2-amino-3-cyano-7,7-dimethyl-4-(4-methylphenyl)-5-oxo-5,6,7,8-tetrahydro-4H-1-benzopyran | 311773-23-6

• 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: 2-amino-3-cyano-7,7-dimethyl-4-(4-methylphenyl)-5-oxo-5,6,7,8-tetrahydro-4H-1-benzopyran
• 英文别名: 2-amino-7,7-dimethyl-5-oxo-4-(p-tolyl)-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile；2-amino-3-cyano-4-(4-methylphenyl)-7,7-dimethyl-5-oxo-4H-5,6,7,8-tetrahydrobenzo[b]pyran；2-amino-7,7-dimethyl-4-(4-methylphenyl)-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile；2-amino-3-cyano-7,7-dimethyl-4-(4-methylphenyl)-5-oxo-4H-5,6,7,8-tetrahydrobenzopyran；2-amino-5,6,7,8-tetrahydro-4-(4-methylphenyl)-7,7-dimethyl-5-oxo-4H-chromene-3-carbonitrile；2-amino-4-(4-methylphenyl)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile；2-amino-5,6,7,8-tetrahydro-7,7-dimethyl-5-oxo-4-p-tolyl-4H-chromene-3-carbonitrile；2-amino-7,7-dimethyl-4-(4-methylphenyl)-5-oxo-6,8-dihydro-4H-chromene-3-carbonitrile
• CAS: 311773-23-6
• 化学式: C₁₉H₂₀N₂O₂
• 分子量: 308.38
• InChiKey: GJKJZOUBSZMRDZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  76.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-amino-3-cyano-7,7-dimethyl-4-(4-methylphenyl)-5-oxo-5,6,7,8-tetrahydro-4H-1-benzopyran 在 水 、 对甲苯磺酸 作用下， 反应 7.0h， 以80%的产率得到7,7-dimethyl-2,5-dioxo-4-p-tolyl-1,2,3,4,5,6,7,8-octahydro-quinoline-3-carbonitrile
  参考文献：
  名称：

  Nano crystalline ZnO catalyzed one pot multicomponent reaction for an easy access of fully decorated 4H-pyran scaffolds and its rearrangement to 2-pyridone nucleus in aqueous media

  摘要：

  A green and highly efficient protocol has been developed for the synthesis of 4H-pyran scaffolds installing a one-pot three-component coupling reaction of an aldehyde, malononitrile, and a 1,3-diketo compound using nano structured ZnO as the catalyst in aqueous alcoholic medium. A greener method to synthesize 3,4-dihydropyridin-2-one has also been developed by rearranging 4H-pyran derivatives in aqueous medium applying p-TSOH as the right catalyst source. A wide spectrum of functional groups was tolerated in both the developed synthetic protocols with good to excellent yield of the targeted molecules. (c) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.06.086
• 作为产物：
  描述：

  对甲基苯甲醛 以 水 为溶剂， 反应 1.08h， 生成 2-amino-3-cyano-7,7-dimethyl-4-(4-methylphenyl)-5-oxo-5,6,7,8-tetrahydro-4H-1-benzopyran
  参考文献：
  名称：

  Catalyst-Free Cascade Synthesis of Densely Functionalized Chromenes in Water

  摘要：

  已开发出一种快速且环保的通用方案，用于在水中通过级联Knoevenagel-Michael-分子内环化合成2-氨基-3-氰基-4H-香豆素。通过简单的过滤技术获得了纯固体产物。在室温下，无水催化剂的水相反应导致高产物收率。

  DOI：

  10.14233/ajchem.2019.22191

文献信息

• Potassium-Exchanged Zirconium Hydrogen Phosphate [α-Zr(KPO4)2]-Catalyzed Synthesis of 2-Amino-4H-pyran Derivatives under Solvent-Free Conditions
  作者：Ornelio Rosati、Azzurra Pelosi、Andrea Temperini、Vittorio Pace、Massimo Curini

  DOI：10.1055/s-0035-1560411

  日期：——

  conditions. A high-yielding, one-pot, three-component synthesis of functionalized 2-amino-4H-pyrans from β-dicarbonyl compounds, activated cyanomethylene compounds, and aldehydes, mediated by potassium-exchanged zirconium hydrogen phosphate [α-Zr(KPO4)2], is reported. The protocol shows excellent versatility, as it can be applied to aromatic, aliphatic, or α,β-unsaturated aldehydes under solvent-free conditions

  摘要 由钾交换磷酸氢锆[α-Zr（KPO）介导的由β-二羰基化合物，活化的氰基亚甲基化合物和醛类合成的高产一锅三组分功能化2-氨基-4 H-吡喃4）2 ]，被报告。该协议具有出色的通用性，因为它可以在无溶剂条件下应用于芳族，脂族或α，β-不饱和醛。 由钾交换磷酸氢锆[α-Zr（KPO）介导的由β-二羰基化合物，活化的氰基亚甲基化合物和醛类合成的高产一锅三组分功能化2-氨基-4 H-吡喃4）2 ]，被报告。该协议具有出色的通用性，因为它可以在无溶剂条件下应用于芳族，脂族或α，β-不饱和醛。
• Synthesis of functionalized chromene and spirochromenes using l -proline-melamine as highly efficient and recyclable homogeneous catalyst at room temperature
  作者：Sakkani Nagaraju、Banoth Paplal、Kota Sathish、Santanab Giri、Dhurke Kashinath

  DOI：10.1016/j.tetlet.2017.09.060

  日期：2017.11

  commercially cheap l-proline and melamine for the synthesis of chromenes and spirochromenes (spirooxindoles) via multicomponent reactions at room temperature. Systematic studies were conducted in order to achieve desired reactivity and recyclability of the catalyst using various α-amino acids and aromatic amines as donor-acceptor pairs. Among the screened combinations, l-proline and melamine (3:1 ratio;

