4-benzyloxy-6-hydroxy-3-methoxy-2-isopropoxyacetophenone | 188927-31-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-benzyloxy-6-hydroxy-3-methoxy-2-isopropoxyacetophenone
• 英文别名: 1-(6-Hydroxy-3-methoxy-4-phenylmethoxy-2-propan-2-yloxyphenyl)ethanone
• CAS: 188927-31-3
• 化学式: C₁₉H₂₂O₅
• 分子量: 330.381
• InChiKey: ZNLYNPNNGPPNHM-UHFFFAOYSA-N

物化性质

• 熔点：
  69–70°C
• 沸点：
  485.1±40.0 °C(Predicted)
• 密度：
  1.157±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-benzyloxy-6-hydroxy-3-methoxy-2-isopropoxyacetophenone 在 palladium on activated charcoal 盐酸 、 氢氧化钾 、 三氯化铝 、 氢气 、 potassium carbonate 、 thallium(III) nitrate 作用下， 以 甲醇 、 乙醇 、 氯仿 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 25.17h， 生成 鸢尾黄酮乙素
  参考文献：
  名称：

  Studies of the Selective O-Alkylation and Dealkylation of Flavonoids. XXIV. A Convenient Method for Synthesizing 6- and 8-Methoxylated 5,7-Dihydroxyisoflavones.

  摘要：

  自2,4-二羟基-3,6-二甲氧基苯乙酮二苄基醚(3)得到的2',4'-双(苄氧基)-3',6'-二甲氧基查耳酮(5),在甲醇中和硝酸铊(III)氧化重排,产物用氢解还原,闭环得到7-羟基-5,8-二甲氧基异黄酮(8)。这些异黄酮以它们的乙酸盐的接触方法定量地脱甲基,得到5,7-二羟基-8-甲氧基异黄酮(2)。5,7-二羟基-6-甲氧基异黄酮(1)以从2,3-二甲氧基或2-异丙氧基-3-甲氧基-4,6-双(苄氧基)苯乙酮(21)得到的查耳酮为原料,通过相似的方法制得。巯豆另一方面,2'和4'位带有二羟基的异黄酮很易通过下述方法合成。2,2',4,4'-四(苄氧基)-3',6'-二甲氧基查耳酮(5f)的重排产物,在醋酸中用盐酸处理,得到2',4',7-三(苄氧基)-5,8-二甲氧基异黄酮(10f).异黄酮(10f)中的5-甲氧基很快裂解得到相应的5-羟基异黄酮(11f),在无水碳酸钾存在下异构成2',4',7-三(苄氧基)-5-羟基-6-甲氧基异黄酮(25f)。两个5-羟基异黄酮中的苄基很容易氢解,分别得到2',4',5,7-四羟基-8-(2f)和6-甲氧基异黄酮(1f)。这些异黄酮的'C-NMR谱支持了多羟基异黄酮的分子结构的推定。两个天然异黄酮的分子结构进行了修订。

  DOI：

  10.1248/cpb.46.222
• 作为产物：
  描述：

  1-(4-benzyloxy-2-hydroxy-3,6-dimethoxy-phenyl)-ethanone 在 aluminum tri-bromide 、 potassium carbonate 、 potassium iodide 、 sodium iodide 作用下， 以 N,N-二甲基甲酰胺 、 丙酮 、 乙腈 为溶剂， 反应 0.25h， 生成 4-benzyloxy-6-hydroxy-3-methoxy-2-isopropoxyacetophenone
  参考文献：
  名称：

  Studies of the Selective O-Alkylation and Dealkylation of Flavonoids. XXII. A Convenient Method for Synthesizing 3,5,7-Trihydroxy-6-methoxyflavones.

  摘要：

  研究了3, 4-二氧化6-甲氧基-2-异丙氧基苯乙酮的脱甲基反应，发现4-苄氧基-6-羟基-3-甲氧基-2-异丙氧基苯乙酮很容易由4-苄氧基-3, 6-二甲氧基得到4-苄氧基-6-羟基-3-甲氧基-2-异丙氧基苯乙酮-2-异丙氧基苯乙酮，用无水溴化铝-碘化钠在乙腈中选择性脱甲基。通过环化然后用二甲基二环氧乙烷氧化将苯乙酮转化为7-苄氧基-3-羟基-6-甲氧基-5-异丙氧基黄酮。用无水氯化铝通过相应的甲苯磺酸盐选择性裂解黄酮中的异丙氧基，得到7-苄氧基-3,5-二羟基-6-甲氧基黄酮，将其转化为所需的3,5,7-三羟基-6-甲氧基黄酮通过氢解作用。该工艺适合作为合成3,5,7-三羟基-6-甲氧基黄酮的通用方法，并合成了5种黄酮。我们还检查了 12 种 3,5,6,7-四氧化 4'-甲氧基黄酮的 13C-NMR 谱，并修改了天然黄酮的提议结构。

