phenyl-(1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4-yl)-methanone | 59563-84-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl-(1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4-yl)-methanone
• 英文别名: Methanone, phenyl(1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4-yl)-；phenyl-(1-phenylpyrazolo[3,4-d]pyrimidin-4-yl)methanone
• CAS: 59563-84-7
• 化学式: C₁₈H₁₂N₄O
• 分子量: 300.319
• InChiKey: GFNJGJVJJLVTAZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  60.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  phenyl-(1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4-yl)-methanone 在 sodium hydroxide 、 potassium hexacyanoferrate(III) 作用下， 以 二甲基亚砜 为溶剂， 生成 1,4-二苯基吡唑并[3,4-d]嘧啶
  参考文献：
  名称：

  Higashino, Takeo; Matsushita, Yasuhiko; Takemoto, Masumi, Heterocycles, 1983, vol. 20, # 1, p. 156

  摘要：

  DOI：
• 作为产物：
  描述：

  2-(苯甲酰氧基)-2-苯基乙腈 在 sodium hydroxide 、 sodium hydride 作用下， 以 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 生成 phenyl-(1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4-yl)-methanone
  参考文献：
  名称：

  Higashino, Takeo; Matsushita, Yasuhiko; Takemoto, Masumi, Chemical and pharmaceutical bulletin, 1983, vol. 31, # 11, p. 3951 - 3958

  摘要：

  DOI：

文献信息

• Carbon-Carbon Bond Cleavage of .ALPHA.-Hydroxybenzylheteroarenes Catalyzed by Cyanide Ion: Retro-Benzoin Condensation Affords Ketones and Heteroarenes and Benzyl Migration Affords Benzylheteroarenes and Arenecarbaldehydes.
  作者：Yumiko SUZUKI、Yuki TAKEMURA、Ken-ichi IWAMOTO、Takeo HIGASHINO、AKira MIYASHITA

  DOI：10.1248/cpb.46.199

  日期：——

  4-(α-Benzyl-α-hydroxybenzyl)quinazoline (4a) underwent retro-benzoin condensation catalyzed by cyanide ion to give deoxybenzoin (2a) and quinazoline (5a). Similarly, several nitrogen-containing heteroarenes (4, 9, 12, 16-19) having an α-hydroxybenzyl group at the α-position of the nitrogen underwent retro-benzoin type condensation to afford ketones (2) and heteroarenes (5). However, similar reaction of pyrazolopyrimidines (13, 14, 15) having an α-benzyl-α-hydroxybenzyl group resulted in benzyl migration, giving benzylpyrazolopyrimidines (8) and arenecarbaldehydes (3). Tetrabutylammonium cyanide (11, Bu4NCN) was a more effective cyanide ion donor than KCN (10). The retro-benzoin condensation was applied to the synthesis of 2-substituted quinazolines (38) from 2-chloro-4-aroylquinazolines (34), using the aroyl group as a protecting and electron-withdrawing group.

  4-(α-苄基-α-羟基苄基)喹唑啉(4a)在氰离子催化下经历逆苯偶姻缩合反应，生成脱氧苯偶姻(2a)和喹唑啉(5a)。同样，多个含氮杂环芳烃(4, 9, 12, 16-19)在其氮原子的α位上具有α-羟基苄基的结构，也经历逆苯偶姻型缩合反应，生成了酮(2)和杂环芳烃(5)。然而，具有α-苄基-α-羟基苄基结构的吡唑嘧啶(13, 14, 15)在类似的反应中引发了苄基迁移，生成了苄基吡唑嘧啶(8)和芳烃羰醛(3)。四丁基铵氰(11, Bu4NCN)比KCN(10)更有效地作为氰离子的供体。逆苯偶姻缩合反应被应用于从2-氯-4-芳酰基喹唑啉(34)合成2-取代喹唑啉(38)，使用芳酰基作为保护和电子 withdrawing 基团。
• Catalytic Action of Azolium Salts. IV. Preparations of 4-Aroylquinazolines and 4-Aroyl-1H-pyrazolo(3,4-d)pyrimidines by Catalytic Action of 1,3-Dimethylimidazolium Iodide.
  作者：Akira MIYASHITA、Hideaki MATSUDA、Yumiko SUZUKI、Ken-ichi IWAMOTO、Takeo HIGASHINO

  DOI：10.1248/cpb.42.2017

  日期：——

  The ability of 1, 3-dimethylimidazolium iodide (1) to catalyze the aroylation of the chloroheteroarenes 4-8 with arenecarbaldehydes 3 as sources of the aroyl groups was examined in order to develop a preparative method of aroylheteroarenes. In the presence of 1, the treatment of the 4-chloroquinazolines (4 : 2-H, 5 : 2-Me, 6 : 2-Ph) with arenecarbaldehyde 3 in refluxing THF (tetrahydrofuran) or dioxane led to the 4-aroylquinazolines (9 : 2-H, 10 : 2-Me, 11 : 2-Ph) in excellent yields, as had been found with 1, 3-dimethylbenzimidazolium iodide (2). Similar reaction of the 4-chloro-1H-pyrazolo[3, 4-d]pyrimidines (7 : 1-Ph, 8 : 1-Me) with arenecarbaldehyde 3 yielded the corresponding 4-aroyl-1H-pyrazolo[3, 4-d]pyrimidines (12 : 1-Ph, 13 : 1-Me). Compound 1 seems to catalyze the aroylation of a wider range of arenecarbaldehydes 3 as compared with 2.

