1,1-diethoxy-5-hydroxy-5-methyl-hex-3-yn-2-one | 1147103-30-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1-diethoxy-5-hydroxy-5-methyl-hex-3-yn-2-one
• 英文别名: 1,1-Diethoxy-5-hydroxy-5-methylhex-3-yn-2-one
• CAS: 1147103-30-7
• 化学式: C₁₁H₁₈O₄
• 分子量: 214.262
• InChiKey: AQOINVSQYTXZHR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,1-diethoxy-5-hydroxy-5-methyl-hex-3-yn-2-one 在 羟胺 作用下， 以 乙醇 、 水 为溶剂， 反应 15.0h， 以87%的产率得到5-diethoxymethyl-5-hydroxy-3-(1-hydroxyisopropyl)-4,5-dihydroisoxazole
  参考文献：
  名称：

  Formation of N-Heterocycles from 1,1-Diethoxy-5-hydroxyalk-3-yn-2-ones

  摘要：

  When treated with hydrazine, guanidine, and hydroxylamine, 1,1-diethoxy-5-hydroxyalk-3-yn-2-ones undergo Michael addition and give the corresponding beta, beta-disubstituted alpha, beta-unsaturated olefinic ketones, which are unstable and undergo secondary reactions to form heterocyclic compounds. Hydrazine affords 3,5-disubstituted pyrazoles and hydroxylamine 5-hydroxy-4,5-dihydroisoxazoles in very good yields. Guanidine, however, furnishes complex reaction mixtures, which include the corresponding 2-aminopyrimidines. These results show that cyclization involves attack of the ketone moiety by the bisnucleophile reactive terminal group and not the hydroxyl group present in the starting material.

  DOI：

  10.1055/s-0034-1378898
• 作为产物：
  描述：

  5,5,6,6-tetraethoxy-2-methylhex-3-yn-2-ol 在 对甲苯磺酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 3.0h， 以95%的产率得到1,1-diethoxy-5-hydroxy-5-methyl-hex-3-yn-2-one
  参考文献：
  名称：

  三和四取代呋喃的新区域特异性合成

  摘要：

  已经显示出β-酰氧基α，β-不饱和炔属酮与有机铜试剂反应并进行环化，然后脱水以得到取代的呋喃作为最终产物。该转化似乎是多用途的，并且在区域化学控制下以中等至良好的产率获得了三和四取代的呋喃。当反应在-60°C左右与含有空间需求取代基的底物和铜酸盐进行反应时，通常可获得最佳收率。所提出的呋喃形成机理已得到实验的支持。

  DOI：

  10.1021/jo9003986

文献信息

• Synthesis and Reactivity of 4-Amino-Substituted Furfurals
  作者：Uranbaatar Erdenebileg、Inger Høstmark、Karina Polden、Leiv K. Sydnes

  DOI：10.1021/jo4026308

  日期：2014.2.7

  reaction with secondary amines followed by treatment with acid in a mixture of THF and water. The stability of the furfurals depends to some extent on the nature of the amino group, whereas the reactivity has been shown to be reagent-dependent. When treated with phosphorus ylids, the expected alkenes are formed with E configuration in high yields, but when exposed to nitroalkanes under basic conditions

  通过与仲胺反应，然后在THF和水的混合物中用酸处理，已将γ-羟基α，β-不饱和炔基酮转化为4-氨基取代的糠醛。糠醛的稳定性在一定程度上取决于氨基的性质，而反应性已显示出是试剂依赖性的。当用磷化氢处理时，预期的烯烃以高收率形成E构型，但是当在碱性条件下暴露于硝基烷烃（亨利反应）时，尽管发生收率低，但似乎会发生异常转化，并获得了2-酰化的呋喃，而不是硝基烷醇。
• New Regiospecific Synthesis of Tri- and Tetra-Substituted Furans
  作者：Leiv K. Sydnes、Bjarte Holmelid、Myagmarsuren Sengee、Miriam Hanstein

  DOI：10.1021/jo9003986

  日期：2009.5.1

  to react with organocuprate reagents and undergo cyclization followed by dehydration to give substituted furans as the final products. The transformation appeared to be versatile, and tri- and tetra-substituted furans were obtained with regiochemical control in moderate to good yields. The best yields were generally obtained when the reactions were performed around −60 °C with substrates and cuprates

  已经显示出β-酰氧基α，β-不饱和炔属酮与有机铜试剂反应并进行环化，然后脱水以得到取代的呋喃作为最终产物。该转化似乎是多用途的，并且在区域化学控制下以中等至良好的产率获得了三和四取代的呋喃。当反应在-60°C左右与含有空间需求取代基的底物和铜酸盐进行反应时，通常可获得最佳收率。所提出的呋喃形成机理已得到实验的支持。
• Formation of N-Heterocycles from 1,1-Diethoxy-5-hydroxyalk-3-yn-2-ones
  作者：Leiv Sydnes、Ingebjørg Nes

  DOI：10.1055/s-0034-1378898

  日期：——

  When treated with hydrazine, guanidine, and hydroxylamine, 1,1-diethoxy-5-hydroxyalk-3-yn-2-ones undergo Michael addition and give the corresponding beta, beta-disubstituted alpha, beta-unsaturated olefinic ketones, which are unstable and undergo secondary reactions to form heterocyclic compounds. Hydrazine affords 3,5-disubstituted pyrazoles and hydroxylamine 5-hydroxy-4,5-dihydroisoxazoles in very good yields. Guanidine, however, furnishes complex reaction mixtures, which include the corresponding 2-aminopyrimidines. These results show that cyclization involves attack of the ketone moiety by the bisnucleophile reactive terminal group and not the hydroxyl group present in the starting material.