  DOI：

  10.1248/cpb.45.446

文献信息

• 13C NMR spectral assignment of the A-ring of polyoxygenated flavones
  作者：Tokunaru Hòrie、Yoshizumi Ohtsuru、Kenichi Shibata、Kazuyo Yamashita、Masao Tsukayama、Yasuhiko Kawamura

  DOI：10.1016/s0031-9422(97)00629-8

  日期：1998.3

  The C-13 NMR spectra of polyhydroxyflavones were systematically examined by using about 70 examples which have a 4-methoxyphenyl B-ring, such as 5,6,7-, 5,7,8 and 5,6,8-trioxygenated and 5,6,7,8-tetraoxygenated flavones and flavonols, and the following results were obtained. In the C-13 NMR spectra of flavones, the signals at the 2-, 3- and 4-positions in the C-ring were hardly affected by the substituents on the A-ring except for those at the 5-position and shifted regularly by introduction of a methoxy or hydroxy group at the 3-position. The signals at the 5- to 10-positions in the A-ring were greatly affected by the substituents and oxygenated patterns on the A-ring and exhibited the respective characteristic pattern reflecting the A-ring substituents without the effects of the substituents on the B- and C-rings. The substituent effects on the A-ring were estimated from the spectral data. Consequently, it is found that the structures of polyhydroxyflavones can be correctly defined by their C-13 NMR spectral assignment. Additionally, we examined the structures of some natural flavones previously reported. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Studies of the Selective O-Alkylation and Dealkylation of Flavonoids. XXIV. A Convenient Method for Synthesizing 6- and 8-Methoxylated 5,7-Dihydroxyisoflavones.
  作者：Tokunaru HORIE、Kenichi SHIBATA、Kazuyo YAMASHITA、Kenichi FUJII、Masao TSUKAYAMA、Yoshizumi OHTSURU

  DOI：10.1248/cpb.46.222

  日期：——

  2', 4'-Bis(benzyloxy)-3', 6'-dimethoxychalcones (5), which were obtained from the dibenzyl ether of 2, 4-dihydroxy-3, 6-dimethoxyacetophenone (3), were oxidatively rearranged with thallium (III) nitrate in methanol and the resultant products were converted into 7-hydroxy-5, 8-dimethoxyisoflavones (8) by hydrogenolysis, followed by cyclization. The isoflavones were quantitatively demethylated to 5, 7-dihydroxy-8-methoxyisoflavones (2) via their acetates. The isomeric 5, 7-dihydroxy-6-methoxyisoflavones (1) were also synthesized from the chalcones, obtained from 2, 3-dimethoxy- (16) or 2-isopropoxy-3-methoxy-4, 6-bis(benzyloxy)acetophenones (21), by a similar method. On the other hand, the isoflavones with two hydroxy groups at the 2'- and 4'-positions were easily synthesized by the following method. Treatment of the rearranged product from 2, 2', 4, 4'-tetrakis(bezyloxy)-3', 6'-dimethoxychalcone (5f) with hydrochloric acid (HCl) in acetic acid afforded 2', 4', 7-tris(benzyloxy)-5, 8-dimethoxyisoflavone (10f). The 5-methoxy group in the isoflavone was quantitatively cleaved to give the corresponding 5-hydroxyisoflavone (11f), which was isomerized to 2', 4', 7-tris(benzyloxy)-5-hydroxy-6-methoxyisoflavone (25f) in the presence of anhydrous potassium carbonate. Hydrogenolysis of the two 5-hydroxyisoflavones proceeded smoothly to give 2', 4', 5, 7-tetrahydroxy-8-(2f) and 6-methoxyisoflavones(1f), respectively. The 13C-NMR spectra of these isoflavones supported the proposed structures of polyhydroxyisoflavones. The proposed structures of two natural isoflavones were revised.

