 15 (six‐membered ring) would be expected. On the contrary however, a combination of 1,3,4‐thiadiazole ring closure and chlorine elimination predominates, giving the 5‐(3‐hydroxypropyl)‐1,3,4‐thiadiazoles 16. This reaction may proceed via the butyrolactone intermediates 18 and could therefore be interpreted as O‐alkylation followed by rearrangement.
• Alkyl 2-Methyldithiocarbazates in Heterocyclic Synthesis: Preparation of 2-Alkylthio-1,3,4-thiadiazolium Cations and 2-Thioxo-2,3-dihydro-1,3,4-Oxadiazole Derivatives
  作者：P. Molina、A. Tárraga、A. Espinosa

  DOI：10.1055/s-1988-27672

  日期：——

  Alkyl 3-acyl-2-methyldithiocarbazates 2, available from alkyl 2-methyldithiocarbazates and acyl chlorides, undergo ring closure by the action of perchloric acid/acetic anhydride to give 2-alkylthio 3-methyl-1,3,4-thiadiazolium salts 4. Compounds 2 also undergo base-catalyzed cyclization to give 4-methyl-2-thioxo-2,3-dihydro-1,3,4-oxadiazoles 3, which react with trimethyloxonium tetrafluoroborate to give 3-methyl-2-methylthio-1,3, 4-oxadiazolium cations 5. 1-Aroyl-2-ethoxyoxalyl-1-phenylhydrazines 6 undergo cyclization by action of trifluoromethanesulfonic acid/acetic anhydride to yield 2-aryl-5-ethoxycarbonyl-3-phenyl-1,3,4-oxadiazolium salts 7.

  烷基 3-酰基-2-甲基二硫代卡巴肼 2 可由烷基 2-甲基二硫代卡巴肼和酰基氯化物制得，在高氯酸/乙酸酐的作用下发生闭环反应，生成 2-烷硫基 3-甲基-1,3,4-噻二唑鎓盐 4。化合物 2 还会在碱催化下发生环化反应，生成 4-甲基-2-硫酮-2,3-二氢-1,3,4-恶二唑 3，再与四氟硼酸三甲基锍反应，生成 3-甲基-2-甲硫基-1,3,4-恶二唑阳离子 5。1-Aroyl-2-ethoxyoxalyl-1-phenylhydrazines 6 在三氟甲磺酸/乙酸酐的作用下发生环化反应，生成 2-芳基-5-乙氧羰基-3-苯基-1,3,4-恶二唑鎓盐 7。