  研究了1,3-二甲基咪唑锭碘化物（1）催化氯杂芳烃4-8与芳烯羰基化合物3的芳酰基化反应的能力，以开发一种合成芳酰杂芳烃的新方法。在存在1的条件下，4-氯喹唑啉（4：2-H，5：2-Me，6：2-Ph）与芳烯羰基化合物3在回流的THF（四氢呋喃）或二噁烷中反应，得到了优良产率的4-芳酰喹唑啉（9：2-H，10：2-Me，11：2-Ph），这与1,3-二甲基苯并咪唑锭碘化物（2）得到的结果一致。类似地，4-氯-1H-吡唑[3,4-d]嘧啶（7：1-Ph，8：1-Me）与芳烯羰基化合物3反应，得到了相应的4-芳酰-1H-吡唑[3,4-d]嘧啶（12：1-Ph，13：1-Me）。与2相比，化合物1似乎能催化更广泛的芳烯羰基化合物3的芳酰基化反应。
• Catalytic action of azolium salts. I. Aroylation of 4-chloro-1H-pyrazolo(3,4-d)pyrimidines with aromatic aldehydes catalyzed by 1,3-dimethylbenzimidazolium iodide.
  作者：Akira MIYASHITA、Hideaki MATSUDA、Chihoko IIJIMA、Takeo HIGASHINO

  DOI：10.1248/cpb.38.1147

  日期：——

  When a mixture of 4-chloro-1-phenyl-1H-pyrazolo[3, 4-d]pyrimidine (9), aromatic aldehyde (5), sodium hydride, and a catalytic amount of 1, 3-dimethylbenzimidazolium iodide (4) in tetrahydrofuran was refluxed, the nucleophilic aroylation occurred, resulting in the formation of the aryl 1-phenyl-1H-pyrazolo[3, 4-d]pyrimidin-4-yl ketones (11).Similar reaction of 4-chloro-1-methyl-1H-pyrazolo[3, 4-d]pyrimidine (10) gave the corresponding aryl 1-methyl-1H-pyrazolo[3, 4-d]pyrimidin-4-yl ketones (12) in moderate yields. Use of dimethylformamide or dimethyl sulfoxide in the above reaction reduced the necessary reaction time and reaction temperature. A plausible reaction pathway for the formation of the ketones 11 and 12 involving the catalytic action of 4 is proposed.

  将 4-氯-1-苯基-1H-吡唑并[3, 4-d]嘧啶（9）、芳香醛（5）、氢化钠和催化剂量的 1、在四氢呋喃中回流 1，3-二甲基苯并咪唑鎓碘化物（4），发生亲核酰化反应，生成芳基 1-苯基-1H-吡唑并[3，4-d]嘧啶-4-基酮（11）。与 4-氯-1-甲基-1H-吡唑并[3, 4-d]嘧啶（10）的类似反应以中等产率得到了相应的芳基 1-甲基-1H-吡唑并[3, 4-d]嘧啶-4-基酮（12）。在上述反应中使用二甲基甲酰胺或二甲基亚砜可缩短必要的反应时间，降低反应温度。在 4 的催化作用下，提出了形成酮 11 和酮 12 的合理反应途径。
• Synthesis and Reactivities of 1,3-Dimethyl-2-(a-hydroxybenzyl)imidazolium and 1,3-Dimethyl-2-(a-hydroxybenzyl)benzimidazolium Iodides
  作者：Akira Miyashita、Akihito Kurachi、Yoshiyuki Matsuoka、Noriko Tanabe、Yumiko Suzuki、Ken-ichi Iwamoto、Takeo Higashino

  DOI：10.3987/com-96-s40

  日期：——

  1,3-Dimethyl-2-(alpha-hydroxybenzyl)benzimidazolium iodide (3a) was synthesized from 1-methylbenzimidazole (10) through two steps involving lithiation and quaternization. Treatment of 3a with 4-chloro-1-phenyl-1H-pyrazolo[3,4-d]pyrimidine (6) afforded 4-benzoyl-1-phenyl-1H-pyrazolo[3,4-d]pyrimidine (15a). 4-Benzoylquinazoline (14a) and 7-benzoyl-3-phenyl-3H-1,2,3-triazolo[4,5-d]pyrimidine (16a) were given by reaction of 3a with 4-chloroquinazolin (5) and 7-chloro-3-phenyl-3H-1,2,3-triazolo[4,5-d]pyrimidine. (7). Treatment of 3a with benzaldehyde (9a) gave benzoin (8a). Similar results were obtained in the reactions of 1,3-dimethyl-2-(alpha-hydroxybenzyl)imidazo iodide (4a).
• Several Approaches to Cyanide Ion-catalyzed Synthesis of 4-Aroyl-1-phenyl-1H-pyrazolo-[3,4-d]pyrimidines
  作者：Akira Miyashita、Yumiko Suzuki、Kiyono Ohta、Ken-ichi Iwamoto、Takeo Higashino

  DOI：10.3987/com-97-s(n)53

  日期：——

  4-Aroyl-1-phenyl-1H-pyrazolo[3,4-d]pyrimidines (5) were formed in low yields by reaction of 4-chloro-1-phenyl-1H-pyrazolo[3,4-d]pyrimidine (4) with arenecarbaldehydes (3) in the presence of potassium cyanide. Similar reaction of 4-tosyl-1-phenyl-1H-pyrazolo [3,4-d]pyrimidine (9) with 3 gave the ketones (5) in higher yields (60-74%). In the presence of catalytic amounts of both sodium p-toluenesulfinate (10) and potassium cyanide, the reaction of 4 with 3 gave the ketones (5) in good yields.