6-(2-Methylenequinoline)tryptanthrin compound and synthetic method thereof

Abstract

The invention discloses a 6-(2-methylenequinoline)tryptanthrin compound and a synthetic method thereof. The method comprises the following steps: directly fully reacting a tryptanthrin compound with 2-methylquinoline in an organic solvent A under a catalyst-free condition, adding a solvent B to a reaction solution obtained after the reaction is finished, fully stirring the reaction solution and the solvent B to precipitate the product, and carrying out centrifugal purification to obtain the 6-(2-methylenequinoline)tryptanthrin derivative. The 6-(2-methylenequinoline)tryptanthrin compound is syntehsized from the tryptanthrin and the 2-methylquinoline under the catalyst-free condition for the first time. The method mainly has the advantages of simplicity in operation, low cost due to the catalyst-free condition, greenness due to no metals or external alkalis, and high reaction yield. The method has high basic research values and high social and economic benefits.

Description

technical field

[0001] The invention relates to the field of organic chemistry, in particular to a 6-(2-methylenequinoline) tryptanthrin compound and a synthesis method thereof. Background technique

[0002] Tryptanthrins are an important class of compounds with good biological and pharmacological activities, and are widely used in the synthesis of natural products and drug molecules. The most representative use is that it has a good effect on anti-oxidation and anti-tumor. It is the key skeleton of Phaitanthrin A, Phaitanthrin B, Candidine, Cruciferance and other drugs (J.Am.Chem.Soc., 1987,109,7881; Bioorg . Med. Chem. Lett., 2013, 23, 1032; Nat. Prod., 2008, 71, 1275; Bioorg. Med. Chem. Lett., 2006, 16, 6246.). Recent studies have shown that such compounds have also made breakthroughs in the field of optics and play an active role (Org. Lett., 2013, 15, 4738; Org. Lett., 2015, 17, 5962). In addition, quinoline compounds also have good physiological activity and are the ...

Examples

Embodiment 1

[0036] Tryptanthrin, 2-methylquinoline is 1.0:10.0 feeding intake with the amount ratio of substance, tryptanthrin 24.8g (0.1mol), 2-methylquinoline 143g (1mol); Organic solvent is tetrahydrofuran 250g, and its total The dosage is 10 times of tryptanthrin quality.

[0037] Put tryptanthrin and 2-methylquinoline into the reaction kettle, add tetrahydrofuran to dissolve, the reaction temperature is 100°C, and the reaction ends after 24 hours.

[0038] After the reaction, cool the reaction system to room temperature, add water with a mass 10 times that of tetrahydrofuran and stir for 0.5 hours so that the product is fully separated, and the product is obtained by centrifugation. After washing and drying, a light yellow solid is obtained, which is 6-(2-methylenequinone Phylo) tryptanthrin product 21.5g, yield 55%, purity 97.3%, concrete structure is

[0039]

[0040] NMR (Bruker): 1 H NMR (500MHz, DMSO) δ (ppm) 4.03 (dd, J 1 =15.5Hz,J 2 =20Hz,2H),6.71(s,1H),7.09(d,J=8.5Hz,1...

Embodiment 2

[0042] Tryptanthrin and 2-methylquinoline are fed with a substance ratio of 1.0:10.0, tryptanthrin 24.8g (0.1mol), 2-methylquinoline 143g (1mol); the organic solvent is N,N-di Methyl formamide 250g, its total consumption is 10 times of tryptanthrin mass.

[0043] Put tryptanthrin and 2-methylquinoline into the reaction kettle, add N,N-dimethylformamide to dissolve, the reaction temperature is 100°C, and the reaction ends after 24 hours.

[0044] The rest is the same as in Example 1 to obtain 22.7 g of 6-(2-methylenequinoline) tryptanthrin product, with a yield of 58% and a purity of 98.1%.

Embodiment 3

[0046] Tryptanthrin and 2-methylquinoline are fed with a material ratio of 1.0:10.0, tryptanthrin 24.8g (0.1mol), 2-methylquinoline 143g (1mol); the organic solvent is N,N-di Methyl formamide 250g, its total consumption is 10 times of tryptanthrin mass.

[0047] Put tryptanthrin and 2-methylquinoline into the reaction kettle, add N,N-dimethylformamide to dissolve, the reaction temperature is 100°C, and the reaction ends after 24 hours.

