4-hydroxy-3-methyl-3-buten-2-one | 40572-79-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-hydroxy-3-methyl-3-buten-2-one
• 英文别名: 2-methyl-3-oxo-butyraldehyde (Z)-1-enol tautomer；(Z)-4-hydroxy-3-methyl-but-3-en-2-one；(Z)-4-hydroxy-3-methylbut-3-en-2-one
• CAS: 40572-79-0
• 化学式: C₅H₈O₂
• 分子量: 100.117
• InChiKey: GRYBUZVQFHGFHA-ARJAWSKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-hydroxy-3-methyl-3-buten-2-one 在 palladium on activated charcoal 吡啶 、 盐酸 、 lithium aluminium tetrahydride 、 氢气 、 对甲苯磺酸 、 三乙胺 、 lithium hexamethyldisilazane 、 三氯氧磷 作用下， 以 四氢呋喃 、 甲醇 、 硝基甲烷 、 氯仿 、 1,2-二氯乙烷 为溶剂， 反应 92.17h， 生成 3,7,18,22-tetraethyl-2,8,12,13,17,23-hexamethyl-25,27,29-trioxasapphyrin
  参考文献：
  名称：

  Synthesis and Characterization of All-Alkyl-Substituted Mono-, Di-, and Trioxosapphyrins

  摘要：

  The synthesis and characterization of the following heterosapphyrins is presented: 3,7,18,22-tetraethyl-2,8,12,13,17,23-hexamethyl-27-oxasapphyrin (5), 3,8,12,13,17,22-hexaethyl-2,7,18,23-tetramethyl-15,29-dioxasapphyrin (6), and 3,7,18,22-tetraethyl-2,8,12,13,17,23-hexamethyl-15,27,29-trioxasapphyrin (7). These macrocycles were synthesized from the hitherto unknown precursors methyl 3,4-dimethylfuran-2-carboxylate (11) and methyl 4-ethyl-3-methylfuran-2-carboxylate (12). Single-crystal X-ray diffraction structures of the bis(hydrochloric acid) salt (5a) and the bis(trifluoroacetic acid) salt (5b) of 5 and of the bis(hydrochloric acid) salt (6a) of 6 were obtained. These structures are compared to those of the parent all-aza sapphyrin 4. In this context, we report the first solid-state structural analysis of a trifluoroacetic acid salt of sapphyrin (4b). Crystals of 5a are triclinic, space group P (1) over bar in a cell of the dimensions a = 11.9686(13) Angstrom, b = 12.790(2) Angstrom, c = 16.236(2) Angstrom, alpha = 80.924(10)degrees, beta = 88.845(9)degrees, gamma = 80.481(10)degrees, V = 2420.5(5) Angstrom(3), F(000) = 1036, rho = 1.38 g cm(3) with Z = 2. Crystals of 5b are monoclinic, space group P2(1)/c, in a cell of the dimensions a = 9.590(1) Angstrom, b = 33.911(3) Angstrom, c = 13.200(1) Angstrom, beta = 94.931(6)degrees, V = 4276.8(6) Angstrom(3), F(000)= 1904, rho = 1.42 g cm(3), with Z = 4. Crystals of 6a are triclinic, space group P (1) over bar, in a cell of the dimensions a = 12.827(3) Angstrom, b = 13.116(3) Angstrom, c = 17.202(7) Angstrom, alpha = 82.89(2)degrees, beta = 82.14(2)degrees, gamma = 80.22(1)degrees, V = 2810(2) Angstrom(3), F(000) = 1184, rho = 136 g cm(3), with Z = 2. Crystals of 4b are triclinic, space group P (1) over bar, in a cell of the dimensions a = 11.431(3) Angstrom, b = 11.563(2) Angstrom, c = 16.367(4) Angstrom, alpha = 88.07(2)degrees, beta = 75.25(2)degrees, gamma = 86.50(2), V = 2087.8(9) Angstrom(3), F(000)= 872, rho = 1.32, with Z = 2. The monooxasapphyrin salt 5a displays a structure very similar to that of the parent all-azasapphyrin (4a) in that one chloride anion is bound 1.936 Angstrom above and one chloride anion 1.814 Angstrom below the plane of the macrocycle. These distances are 1.774 and 1.877 Angstrom, respectively, for 4a. Almost the same behavior is found for 5b. Here, the carboxylate anions are bound 1.085 Angstrom above and 1.870 Angstrom below the plane of the macrocycle. These distances are 1.305 and 1.444 Angstrom, respectively, for 4b. Completely different behavior is observed in the case of 6a. In this instance, only one chloride anion is bound directly with a distance of 1.685 Angstrom above the plane of the macrocycle, while the other chloride anion is well removed from the dioxasapphyrin and solvated by four chloroform molecules.

