SU910586A1 - Process for producing 1-azido-2-methyl anthraquinone - Google Patents

Description

(54) METHOD OF nOJFHEHHH 1-AZIDO-2-METHILANTHRAINOINONE

3 The dissolution of amines in concentrated sulfuric acid takes a long time and is carried out with cooling. The preparation of nitrosylsulfuric acid is accompanied by the need to slowly dissolve the nitrite of sodium nitrate-concentrated sulfuric acid with subsequent slots during cooling and heating. The process of diazotization in concentrated sulfuric acid is slow (up to 4 hours). The isolation of sulfuric acid of diazonium salts is associated with significant losses, which leads to a low yield of the desired product. In addition, some diazo salts are unstable in dilute sulfuric acid; therefore, it is not possible to isolate them by pouring a sulfuric acid solution into ice. Another disadvantage of the known method is the low yield of the target product. The aim of the invention is to simplify the process technology and increase the yield of the target product. According to the invention, the goal is achieved in that 1-azi to-2-methylanthraquinone is obtained by reacting a 2-methylanthraquinone derivative with an alkali metal azide in a solvent medium, and a distinctive feature is the use of 1-nitro-2 as a derivative, 2-methanthraquinone - methylanthraquinone, carrying out the process at a molar ratio of 1-nitro-2-methylanthraquinone: alkali metal azide, equal to 1: 1-1: 10 at a temperature of 20-65 ° C and using an aprotic organic solvent as a solvent. In the present invention, the starting material for the preparation of 1-azido-2-methylanthraquinone is readily available 1-nitro-2-methanthraquinone. The process is expediently carried out at a temperature of 20-60 ° C, which contributes to the increase in the solubility of the starting products. Control over the course of the reaction is carried out by thin-layer chromatography. From those in the next way. At different time intervals (3-4 times for each experiment), a drop of the reaction mass is introduced into I ml of toluene. A drop of the resulting diluted solution is applied to a gshastinka silufol, 5 cm in size, 0.5-1 cm from the edge. Near the site of application of the test solution (after 0.5 cm), a drop of solutions of pure 1-nitro-2-methylanthraquinone and 1-azido-2-methylanthraquinone is placed. Then the plate is dried at room temperature 15-25 ° C for 1-5 minutes and placed in a chromatographic chamber containing a toluene-acetone mixture of 3: 1 (by volume). The plate is kept in the chamber until the front of the solvent rises a distance of 6-6.5 cm. On the chromatogram obtained, a spot of the starting 1-nitro-2-methylanthraquinone is marked with the witness number CR.JP 0.277 and the final -Azido-2-methyl anthrafinpe-witness along with ( R 0.338). Example 1. To a solution of 0.67 g (o, 0025 mol) of 1-nitro-2-methylanthraquinone in 20 ml of dimethylformamide was added 0.325 g (0.005 mol) of sodium azide. Synthesis is carried out with constant stirring at a temperature of 45-50 ° C for 5 hours. Monitoring the progress of the reaction is carried out with the aid of those on Silufol plates, 1-azido-2-methylanthraquinone is isolated by filtration as a yellow precipitate. The 1-azido-2-methylanthraquinone is purified by recrystallization from toluene. The yield of purified α-azido-2-methylanthraquinone - 0.51 g (78.4%). Found%: N 16,12; . Calculated%: N 15.96. Example 2. To a solution of 0.67 g (o, 0025 mol) of 1-nitro-2-methanthraquinone in 30 ml of dimethyl sulfoxide, 0.325 g (0.005 mol) of sodium azide was added. The synthesis is carried out at a constant displacement at a temperature of 50-60 ° C for 4 hours. The progress of the reaction is monitored by using those on Silufol plates, 1-azido-2-methylanthraquinone is isolated by filtration as a yellow color. The precipitate is washed with water, dried and recrystallized from toluene. Yield 0.58 g (87.88%; Found,%: N 15.9, 15.86. Calculated,%: N 15.96. Example 3. To a solution of 0.67 (0.0025 mol) 1-nitro -2-mets1 anthraquinone in 20 nl sulfolane was added 0.325 g (0.005 mol) of sodium azide.The synthesis is carried out with constant stirring at a temperature of 6065 ° C for 3 hours. The selection of the target product is similar to the example. Output 0.52 g I. 78.79% Found: 15.60 15.60%, Example 4. To a solution of 0.67 (o, 0025 mol) of 1-nitro-2-methanthraquinone in 20 ml of hexamethanol, 0.325 g (:, 005 mol) of sodium azide was added. Synthesis is carried out with constant stirring at room temperature for 3 hours. Isolation of a product of the same product as the RU 1., Output 0.58 g VB7.88%) Found: 15.62, 15.70. Example 5. To a solution of 0.67 (0.0025 mol) of 1-nitro-2-methylanthraquinone in 20 ml of dimethylformamide, 0.405 g (0.005 mol) of Asian and potassium was added. Synthesis is carried out under constant stirring at room temperature for 5 hours. Isolation of 1-azido-2-methylanthraquinone is similar to Example 1. Yield 0.56 g (84.85%) Found: 15.85, 15.78. Example 6. To a solution of 0.67 (0.0025 mol) of 1-nitro-2-methylanthra non in 30 ml of dimethyl sulphoxide, 0.405 g (0.005 mol) of potassium azide was added. Synthesis is carried out with constant stirring at a temperature of 6065s for 3 hours. The allocation of the final product is similar to Example 1.

