4,4-dimethyl-5-phenyl-1,3-cyclohexanedione | 84168-03-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4,4-dimethyl-5-phenyl-1,3-cyclohexanedione
• 英文别名: 4,4-dimethyl-5-phenylcyclohexane-1,3-dione
• CAS: 84168-03-6
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: FDTRWJLJJZIELS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4-dimethyl-5-phenyl-1,3-cyclohexanedione 在 盐酸 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 生成 6,6-dimethyl-5-phenyl-2-cyclohexen-1-one
  参考文献：
  名称：

  Revisiting [3 + 3] Route to 1,3-Cyclohexanedione Frameworks:  Hidden Aspect of Thermodynamically Controlled Enolates

  摘要：

  We have revisited the traditional consecutive Michael-Claisen [3 + 3] process (MC-[3 + 3]) promising the synthesis of a cyclohexane-1,3-dione derivatives from nonactivated simple ketones and enoates and evaluated its potential in modern organic synthesis. Twenty to thirty examples were demonstrated to be effective. The reactions exhibited remarkable regioselectivity with the Michael addition proceeding through nucleophilic attack by the more hindered site of the ketones without exception. The subsequent Claisen condensation resulted in the formation of carbon-carbon bonds between less hindered site of the ketones and acyl carbon of the enoates. The MC-[3 + 3] process described is useful for the synthesis of Taxol A-ring synthons in multigram quantities and for the synthesis of other six-membered carbocyclic compounds. A number of control experiments have been conducted to provide strong support for the mechanism of this MC-[3 + 3].

  DOI：

  10.1021/jo010325d
• 作为产物：
  描述：

  3-甲基-2-丁酮 、 Methyl cinnamate 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以68%的产率得到4,4-dimethyl-5-phenyl-1,3-cyclohexanedione
  参考文献：
  名称：

  Revisiting [3 + 3] Route to 1,3-Cyclohexanedione Frameworks:  Hidden Aspect of Thermodynamically Controlled Enolates

  摘要：

  We have revisited the traditional consecutive Michael-Claisen [3 + 3] process (MC-[3 + 3]) promising the synthesis of a cyclohexane-1,3-dione derivatives from nonactivated simple ketones and enoates and evaluated its potential in modern organic synthesis. Twenty to thirty examples were demonstrated to be effective. The reactions exhibited remarkable regioselectivity with the Michael addition proceeding through nucleophilic attack by the more hindered site of the ketones without exception. The subsequent Claisen condensation resulted in the formation of carbon-carbon bonds between less hindered site of the ketones and acyl carbon of the enoates. The MC-[3 + 3] process described is useful for the synthesis of Taxol A-ring synthons in multigram quantities and for the synthesis of other six-membered carbocyclic compounds. A number of control experiments have been conducted to provide strong support for the mechanism of this MC-[3 + 3].

  DOI：

  10.1021/jo010325d

文献信息

• Domino Ring Expansion: Regioselective Access to 9-Membered Lactones with a Fused Indole Unit from 2-Nitrophenyl-1,3-cyclohexanediones
  作者：David Reyes Loya、Alexandre Jean、Morgan Cormier、Catherine Fressigné、Stefano Nejrotti、Jérôme Blanchet、Jacques Maddaluno、Michaël De Paolis

  DOI：10.1002/chem.201705645

  日期：2018.2.9

  of nucleophiles, involves the generation of an intermediate hydroxylate followed by the regioselective formation and fragmentation of an intermediate lactolate into enolate. This strategy, devoid of any protecting group, enlarges the initial ring and provides an original access to decorated 9‐membered lactones with a fused indole unit.

  公开了含有亲电子附件（如醛和环氧化物）的2-硝基苯基-1,3-环己二酮的多米诺阴离子片段。该反应是由一系列亲核试剂引发的，涉及到生成中间体羟基化物，然后进行区域选择性形成，并将中间体乳酸酯碎裂为烯醇化物。此策略不含任何保护基，可扩大初始环并提供原始接触带有稠合吲哚单元的装饰性9元内酯的途径。
• Certain 2-(substituted benzoyl)-5-(substituted or unsubstituted
  申请人：Stauffer Chemical Company