  DOI：

  10.1021/jo9715736
• 作为产物：
  描述：

  甲酸甲酯 、 丁酮 在 盐酸 、 sodium 作用下， 生成 4-hydroxy-3-methyl-3-buten-2-one
  参考文献：
  名称：

  Synthesis and Characterization of All-Alkyl-Substituted Mono-, Di-, and Trioxosapphyrins

  摘要：

  The synthesis and characterization of the following heterosapphyrins is presented: 3,7,18,22-tetraethyl-2,8,12,13,17,23-hexamethyl-27-oxasapphyrin (5), 3,8,12,13,17,22-hexaethyl-2,7,18,23-tetramethyl-15,29-dioxasapphyrin (6), and 3,7,18,22-tetraethyl-2,8,12,13,17,23-hexamethyl-15,27,29-trioxasapphyrin (7). These macrocycles were synthesized from the hitherto unknown precursors methyl 3,4-dimethylfuran-2-carboxylate (11) and methyl 4-ethyl-3-methylfuran-2-carboxylate (12). Single-crystal X-ray diffraction structures of the bis(hydrochloric acid) salt (5a) and the bis(trifluoroacetic acid) salt (5b) of 5 and of the bis(hydrochloric acid) salt (6a) of 6 were obtained. These structures are compared to those of the parent all-aza sapphyrin 4. In this context, we report the first solid-state structural analysis of a trifluoroacetic acid salt of sapphyrin (4b). Crystals of 5a are triclinic, space group P (1) over bar in a cell of the dimensions a = 11.9686(13) Angstrom, b = 12.790(2) Angstrom, c = 16.236(2) Angstrom, alpha = 80.924(10)degrees, beta = 88.845(9)degrees, gamma = 80.481(10)degrees, V = 2420.5(5) Angstrom(3), F(000) = 1036, rho = 1.38 g cm(3) with Z = 2. Crystals of 5b are monoclinic, space group P2(1)/c, in a cell of the dimensions a = 9.590(1) Angstrom, b = 33.911(3) Angstrom, c = 13.200(1) Angstrom, beta = 94.931(6)degrees, V = 4276.8(6) Angstrom(3), F(000)= 1904, rho = 1.42 g cm(3), with Z = 4. Crystals of 6a are triclinic, space group P (1) over bar, in a cell of the dimensions a = 12.827(3) Angstrom, b = 13.116(3) Angstrom, c = 17.202(7) Angstrom, alpha = 82.89(2)degrees, beta = 82.14(2)degrees, gamma = 80.22(1)degrees, V = 2810(2) Angstrom(3), F(000) = 1184, rho = 136 g cm(3), with Z = 2. Crystals of 4b are triclinic, space group P (1) over bar, in a cell of the dimensions a = 11.431(3) Angstrom, b = 11.563(2) Angstrom, c = 16.367(4) Angstrom, alpha = 88.07(2)degrees, beta = 75.25(2)degrees, gamma = 86.50(2), V = 2087.8(9) Angstrom(3), F(000)= 872, rho = 1.32, with Z = 2. The monooxasapphyrin salt 5a displays a structure very similar to that of the parent all-azasapphyrin (4a) in that one chloride anion is bound 1.936 Angstrom above and one chloride anion 1.814 Angstrom below the plane of the macrocycle. These distances are 1.774 and 1.877 Angstrom, respectively, for 4a. Almost the same behavior is found for 5b. Here, the carboxylate anions are bound 1.085 Angstrom above and 1.870 Angstrom below the plane of the macrocycle. These distances are 1.305 and 1.444 Angstrom, respectively, for 4b. Completely different behavior is observed in the case of 6a. In this instance, only one chloride anion is bound directly with a distance of 1.685 Angstrom above the plane of the macrocycle, while the other chloride anion is well removed from the dioxasapphyrin and solvated by four chloroform molecules.

