Preparation of Optically Pure (s)-3-Pivaloyloxy-6,7-Dimethoxyphenanthroindolizidine
A technology of phenanthrene-indolizidine and indolizidine, which is applied in the fields of organic chemistry, chemical instruments and methods, and compounds of Group 4/14 elements of the periodic table, etc., which can solve cumbersome operations and difficult large-scale preparations , Optical purity is not clear and other issues, to achieve the effect of simple operation and easy amplification of the reaction
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Embodiment 1
[0042] Embodiment 1: Synthesis of (E)-2-(3,4-dimethoxyphenyl)-3-(4-acetoxyphenyl)acrylic acid (1)
[0043]
[0044] Add 1,000g of 3,4-dimethoxyphenylacetic acid, 632g of p-hydroxybenzaldehyde and 2,000ml of acetic anhydride into the reactor in sequence, add 1,000ml of triethylamine dropwise under stirring, after the drop is complete, raise the temperature of the reaction solution to 120°C, and continue the reaction After the raw materials were completely prepared, the temperature of the reaction solution was lowered to 50°C, 4L of water was added, a large amount of solids were precipitated under stirring, the solids were suction-filtered, and the filter cake was washed with water and dried by air at 60°C to obtain 1460g of (E)-2-(3 ,4-dimethoxyphenyl)-3-(4-acetoxyphenyl)acrylic acid. 1 H NMR (500MHz, MeOD) δ7.78(s, 1H), 7.12–7.08(m, 2H), 6.93(d, J=8.2Hz, 1H), 6.92–6.88(m, 2H), 6.73–6.70( m,2H),3.82(s,3H), 3.69(s,3H),2.20(s,3H). 13 C NMR (125MHz, MeOD) δ171.1, 170.8, 152.6...
Embodiment 2
[0045] Embodiment 2: Synthesis of (E)-2-(3,4-dimethoxyphenyl)-3-(4-hydroxyphenyl)methyl acrylate (2)
[0046]
[0047] Dissolve 1000g of (E)-2-(3,4-dimethoxyphenyl)-3-(4-acetoxyphenyl)acrylic acid in 10L of methanol, then quickly add 500ml of concentrated sulfuric acid, and reflux until the reaction is complete Afterwards, most of the solvent was evaporated to 2000ml and a large amount of solids were precipitated, filtered, the filter cake was beaten with 5L of water, and then air-dried to obtain 600g of (E)-2-(3,4-dimethoxyphenyl)-3- Methyl (4-hydroxyphenyl)acrylate. 1 H NMR (400MHz, DMSO) δ9.92(s, 1H), 7.66(s, 1H), 6.99-6.95(m, 3H), 6.75(d, J=1.8Hz, 1H), 6.69(dd, J= 8.2,1.9Hz,1H),6.60(d, J=8.7Hz,2H),3.80(s,3H),3.68(s,3H),3.67(s,3H).
Embodiment 3
[0048] Embodiment 3: Synthesis of 3-hydroxy-6,7-dimethoxy-9-phenanthrene acid methyl ester (3)
[0049]
[0050] After dissolving 200g of ferric chloride in 1500ml of dichloromethane, add 100g of (E)-2-(3,4-dimethoxyphenyl)-3-(4-hydroxyphenyl)methacrylate dropwise under nitrogen protection A mixed solution of dichloromethane (3000ml) and trifluoroacetic acid (100ml) of the ester, keep the system temperature at 20-25°C during the dropwise addition, stir at room temperature after the dropwise addition is complete, add 4.5L of water and continue stirring until After the solution is clarified, let it stand for 30 minutes to separate the layers. After the organic phase is evaporated to dryness, the obtained crude product is air-dried, then added to acetonitrile and heated to 60°C for beating for 2 hours, then cooled to -5°C and stirred for 4 hours to crystallize and then filtered. Acetonitrile was filtered and washed once to obtain a wet pure product, and after air-drying at 50°...
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