  公开号：US04767447A1

  公开（公告）日：1988-08-30

  Compounds of the formula ##STR1## wherein R is halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 alkoxy; trifluoromethoxy or difluoromethoxy; nitro; cyano; C.sub.1 -C.sub.2 haloalkyl; R.sup.a SO.sub.n -- wherein n is 0 or 2 and R.sup.a is C.sub.1 -C.sub.2 alkyl, trifluoromethyl or difluoromethyl; R.sup.1 is hydrogen or C.sub.1 -C.sub.4 alkyl; R.sup.2 is hydrogen or C.sub.1 -C.sub.4 alkyl; or R.sup.1 and R.sup.2 together are C.sub.2 -C.sub.5 alkylene; R.sup.3 is hydrogen or C.sub.1 -C.sub.4 alkyl; R.sup.4 is hydrogen or C.sub.1 -C.sub.4 alkyl; or R.sup.3 and R.sup.4 together are C.sub.2 -C.sub.5 alkylene; R.sup.5, R.sup.6, R.sup.7 and R.sup.8 independently are (1) hydrogen; (2) halogen; (3) C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl; (9) R.sup.b SO.sub.n -- wherein n is the integer 0, 1 or 2; and R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; (b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) benzyl; (10) --NR.sup.c R.sup.d and wherein R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)-- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; or (12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined; and (13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.c and R.sup.d are as defined; and R.sup.9 is hydrogen or C.sub.1 -C.sub.4 alkyl, and their salts.

  化合物的公式为 ##STR1## 其中 R 是卤素；C.sub.1 - C.sub.2 烷基；C.sub.1 - C.sub.2 烷氧基；三氟甲氧基或二氟甲氧基；硝基；氰基；C.sub.1 - C.sub.2 卤代烷基；R.sup.a SO.sub.n --，其中 n 为 0 或 2，R.sup.a 为 C.sub.1 - C.sub.2 烷基，三氟甲基或二氟甲基；R.sup.1 为氢或 C.sub.1 - C.sub.4 烷基；R.sup.2 为氢或 C.sub.1 - C.sub.4 烷基；或 R.sup.1 和 R.sup.2 一起为 C.sub.2 - C.sub.5 亚烷基；R.sup.3 为氢或 C.sub.1 - C.sub.4 烷基；R.sup.4 为氢或 C.sub.1 - C.sub.4 烷基；或 R.sup.3 和 R.sup.4 一起为 C.sub.2 - C.sub.5 亚烷基；R.sup.5、R.sup.6、R.sup.7 和 R.sup.8 独立地为 (1) 氢；(2) 卤素；(3) C.sub.1 - C.sub.4 烷基；(4) C.sub.1 - C.sub.4 烷氧基；(5) 三氟甲氧基；(6) 氰基；(7) 硝基；(8) C.sub.1 - C.sub.4 卤代烷基；(9) R.sup.b SO.sub.n --，其中 n 为整数 0、1 或 2；R.sup.b 为 (a) C.sub.1 - C.sub.4 烷基；(b) 用卤素或氰基取代的 C.sub.1 - C.sub.4 烷基；(c) 苯基；或 (d) 苄基；(10) --NR.sup.c R.sup.d，其中 R.sup.c 和 R.sup.d 独立地为氢或 C.sub.1 - C.sub.4 烷基；(11) R.sup.e C(O)--，其中 R.sup.e 为 C.sub.1 - C.sub.4 烷基或 C.sub.1 - C.sub.4 烷氧基；或 (12) --SO.sub.2 NR.sup.c R.sup.d，其中 R.sup.c 和 R.sup.d 如上定义；以及 (13) --N(R.sup.c)C(O)R.sup.d，其中 R.sup.c 和 R.sup.d 如上定义；R.sup.9 为氢或 C.sub.1 - C.sub.4 烷基，以及它们的盐。
• LEE, DAVID L.;MICHAELY, WILLIAM J.
  作者：LEE, DAVID L.、MICHAELY, WILLIAM J.

  DOI：——

  日期：——
• Verbessertes Verfahren zur Herstellung von Cyclohexan-1,3-dionen sowie einige neue bicyclische Cyclohexan-1,3-dione
  申请人：BASF Aktiengesellschaft

  公开号：EP0061669B1

  公开（公告）日：1984-07-25
• US4767447A
  申请人：——

  公开号：US4767447A

  公开（公告）日：1988-08-30