[0048] After the reaction, cool the reaction system to room temperature, add ethanol 10 times the mass of N,N-dimethylformamide and stir for 0.5 hours so that the product is fully separated, centrifuged to obtain the product, washed and dried with ethanol to obtain a light yellow solid, that is, The 6-(2-methylenequinoline) tryptanthrin product was 25.4 g, the yield was 65%, and the purity was 99.3%.

technical field

[0001] The invention relates to the field of organic chemistry, in particular to a 6-(2-methylenequinoline) tryptanthrin compound and a synthesis method thereof. Background technique

[0002] Tryptanthrins are an important class of compounds with good biological and pharmacological activities, and are widely used in the synthesis of natural products and drug molecules. The most representative use is that it has a good effect on anti-oxidation and anti-tumor. It is the key skeleton of Phaitanthrin A, Phaitanthrin B, Candidine, Cruciferance and other drugs (J.Am.Chem.Soc., 1987,109,7881; Bioorg . Med. Chem. Lett., 2013, 23, 1032; Nat. Prod., 2008, 71, 1275; Bioorg. Med. Chem. Lett., 2006, 16, 6246.). Recent studies have shown that such compounds have also made breakthroughs in the field of optics and play an active role (Org. Lett., 2013, 15, 4738; Org. Lett., 2015, 17, 5962). In addition, quinoline compounds also have good physiological activity and are the ...

Examples

Embodiment 1

[0036] Tryptanthrin, 2-methylquinoline is 1.0:10.0 feeding intake with the amount ratio of substance, tryptanthrin 24.8g (0.1mol), 2-methylquinoline 143g (1mol); Organic solvent is tetrahydrofuran 250g, and its total The dosage is 10 times of tryptanthrin quality.

[0037] Put tryptanthrin and 2-methylquinoline into the reaction kettle, add tetrahydrofuran to dissolve, the reaction temperature is 100°C, and the reaction ends after 24 hours.

[0038] After the reaction, cool the reaction system to room temperature, add water with a mass 10 times that of tetrahydrofuran and stir for 0.5 hours so that the product is fully separated, and the product is obtained by centrifugation. After washing and drying, a light yellow solid is obtained, which is 6-(2-methylenequinone Phylo) tryptanthrin product 21.5g, yield 55%, purity 97.3%, concrete structure is

[0039]

[0040] NMR (Bruker): 1 H NMR (500MHz, DMSO) δ (ppm) 4.03 (dd, J 1 =15.5Hz,J 2 =20Hz,2H),6.71(s,1H),7.09(d,J=8.5Hz,1...

Embodiment 2

[0042] Tryptanthrin and 2-methylquinoline are fed with a substance ratio of 1.0:10.0, tryptanthrin 24.8g (0.1mol), 2-methylquinoline 143g (1mol); the organic solvent is N,N-di Methyl formamide 250g, its total consumption is 10 times of tryptanthrin mass.

[0043] Put tryptanthrin and 2-methylquinoline into the reaction kettle, add N,N-dimethylformamide to dissolve, the reaction temperature is 100°C, and the reaction ends after 24 hours.

[0044] The rest is the same as in Example 1 to obtain 22.7 g of 6-(2-methylenequinoline) tryptanthrin product, with a yield of 58% and a purity of 98.1%.

Embodiment 3

[0046] Tryptanthrin and 2-methylquinoline are fed with a material ratio of 1.0:10.0, tryptanthrin 24.8g (0.1mol), 2-methylquinoline 143g (1mol); the organic solvent is N,N-di Methyl formamide 250g, its total consumption is 10 times of tryptanthrin mass.

[0047] Put tryptanthrin and 2-methylquinoline into the reaction kettle, add N,N-dimethylformamide to dissolve, the reaction temperature is 100°C, and the reaction ends after 24 hours.

[0048] After the reaction, cool the reaction system to room temperature, add ethanol 10 times the mass of N,N-dimethylformamide and stir for 0.5 hours so that the product is fully separated, centrifuged to obtain the product, washed and dried with ethanol to obtain a light yellow solid, that is, The 6-(2-methylenequinoline) tryptanthrin product was 25.4 g, the yield was 65%, and the purity was 99.3%.

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