(86.36%).

Yield 0.57 g

N 15.8, 15.83. Found%:

Example 7. To a solution of 0.67 g (0.0025 mol) of 1-nitro-2-methylanthraquinone in 20 ml of sulfolane was added 0.405 g (0.005 mol) of potassium azide. The synthesis is carried out with constant stirring for 2 hours at a temperature of 50-60 C. The isolation of the final product is similar to example 1.

Yield 0.54 g (81.82%).

Found,%: N 15.78; 15.73.

Example 8. To a solution of 0.67 g (o, 0025 mol) of 1-nitro-2-methylanthraquinone B 20 ml of hexamethanol add 0.405 g (0.005 mol) of azide

Claims (1)

Invention Formula The method of producing 1-azido-2-methyl anthraquinone by reacting a 2-methylanthraquinone derivative with an alkali metal azide in a solvent medium, characterized in that, in order to simplify the process technology and increase the yield of the target product, 1-nitro is used as a 2-mec anthrahinone derivative -2-methylanthraquinone, the process is carried out at a molar ratio of 1-nitro-2-methylanthraquinone and an alkali metal azide, equal to 1: 1-1: 10 at 20-65 s, and on the swing. Synthesis is carried out under constant stirring at a temperature of 2022 ° C for 5 hours. Isolation of the final 1-azido-2-methy-anthraquinone is similar to Example I. Yield 0.55 g (83.33%) Found%: N 15.85-, 15, 89, Example 9. To a solution of 0.67 g (0.0025 mol) of 1-nitro-2-methyl anthraquine in 20 MP of dimethylformamide, 0.163 g (0.0025 mol) of sodium azide was added. Synthesis is carried out with constant stirring at a temperature of 50-60 ° C for 5 hours. Monitoring the progress,. . reactions were performed by TLC on Silufol plates. The yellow precipitate of the precipitated 1-azido-2-methanthraquinone is isolated by filtration. The 1-azido-2-methylactraquinone is purified by recrystallization from toluene. Yield 1-azido-2-methylanthrachinoia 0.5 g (78.4%) Found%: N 15.92 15.90. Calculated%: N 15.96. Example 10. To a solution of 0.67 g (o, 0025, mol) of 1-1 Shtro-2-methylanthraquinone and 30 ml of dimethylformamide, 1, 63 g (0.025 mol) of sodium azide was added. The synthesis is carried out under constant stirring at a temperature of 5060 ° C for 2 hours. The reaction is monitored by TLC on Silufol plates. The yellow precipitate of precipitated 1-azido-2-methylanthraquinone is isolated by filtration. The 1-azido-2-methylanthraquinone is purified by recrystallization from toluene. Yield 0.52 g (78.79%) Found% N 15.84, 15.88. Calculated 16.96. N 79105868 solvent is used with apro-1. Dokunikhin, N.S. Galitsyna L.V. ton organic solvent. The azides of the anthraquinone order. Report  Sources of information, Academy of Sciences of the USSR, 1968, t. 179, No. 5, p. 1099 taken into account in the examination of 1101 (prototype).