2,2-二甲基-5-({[(4-甲基苯基)磺酰基]氧基}亚氨基)-1,3-二恶烷-4,6-二酮 | 215436-24-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2,2-二甲基-5-({[(4-甲基苯基)磺酰基]氧基}亚氨基)-1,3-二恶烷-4,6-二酮
• 英文名称: 2,2-dimethyl-5-(p-tosyloxyimino)-1,3-dioxane-4,6-dione
• 英文别名: 5-(tosyloxyimino)-2,2-dimethyl-1,3-dioxane-4,6-dione；5-tosyloxyimino-2,2-dimthyl-1,3-dioxane-4,6-dione；2,2-dimethyl-1,3-dioxane-4,5,6-trione 5-O-[(4-methylphenyl)sulfonyl]oxime；2,2-Dimethyl-5-{[(4-methylbenzene-1-sulfonyl)oxy]imino}-1,3-dioxane-4,6-dione；[(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)amino] 4-methylbenzenesulfonate
• CAS: 215436-24-1
• 化学式: C₁₃H₁₃NO₇S
• 分子量: 327.315
• InChiKey: IFNDHYIZZLDILT-UHFFFAOYSA-N

物化性质

• 熔点：
  155-156 °C
• 沸点：
  417.4±38.0 °C(Predicted)
• 密度：
  1.44±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  117
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,2-二甲基-5-({[(4-甲基苯基)磺酰基]氧基}亚氨基)-1,3-二恶烷-4,6-二酮 在 二甲基氯化铝 作用下， 以 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 4.5h， 生成 2,8,8-trimethyl-7,9-dioxa-1-azaspiro[4.5]dec-1-ene-6,10-dione
  参考文献：
  名称：

  Synthesis of Substituted Pyridines via Regiocontrolled [4 + 2] Cycloadditions of Oximinosulfonates

  摘要：

  Diels-Alder cycloadditions of oximinosulfonate 8 with a variety of 1,3-dienes proceed with regiochemistry opposite to that observed with conventional imino dienophiles, providing expeditious synthetic routes to substituted pyridines, tetrahydropyridines, and pyrrolines. The oximinosulfonate 8 is prepared in one convenient synthetic operation from Meldrum's acid and reacts with conjugated dienes at -78 degrees C in the presence of 2 equiv of dimethylaluminum chloride to afford [4 + 2] cycloadducts in good to excellent yield. Exposure of these cycloadducts to the action of NaOMe and N-chlorosuccinimide in methanol-THF at room temperature then produces substituted pyridines. The utility of this new two-step annulation protocol is demonstrated in total syntheses of the pyridine alkaloids fusaric acid and (S)-(+)-fusarinolic acid. Heating the [4 + 2] cycloadducts derived from 8 in a mixture of acetonitrile and pH 7 phosphate buffer induces an unusual Stieglitz-type rearrangement leading to the formation of interesting spirobicyclic pyrrolines.

  DOI：

  10.1021/jo981014e
• 作为产物：
  描述：

  对甲苯磺酰氯 、 5-hydroxyimino-2,2-dimethyl-1,3-dioxane-4,6-dione sodium salt 以 丙酮 为溶剂， 反应 5.0h， 以79%的产率得到2,2-二甲基-5-({[(4-甲基苯基)磺酰基]氧基}亚氨基)-1,3-二恶烷-4,6-二酮
  参考文献：
  名称：

  Cyanocarbonylation of Amines with 5-Tosyloxyimino-2,2-dimethyl-1,3-dioxane-4,6-dione

  摘要：

  5-Tosyloxyimino-2,2-dimethyl-1,3-dioxane-4,6-dione (3), prepared by the reaction of 5-hydroxyimino-2,2-dimethyl-1,3-dioxane-4,6-dione sodium salt (2) with tosyl chloride, was treated with various amines (4a-c and 6a,b) in the presence of triethylamine to give the corresponding N-cyanocarbonyl derivatives (5a-c and 7a,b). However, reaction of 3 with benzyl alcohol gave rise to the formation of dibenzyl carbonate (10).

  DOI：

  10.3987/com-99-s22

文献信息

• Exploiting <i>N</i>-Centered Umpolung Reactivity of α-Iminomalonates for the Synthesis of <i>N</i>-Sulfenylimines and Sulfonamides
  作者：Sourav Roy、Krishnapriya Anattil Unnikrishnan、Arijit Chakraborty、Rositha Kuniyil、Indranil Chatterjee

  DOI：10.1021/acs.orglett.4c00110

  日期：2024.3.1

  An efficient and interesting N-centered umpolung method has been disclosed to construct beneficial S–N bonds, furnishing N-sulfenylimines, which can readily be converted into the corresponding sulfonamide derivatives in a one-pot sequential operation. N-Sulfenylimines are potent intermediates in organic synthesis, whereas sulfonamides are of major molecular interest due to their rich biological activities