  DOI：

  10.1021/jo9715736

文献信息

• Synthesis and SAR of a New Series of COX-2-Selective Inhibitors:  Pyrazolo[1,5-<i>a</i>]pyrimidines
  作者：Carmen Almansa、Alberto F. de Arriba、Fernando L. Cavalcanti、Luis A. Gómez、Agustí Miralles、Manuel Merlos、Julián García-Rafanell、Javier Forn

  DOI：10.1021/jm0009383

  日期：2001.2.1

  The synthesis and pharmacological activity of a series of bicyclic pyrazolo[1,5-a]pyrimidines as potent and selective cyclooxygenase-2 (COX-2) inhibitors are described. The new compounds were evaluated both in vitro (COX-1 and COX-2 inhibition in human whole blood) and in vive (carrageenan-induced paw edema and air-pouch model). Modification of the pyrimidine substituents showed that 6,7-disubstitution provided the best activity and led to the identification of 3-(4-fluorophenyl)-6,7-dimethyl-2-(4-methylsulfonylphenyl)pyrazolo[1,5-a]pyrimidine (10f) as one of the most potent and selective COX-2 inhibitor in this series.
• Synthesis and Characterization of All-Alkyl-Substituted Mono-, Di-, and Trioxosapphyrins
  作者：Jonathan L. Sessler、Michael C. Hoehner、Andreas Gebauer、Andrei Andrievsky、Vincent Lynch

  DOI：10.1021/jo9715736

  日期：1997.12.1

  The synthesis and characterization of the following heterosapphyrins is presented: 3,7,18,22-tetraethyl-2,8,12,13,17,23-hexamethyl-27-oxasapphyrin (5), 3,8,12,13,17,22-hexaethyl-2,7,18,23-tetramethyl-15,29-dioxasapphyrin (6), and 3,7,18,22-tetraethyl-2,8,12,13,17,23-hexamethyl-15,27,29-trioxasapphyrin (7). These macrocycles were synthesized from the hitherto unknown precursors methyl 3,4-dimethylfuran-2-carboxylate (11) and methyl 4-ethyl-3-methylfuran-2-carboxylate (12). Single-crystal X-ray diffraction structures of the bis(hydrochloric acid) salt (5a) and the bis(trifluoroacetic acid) salt (5b) of 5 and of the bis(hydrochloric acid) salt (6a) of 6 were obtained. These structures are compared to those of the parent all-aza sapphyrin 4. In this context, we report the first solid-state structural analysis of a trifluoroacetic acid salt of sapphyrin (4b). Crystals of 5a are triclinic, space group P (1) over bar in a cell of the dimensions a = 11.9686(13) Angstrom, b = 12.790(2) Angstrom, c = 16.236(2) Angstrom, alpha = 80.924(10)degrees, beta = 88.845(9)degrees, gamma = 80.481(10)degrees, V = 2420.5(5) Angstrom(3), F(000) = 1036, rho = 1.38 g cm(3) with Z = 2. Crystals of 5b are monoclinic, space group P2(1)/c, in a cell of the dimensions a = 9.590(1) Angstrom, b = 33.911(3) Angstrom, c = 13.200(1) Angstrom, beta = 94.931(6)degrees, V = 4276.8(6) Angstrom(3), F(000)= 1904, rho = 1.42 g cm(3), with Z = 4. Crystals of 6a are triclinic, space group P (1) over bar, in a cell of the dimensions a = 12.827(3) Angstrom, b = 13.116(3) Angstrom, c = 17.202(7) Angstrom, alpha = 82.89(2)degrees, beta = 82.14(2)degrees, gamma = 80.22(1)degrees, V = 2810(2) Angstrom(3), F(000) = 1184, rho = 136 g cm(3), with Z = 2. Crystals of 4b are triclinic, space group P (1) over bar, in a cell of the dimensions a = 11.431(3) Angstrom, b = 11.563(2) Angstrom, c = 16.367(4) Angstrom, alpha = 88.07(2)degrees, beta = 75.25(2)degrees, gamma = 86.50(2), V = 2087.8(9) Angstrom(3), F(000)= 872, rho = 1.32, with Z = 2. The monooxasapphyrin salt 5a displays a structure very similar to that of the parent all-azasapphyrin (4a) in that one chloride anion is bound 1.936 Angstrom above and one chloride anion 1.814 Angstrom below the plane of the macrocycle. These distances are 1.774 and 1.877 Angstrom, respectively, for 4a. Almost the same behavior is found for 5b. Here, the carboxylate anions are bound 1.085 Angstrom above and 1.870 Angstrom below the plane of the macrocycle. These distances are 1.305 and 1.444 Angstrom, respectively, for 4b. Completely different behavior is observed in the case of 6a. In this instance, only one chloride anion is bound directly with a distance of 1.685 Angstrom above the plane of the macrocycle, while the other chloride anion is well removed from the dioxasapphyrin and solvated by four chloroform molecules.