  使用便宜的1-脯氨酸和三聚氰胺开发了一种有效且可循环使用的均相催化剂，用于在室温下通过多组分反应合成色烯和螺环色酮（螺并辛多烯）。为了使用各种α-氨基酸和芳族胺作为供体-受体对，进行系统研究以实现所需的反应性和催化剂的可回收性。在筛选的组合中，l脯氨酸和三聚氰胺（3：1的比例；占总重量的3 mol％）被认为是最佳的催化剂，可以在室温下非常短的时间内（1-15分钟）以优异的产率（高达99％）提供所需的产品在DMSO中作为溶剂。通过添加EtOAc来回收催化剂，并且在不损失催化活性的情况下重复使用多达5个循环。
• One-Pot, Catalyst-Free Synthesis of Spirooxindole and 4<i>H</i>-Pyran Derivatives
  作者：Thanasekaran Ponpandian、Shanmugam Muthusubramanian

  DOI：10.1080/00397911.2013.837488

  日期：2014.3.19

  Abstract The synthesis of biologically valuable spirooxindoles and 4H-pyrans is described under catalyst-free conditions through sequential Knoevenagel–Michael–cyclization reactions from isatin or aromatic aldehyde, malononitrile, and 1,3-dicarbonyl compounds. The reaction conditions are very simple, providing excellent yield. [Supplementary materials are available for this article. Go to the publisher's

  摘要 在无催化剂条件下，通过靛红或芳香醛、丙二腈和 1,3-二羰基化合物的连续 Knoevenagel-Michael-环化反应，合成了具有生物学价值的螺环吲哚和 4H-吡喃。反应条件非常简单，产率极好。[本文提供补充材料。访问出版商的 Synthetic Communications® 在线版，获取以下免费补充资源：完整的实验和光谱细节。] 图形摘要
• An approach to the synthesis and characterization of HMS/Pr-Rh-Zr as efficient catalyst for synthesis of tetrahydrobenzo[b]pyran and 1,4-dihydropyrano[2,3-c]pyrazole derivatives
  作者：Sahar Abdolahi、Maryam Hajjami、Fatemeh Gholamian

  DOI：10.1007/s11164-021-04411-z

  日期：2021.5

  HMS/Pr-Rh-Zr was successfully synthesized. Also the catalytic activity of HMS/Pr-Rh-Zr is investigated for the synthesis of tetrahydrobenzo[b]pyran derivatives from reaction between aldehyde, malononitrile, dimedone in PEG at 80 °C and synthesis of 1,4-dihydropyrano[2,3-c]pyrazole derivatives from reaction between aldehyde, ethyl acetoacetate, malononitrile and hydrazine hydrate in H2O:EtOH at 35 °C

  本研究的目的是基于六角形介孔二氧化硅的介孔催化剂的合成。HMS支撑物具有出色的特性，例如易于合成，高表面积，大孔体积和虫孔。这些独特的特性似乎将其用作合成非均相催化剂的载体。通过HMS的功能化和将Zr-罗丹宁复合物固定到功能化的HMS中，获得了HMS / Pr-Rh-Zr。FT-IR，XRD，TGA，SEM，EDX，77 K氮气吸附-脱附和ICP技术表征了新型合成催化剂（HMS / Pr-Rh-Zr）。这些技术证实了成功地合成了HMS / Pr-Rh-Zr的非均相催化剂。还研究了HMS / Pr-Rh-Zr的催化活性，用于由醛之间的反应合成四氢苯并[b]吡喃衍生物。在35°C下2 O：EtOH。这些结果证实了HMS / Pr-Rh-Zr表现出良好的催化性能。此外，合成的非均相催化剂可以在反应后回收并重复使用几次而没有任何明显的活性损失。还研究了HMS / Pr-Rh-Zr的锆浸出，因此催化剂的金属浸出非常低。
• One-pot synthesis of 2-amino-3-cyano-4<i>H</i>-pyrans and pyran-annulated heterocycles using sodium citrate as an organo-salt based catalyst in aqueous ethanol
  作者：Aiborlang Thongni、Pynskhemborlang T. Phanrang、Arup Dutta、Rishanlang Nongkhlaw

  DOI：10.1080/00397911.2021.1998535

  日期：2022.1.2

  shorter reaction time, utilization of eco-friendly solvents, operational simplicity, mild reaction conditions, and maximum product yield. Moreover, the use of sodium citrate as an easily available, cheap and benign catalyst plays a pivotal role from a green perspective, considering its high recyclability and easy recovery. Therefore, this present methodology offers numerous possibilities in terms of large-scale

  摘要 柠檬酸钠作为一种高效催化剂被开发用于合成官能化的 2-氨基-3-氰基-4 H-吡喃和吡喃环化杂环。该方法涉及芳香醛、丙二腈和 1,3-二羰基化合物与 EtOH 的一锅三组分反应：H 2O (1:1 v/v) 在室温下作为溶剂。该协议具有几个优点，例如更短的反应时间、环保溶剂的利用、操作简单、反应条件温和和产品收率最高。此外，考虑到柠檬酸钠的高可回收性和易回收性，从绿色角度来看，柠檬酸钠作为一种易于获得、廉价和良性的催化剂发挥着关键作用。因此，本方法在大规模工业合成或应用于众多有机转化方面提供了许多可能性。此外，还对产物4aa形成的机理途径进行了理论研究，以确定柠檬酸钠对DFT法反应可行性的催化作用，使用B3LYP泛函。