  已经公开了一种有效且有趣的N中心 umpolung 方法来构建有益的 S-N 键，提供N -硫基亚胺，它可以在一锅顺序操作中轻松转化为相应的磺酰胺衍生物。 N-磺基亚胺是有机合成中有效的中间体，而磺酰胺由于其丰富的生物活性和在药物化学中的广泛适用性而备受分子关注。由于反应条件和设置简单，该方案显示出广泛且通用的底物范围，从而对N-硫基亚胺和磺酰胺的合成具有优异的官能团耐受性。针对这种独特的方法，提出了一种经过计算和实验支持的密度泛函理论（DFT）的便捷机制。
• Synthesis, enzyme kinetics and computational evaluation of N-(β-d-glucopyranosyl) oxadiazolecarboxamides as glycogen phosphorylase inhibitors
  作者：Mária Polyák、Gergely Varga、Bence Szilágyi、László Juhász、Tibor Docsa、Pál Gergely、Jaida Begum、Joseph M. Hayes、László Somsák

  DOI：10.1016/j.bmc.2013.07.024

  日期：2013.9

  All possible isomers of N-beta-D-glucopyranosyl aryl-substituted oxadiazolecarboxamides were synthesised. O-Peracetylated N-cyanocarbonyl-beta-D-glucopyranosylamine was transformed into the corresponding N-glucosyl tetrazole-5-carboxamide, which upon acylation gave N-glucosyl 5-ary1-1,3,4-oxadiazole-2-carboxamides. The nitrite group of the N-cyanocarbonyl derivative was converted to amidoxime which was ring closed by acylation to N-glucosyl 5-aryl-1,2,4-oxadiazole-3-carboxamides. A one-pot reaction of protected beta-D-glucopyranosylamine with oxalyl chloride and then with arenecarboxamidoximes furnished N-glucosyl 3-aryl-1,2,4-oxadiazole-5-carboxamides. Removal of the O-acetyl protecting groups by the Zemplen Method produced test compounds which were evaluated as inhibitors of glycogen phosphorylase. Best inhibitors of these series were N-(beta-D-glucopyranosyl) 5-(naphth-1-yl)-1,2,4-oxadiazol-3-carboxamide (K-i = 30 mu M), N-(beta-D-glucopyranosyl) 5-(naphth-2-y1)-1,3,4-oxadiazol-2-carboxamide (K-i= 33 mu M), and N-(beta-D-glucopyranosyl) 3-phenyl-1,2,4-oxadiazol-5-carboxamide (K-i= 104 mu M). ADMET property predictions revealed these compounds to have promising oral drug-like properties without any toxicity. (C) 2013 Elsevier Ltd. All rights reserved.
• PREPARATION OF SUBSTITUTED PYRIDINES VIA REGIOCONTROLLED [4 + 2] CYCLOADDITIONS OF OXIMINOSULFONATES: METHYL 5-METHYLPYRIDINE-2-CARBOXYLATE
  作者：Danheiser, Rick L.、Renslo, Adam R.、Amos, David T.、Wright, Graham T.、Krause, Helga、Fürstner, Alois

  DOI：10.15227/orgsyn.080.0133

  日期：——
• Synthesis of Substituted Pyridines via Regiocontrolled [4 + 2] Cycloadditions of Oximinosulfonates
  作者：Adam R. Renslo、Rick L. Danheiser

  DOI：10.1021/jo981014e

  日期：1998.10.1

  Diels-Alder cycloadditions of oximinosulfonate 8 with a variety of 1,3-dienes proceed with regiochemistry opposite to that observed with conventional imino dienophiles, providing expeditious synthetic routes to substituted pyridines, tetrahydropyridines, and pyrrolines. The oximinosulfonate 8 is prepared in one convenient synthetic operation from Meldrum's acid and reacts with conjugated dienes at -78 degrees C in the presence of 2 equiv of dimethylaluminum chloride to afford [4 + 2] cycloadducts in good to excellent yield. Exposure of these cycloadducts to the action of NaOMe and N-chlorosuccinimide in methanol-THF at room temperature then produces substituted pyridines. The utility of this new two-step annulation protocol is demonstrated in total syntheses of the pyridine alkaloids fusaric acid and (S)-(+)-fusarinolic acid. Heating the [4 + 2] cycloadducts derived from 8 in a mixture of acetonitrile and pH 7 phosphate buffer induces an unusual Stieglitz-type rearrangement leading to the formation of interesting spirobicyclic pyrrolines.
• Cyanocarbonylation of Amines with 5-Tosyloxyimino-2,2-dimethyl-1,3-dioxane-4,6-dione
  作者：Nobuya Katagiri、Minoru Ishikura、Yoshihiro Morishita、Masahiko Yamaguchi

  DOI：10.3987/com-99-s22

  日期：——

  5-Tosyloxyimino-2,2-dimethyl-1,3-dioxane-4,6-dione (3), prepared by the reaction of 5-hydroxyimino-2,2-dimethyl-1,3-dioxane-4,6-dione sodium salt (2) with tosyl chloride, was treated with various amines (4a-c and 6a,b) in the presence of triethylamine to give the corresponding N-cyanocarbonyl derivatives (5a-c and 7a,b). However, reaction of 3 with benzyl alcohol gave rise to the formation of dibenzyl carbonate (10).