6-methoxycarbonyl-5-oxohexanoic acid | 264601-66-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 6-methoxycarbonyl-5-oxohexanoic acid
• 英文别名: 7-Methoxy-5,7-dioxoheptanoic acid
• CAS: 264601-66-3
• 化学式: C₈H₁₂O₅
• 分子量: 188.18
• InChiKey: ZOQNFPHVPGPISD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  80.7
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  6-methoxycarbonyl-5-oxohexanoic acid 在 4-二甲氨基吡啶 、 对甲苯磺酰叠氮 、 三氟化硼乙醚 、 potassium carbonate 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 2.0h， 生成 methyl 2-diazo-6-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)-3-oxohexanoate
  参考文献：
  名称：

  Three- to Six-Carbon Ring-Enlargement Reaction of Cyclic Ortho Esters Bearing a Diazocarbonyl Side Chain. Use of the Intramolecular Formation of Tricyclooxonium Ylides

  摘要：

  Two types of bicyclic ortho esters 14 and 18, which are tethered to a diazocarbonyl group by polymethylene linkages -(CH2)(n)- of different lengths (n = 1-3 for 14 and 1-4 for 18), were prepared and catalytically decomposed by treatment with Rh-2(OAc)(4) either in the presence or absence of a protic nucleophile (MeOH, PhOH, AcOH) to give ring-enlargement product lactones 25 and 30 of different sizes. With 14, the enlargement took place when n = 1 or 2, but not when n = 3. With 18, in which the diazo carbon is substituted with a methoxycarbonyl group, the length of the chain can be extended further to n. = 4 to obtain ring-enlargement products or their derivatives. All of these reactions could be explained in terms of the intermediacy of tricyclooxonium ylides 22 and 28. The ylides form an equilibrium with the corresponding ring-opened zwitterions 22' and 28', respectively, which, after protonation by a protic nucleophile, undergo mainly ring-enlargement to form medium-sized or large oxalactones rather than 1,2-rearrangement.

  DOI：

  10.1021/jo991332t
• 作为产物：
  描述：

  戊二酸酐 、 lithium enolate of methyl acetate 以 四氢呋喃 为溶剂， 以54%的产率得到6-methoxycarbonyl-5-oxohexanoic acid
  参考文献：
  名称：

  Three- to Six-Carbon Ring-Enlargement Reaction of Cyclic Ortho Esters Bearing a Diazocarbonyl Side Chain. Use of the Intramolecular Formation of Tricyclooxonium Ylides

  摘要：

  Two types of bicyclic ortho esters 14 and 18, which are tethered to a diazocarbonyl group by polymethylene linkages -(CH2)(n)- of different lengths (n = 1-3 for 14 and 1-4 for 18), were prepared and catalytically decomposed by treatment with Rh-2(OAc)(4) either in the presence or absence of a protic nucleophile (MeOH, PhOH, AcOH) to give ring-enlargement product lactones 25 and 30 of different sizes. With 14, the enlargement took place when n = 1 or 2, but not when n = 3. With 18, in which the diazo carbon is substituted with a methoxycarbonyl group, the length of the chain can be extended further to n. = 4 to obtain ring-enlargement products or their derivatives. All of these reactions could be explained in terms of the intermediacy of tricyclooxonium ylides 22 and 28. The ylides form an equilibrium with the corresponding ring-opened zwitterions 22' and 28', respectively, which, after protonation by a protic nucleophile, undergo mainly ring-enlargement to form medium-sized or large oxalactones rather than 1,2-rearrangement.

  DOI：

  10.1021/jo991332t

文献信息

• Substituted hexahydropyrrolo(1,2-a)-quinoline, hexahydro-1H-pyrido(1,2-a)-quinoline, hexahydrobenzo(3)indene and octahydrophenanthrene CNS agents
  申请人：PFIZER INC.

  公开号：EP0090516A1

  公开（公告）日：1983-10-05

  Tricyclic benzo fused compounds of the formula and pharmaceutically acceptable cationic and acid addition salts thereof, wherein n is zero, 1 or 2, and t is 1 or 2; M is CH or N, R1 is H or certain acyl groups; Q is CO2R4, CORS, C(OR7)R5R6, CN, CONR9R10, CH2NR9R10, CH2NHCOR11, CH2NHSO2R12, 5-tetrazolyl or when n is 1, Q and OR1 together form a lactone or certain reduced derivatives thereof; and Z is certain alkyl, alkoxy, alkoxyalkyl, aralkyl, aralkoxy, aryloxyalkyl or aralkoxyalkyl groups, are valuable central nervous system active agents, methods for their use, pharmaceutical compositions containing them and certain intermediates therefor.

  式中的三环苯并融合化合物 及其药学上可接受的阳离子盐和酸加成盐，其中 n 为零、1 或 2，t 为 1 或 2；M 为 CH 或 N，R1 为 H 或某些酰基；Q 为 CO2R4、CORS、C(OR7)R5R6、CN、CONR9R10、CH2NR9R10、CH2NHCOR11、CH2NHSO2R12、5-四唑基，或当 n 为 1 时，Q 和 OR1 共同形成内酯或其某些还原衍生物；和 Z 是某些烷基、烷氧基、烷氧基烷基、芳基、芳氧基烷基或芳氧基烷基，这些都是有价值的中枢神经系统活性剂、使用方法、含有它们的药物组合物及其某些中间体。
• Three- to Six-Carbon Ring-Enlargement Reaction of Cyclic Ortho Esters Bearing a Diazocarbonyl Side Chain. Use of the Intramolecular Formation of Tricyclooxonium Ylides
  作者：Akira Oku、Munenori Numata

  DOI：10.1021/jo991332t

  日期：2000.4.1

  Two types of bicyclic ortho esters 14 and 18, which are tethered to a diazocarbonyl group by polymethylene linkages -(CH2)(n)- of different lengths (n = 1-3 for 14 and 1-4 for 18), were prepared and catalytically decomposed by treatment with Rh-2(OAc)(4) either in the presence or absence of a protic nucleophile (MeOH, PhOH, AcOH) to give ring-enlargement product lactones 25 and 30 of different sizes. With 14, the enlargement took place when n = 1 or 2, but not when n = 3. With 18, in which the diazo carbon is substituted with a methoxycarbonyl group, the length of the chain can be extended further to n. = 4 to obtain ring-enlargement products or their derivatives. All of these reactions could be explained in terms of the intermediacy of tricyclooxonium ylides 22 and 28. The ylides form an equilibrium with the corresponding ring-opened zwitterions 22' and 28', respectively, which, after protonation by a protic nucleophile, undergo mainly ring-enlargement to form medium-sized or large oxalactones rather than 1,2-rearrangement.