  自2,4-二羟基-3,6-二甲氧基苯乙酮二苄基醚(3)得到的2',4'-双(苄氧基)-3',6'-二甲氧基查耳酮(5),在甲醇中和硝酸铊(III)氧化重排,产物用氢解还原,闭环得到7-羟基-5,8-二甲氧基异黄酮(8)。这些异黄酮以它们的乙酸盐的接触方法定量地脱甲基,得到5,7-二羟基-8-甲氧基异黄酮(2)。5,7-二羟基-6-甲氧基异黄酮(1)以从2,3-二甲氧基或2-异丙氧基-3-甲氧基-4,6-双(苄氧基)苯乙酮(21)得到的查耳酮为原料,通过相似的方法制得。巯豆另一方面,2'和4'位带有二羟基的异黄酮很易通过下述方法合成。2,2',4,4'-四(苄氧基)-3',6'-二甲氧基查耳酮(5f)的重排产物,在醋酸中用盐酸处理,得到2',4',7-三(苄氧基)-5,8-二甲氧基异黄酮(10f).异黄酮(10f)中的5-甲氧基很快裂解得到相应的5-羟基异黄酮(11f),在无水碳酸钾存在下异构成2',4',7-三(苄氧基)-5-羟基-6-甲氧基异黄酮(25f)。两个5-羟基异黄酮中的苄基很容易氢解,分别得到2',4',5,7-四羟基-8-(2f)和6-甲氧基异黄酮(1f)。这些异黄酮的'C-NMR谱支持了多羟基异黄酮的分子结构的推定。两个天然异黄酮的分子结构进行了修订。
• Studies of the Selective O-Alkylation and Dealkylation of Flavonoids. XXII. A Convenient Method for Synthesizing 3,5,7-Trihydroxy-6-methoxyflavones.
  作者：Tokunaru HORIE、Kenichi SHIBATA、Kazuyo YAMASHITA、Yasuhiko KAWAMURA、Masao TSUKAYAMA

  DOI：10.1248/cpb.45.446

  日期：——

  The demethylation of 3, 4-dioxygenated 6-methoxy-2-isopropoxyacetophenones was studied and it was found that 4-benzyloxy-6-hydroxy-3-methoxy-2-isopropoxyacetophenone was easily obtained from 4-benzyloxy-3, 6-dimethoxy-2-isopropoxyacetophenone by selective demethylation with anhydrous aluminum bromide-sodium iodide in acetonitrile. The acetophenone was converted into 7-benzyloxy-3-hydroxy-6-methoxy-5-isopropoxyflavones by cyclization followed by oxidation with dimethyldioxirane. The isopropoxy group in the flavones was selectively cleaved with anhydrous aluminum chloride via the corresponding tosylates to give 7-benzyloxy-3, 5-dihydroxy-6-methoxyflavones, which were converted into the desired 3, 5, 7-trihydroxy-6-methoxyflavones by hydrogenolysis. The process was suitable as a general method for synthesizing 3, 5, 7-trihydroxy-6-methoxyflavones and five flavones were synthesized. We also examined the 13C-NMR spectra of twelve kinds of 3, 5, 6, 7-tetraoxygenated 4'-methoxyflavones and revised the proposed structure of a natural flavone.

  研究了3, 4-二氧化6-甲氧基-2-异丙氧基苯乙酮的脱甲基反应，发现4-苄氧基-6-羟基-3-甲氧基-2-异丙氧基苯乙酮很容易由4-苄氧基-3, 6-二甲氧基得到4-苄氧基-6-羟基-3-甲氧基-2-异丙氧基苯乙酮-2-异丙氧基苯乙酮，用无水溴化铝-碘化钠在乙腈中选择性脱甲基。通过环化然后用二甲基二环氧乙烷氧化将苯乙酮转化为7-苄氧基-3-羟基-6-甲氧基-5-异丙氧基黄酮。用无水氯化铝通过相应的甲苯磺酸盐选择性裂解黄酮中的异丙氧基，得到7-苄氧基-3,5-二羟基-6-甲氧基黄酮，将其转化为所需的3,5,7-三羟基-6-甲氧基黄酮通过氢解作用。该工艺适合作为合成3,5,7-三羟基-6-甲氧基黄酮的通用方法，并合成了5种黄酮。我们还检查了 12 种 3,5,6,7-四氧化 4'-甲氧基黄酮的 13C-NMR 谱，并修改了天然黄酮的提议结构。