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Method for synthesizing 2-(9,10-dihydrophenanthrene-9-yl) malonate

A synthesis method and technology of malonate, applied in the preparation of carboxylic acid esters, chemical instruments and methods, preparation of organic compounds, etc., can solve the problems of harsh reaction conditions and expensive, and achieve the effect of mild reaction conditions

Active Publication Date: 2019-09-20
WENZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0012] However, the above-mentioned methods all have some defects, such as the need for harsh reaction conditions (metal sodium / liquid ammonia, light) or the need to use expensive metal catalysts and ligands

Method used

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  • Method for synthesizing 2-(9,10-dihydrophenanthrene-9-yl) malonate
  • Method for synthesizing 2-(9,10-dihydrophenanthrene-9-yl) malonate
  • Method for synthesizing 2-(9,10-dihydrophenanthrene-9-yl) malonate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041]

[0042] Add a stirring magnet and the above formula (I) compound (0.3mmol) to the Schlenk tube, nitrogen protection, add dichloromethane (3mL), and then add trifluoromethanesulfonic acid (0.12mmol, 0.4 molar equivalent) under stirring at 0°C , then sealed, and stirred at 0°C for 12 hours. The solvent and trifluoromethanesulfonic acid were distilled off under reduced pressure, and the residue was purified by column chromatography to obtain the compound of formula (II) with a yield of 78%.

[0043] 1 H NMR (400MHz, CDCl 3 )δ7.79-7.74(m,2H),7.36-7.32(t,J=7.4Hz,2H),7.26-7.23(m,2H),7.22-7.17(m,2H),4.22-4.17(m, 2H), 3.97-3.84(m, 2H), 3.76-3.72(m, 1H), 3.36(d, J=11.0Hz, 1H), 3.17(dd, J=4.7Hz, J=15.7Hz, 1H), 2.90(dd, J=2.2Hz, J=15.7Hz, 1H), 1.25(t, J=7.1Hz, 3H), 0.98(t, J=7.1Hz, 3H). 13 C NMR (125MHz, CDCl 3 )δ 168.21, 168.16, 136.06, 134.00, 133.81, 133.72, 129.14, 129.12, 128.03, 127.83, 127.37, 127.28, 124.08, 123.58, 61.30, 61.00, 53.86, 38.339, 14.3

Embodiment 2

[0045]

[0046] Add a stirring magnet and the above formula (I) compound (0.3mmol) to the Schlenk tube, nitrogen protection, add dichloromethane (3mL), and then add trifluoromethanesulfonic acid (0.15mmol, 0.5 molar equivalent) under stirring at 0°C , then sealed, and stirred at 0°C for 12 hours. The solvent and trifluoromethanesulfonic acid were distilled off under reduced pressure, and the residue was purified by column chromatography to obtain the compound of formula (II) with a yield of 78%.

[0047] 1 H NMR (400MHz, CDCl 3 )δ7.76(t, J=7.9Hz, 1H), 7.39-7.29(m, 2H), 7.27-7.19(m, 3H), 7.17(d, J=7.4Hz, 1H), 3.76-3.73(m ,1H),3.72(s,3H),3.44(s,3H),3.40(d,J=10.9Hz,1H),3.17(dd,J=5.0Hz,J=15.9Hz,1H),2.89(dd ,J=2.0Hz,J=15.8Hz,1H). 13 CNMR (125MHz, CDCl 3 )δ 168.61, 168.55, 135.90, 133.98, 133.68, 133.66, 129.16, 128.96, 128.17, 127.94, 127.45, 127.38, 124.21, 123.65, 53.72, 52.38, 52.08, 328.40, 3

Embodiment 3

[0049]

[0050] Add a stirring magnet and the above formula (I) compound (0.3mmol) to the Schlenk tube, under nitrogen protection, add dichloromethane (3mL), and then add trifluoromethanesulfonic acid (0.09mmol, 0.3 molar equivalent) under stirring at 0°C , then sealed, and stirred at 0°C for 12 hours. The solvent and trifluoromethanesulfonic acid were distilled off under reduced pressure, and the residue was purified by column chromatography to obtain the compound of formula (II) with a yield of 87%.

[0051] 1 H NMR (400MHz, CDCl 3 )δ7.74(d, J=7.7Hz, 1H), 7.64(d, J=7.9Hz, 1H), 7.31(t, J=7.5Hz, 1H), 7.21(t, J=7.4Hz, 1H) ,7.16-7.14(m,2H),7.07(s,1H),4.19(qd,J=2.1Hz,J=7.2Hz,12H),3.91(q,J=7.2Hz,2H),3.68(ddd, J=2.1Hz, J=5.1Hz, J=10.8Hz, 1H), 3.35(d, J=10.9Hz, 1H), 3.14(dd, J=5.1Hz, J=15.8Hz, 1H), 2.89(dd ,J=2.1Hz,J=15.8Hz,1H),2.33(s,3H),1.25(t,J=7.1Hz,3H),1.00(t,J=7.1Hz,3H). 13 C NMR (125MHz, CDCl 3 )δ168.32,168.23,137.08,136.00,133.85,133.57,131.31,129.76,129.12,128.76,1...

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Abstract

The invention discloses a method for synthesizing 2-(9,10-dihydrophenanthrene-9-yl) malonate. According to the technical scheme, an open-loop cyclization reaction of 2-biaryl cyclopropyl-1,1-dicarboxylate is implemented through trifluoromethanesulfonic acid catalysis, and thus 2-(9,10-dihydrophenanthrene-9-yl) malonate is synthesized. The method specifically comprises the following steps: by taking dichloromethane as a reaction solvent, adding 30-100mol% of trifluoromethanesulfonic acid, and carrying out a reaction under a condition of 0 DEG C, so as to obtain a target product. The method is easy in raw material obtaining, simple to operate, high in yield and good in universality.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for synthesizing 2-(9,10-dihydrophenanthrene-9-yl)malonate under strong acid catalysis. Background technique [0002] Many biologically active natural products contain 9-substituted 9,10-dihydrophenanthrene structures. Cedrelin A isolated from the bark of a leguminous plant has moderate inhibitory effects on Staphylococcus aureus and Bacillus subtilis (Tetrahedron Lett. 1991, 32, 2793-2796); Isolated Paralycolin A has in vitro cytotoxicity to oral cancer cells and P388 leukemia cells (Tetrahedron Lett. 1987, 28, 563-566). [0003] [0004] Currently, there are limited methods for synthesizing 9-substituted 9,10-dihydrophenanthrene compounds. The earliest applied method was the Birch reduction of 9-substituted phenanthrenes. Redden et al used sodium / liquid ammonia to reduce the 9-arylphenanthrene compound to obtain the target product when synth...

Claims

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Application Information

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IPC IPC(8): C07C67/333C07C69/65C07C69/616
CPCC07C67/333C07C2603/26C07C69/65C07C69/616
Inventor 李欢
Owner WENZHOU UNIVERSITY
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