CN110972530B - Synthesis method of 1-methyl-3, 3-diphenyl urea - Google Patents
Synthesis method of 1-methyl-3, 3-diphenyl urea Download PDFInfo
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- CN110972530B CN110972530B CN201110011355.7A CN201110011355A CN110972530B CN 110972530 B CN110972530 B CN 110972530B CN 201110011355 A CN201110011355 A CN 201110011355A CN 110972530 B CN110972530 B CN 110972530B
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Abstract
The invention discloses a method for synthesizing 1-methyl-3, 3-diphenylurea, which takes diphenylamine as a raw material and comprises the following steps of adding dichloromethane, pyridine and diphenylamine into an ① reaction bottle, dropwise adding a solid phosgene-dichloromethane solution under stirring at the temperature of 10-45 ℃, reacting for 2-6 h after dropwise adding, wherein the molar ratio of dichloromethane, diphenylamine, pyridine and solid phosgene is 4-8: 0.37-0.74: 0.12-0.25, adding diphenylamine-carbonyl chloride and triethylamine obtained in the step ① into the reaction bottle by ②, reacting for 0.5-4 h after methylamine gas is introduced at the temperature of 20-45 ℃, wherein the molar ratio of dichloromethane, diphenylamine-carbonyl chloride, triethylamine and methylamine is 4-8: 0.37-0.74: 0.37-0.74, and the invention is mainly used for synthesizing 1-methyl-3, 3-diphenylurea.
Description
Technical Field
The invention relates to a method for synthesizing 1-methyl-3, 3-diphenyl urea (AK-II), belonging to organic synthesis.
Background
1-methyl-3, 3-diphenyl urea is an important stabilizer for propellant and solid propellant. The synthesis method of AK-II is characterized by that it utilizes the reaction of diphenylamine and gaseous phosgene or cyanogen chloride to synthesize intermediate diphenylamine-base carbonyl chloride, and makes the diphenylamine-base carbonyl chloride react with methylamine in acetone or toluene to synthesize AK-II. In the known AK-II synthesis method, the reaction is mostly carried out under the conditions of poor process safety, high energy consumption, long reaction period and high solvent toxicity. For example, Robinson J R, Brown W H and Ontario A C, et al, in Diphenylcyanamidedidervatives, Canadian Journal of Chemistry, 1951, 29: 1069-1074 discloses a synthesis method of AK-II, which comprises three steps of cyanidation, acylation and chlorination of cyanogen chloride (which has high toxicity, difficult preparation, poor stability and high cost) and diphenylamine to obtain intermediate diphenylamine-carbonyl chloride with a yield of 54%; then, dissolving the intermediate in ether, and introducing methylamine gas to obtain AK-II with yield of 78%; the total yield of the method is 42%, but the method has more reaction steps and lower total reaction yield.
Disclosure of Invention
The invention aims to overcome the defects in the background technology and provide a synthesis method of 1-methyl-3, 3-diphenylurea with fewer reaction steps and higher reaction yield.
The invention has the conception that the inventor researches and discovers that the solid phosgene has higher melting point, is not easy to decompose and volatilize at normal temperature, has smaller toxicity and good safety, is prepared into a solution for use, has a homogeneous reaction system, less byproducts and higher reaction yield, has multiple ways for improving the reaction yield, but has relatively fixed raw materials in the AK-II synthesis, and finds an acid-binding system for improving the reaction yield of the AK-II in the most effective way.
In order to solve the technical problem, the synthesis method of AK-II comprises the following steps of adding solvents of dichloromethane, pyridine and diphenylamine into an ① reaction bottle, dripping a solid phosgene-dichloromethane solution under stirring at the temperature of 10-45 ℃, reacting for 2-6 h at the temperature of 10-45 ℃ after dripping the solid phosgene-dichloromethane solution, filtering out solids, evaporating to remove dichloromethane to obtain dianilinoyl carbonyl chloride, wherein the molar ratio of the solvents of dichloromethane, pyridine and solid phosgene is 4-8: 0.37-0.74: 0.12-0.25, adding the dianilinoyl chloride, dichloromethane and triethylamine obtained in the step ① into the reaction bottle, introducing methylamine gas at the temperature of 20-45 ℃, continuing to perform heat preservation reaction for 0.5-4 h after introducing the methylamine gas, filtering, washing filter cakes, and performing ethanol recrystallization, wherein the molar ratio of the solvents of dichloromethane, triethylamine and triethylamine to the methylamine is 4-0.37.74: 0.37-0.74: 0.12-0.25,
the synthesis method of AK-II comprises the following steps of adding 200mL (3.11mol) of solvent dichloromethane, 34.6g (0.5mol) of pyridine and 84.5g (0.5mol) of diphenylamine into an ① reaction bottle, dropwise adding 150mL (2.33mol) of dichloromethane solution containing 49.5g (0.167mol) of solid phosgene at the temperature of 30-32 ℃ under stirring, reacting at the temperature of 30-32 ℃ for 4h, filtering to remove solids, evaporating dichloromethane from filtrate to obtain 110g of diphenylamino carbonyl chloride, adding 115.8g (0.5mol) of diphenylamino carbonyl chloride obtained in the step ① into the reaction bottle, adding 400mL (6.21mol) of dichloromethane and 50.5g (0.5mol) of triethylamine, introducing 17.1g (0.55mol) of methylamine gas at the temperature of 25-27 ℃, continuing the heat preservation reaction for 3h after introducing the methylamine gas, filtering, washing, recrystallizing with ethanol to obtain 1-3 g of filter cake, and obtaining 101-3 g-diphenylamino urea.
The invention has the beneficial effects that:
the synthesis method of the 1-methyl-3, 3-diphenyl urea has high yield, the total yield of the two-step reaction can reach 84.9 percent, and the total yield of the four-step reaction of the synthesis method of the comparison document is 42 percent; the synthesis method of 1-methyl-3, 3-diphenylurea of the present invention has fewer reaction steps, which is a two-step reaction, while the synthesis method of the reference document has four reaction steps.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The product purity testing instrument is GC-2010 high pressure liquid chromatography.
(1) Preparation of diphenylamino-carbonyl chloride
Example 1
84.5g (0.5mol) of diphenylamine, 34.6g (0.5mol) of pyridine and 200mL (3.11mol) of methylene chloride were charged into a reaction flask equipped with a stirrer, a condenser, a dropping funnel and a gas-absorbing device. At the temperature of 30-32 ℃, under stirring, 150mL (2.33mol) of dichloromethane solution containing 49.5g (0.167mol) of solid phosgene is added dropwise, and tail gas generated by the reaction is absorbed by sodium carbonate aqueous solution. After the dichloromethane solution containing the solid phosgene is dripped, the reaction is carried out for 4 hours at the temperature of 30-32 ℃. Filtering to remove solid, evaporating dichloromethane from the filtrate to obtain 110g of diphenylamine-base carbonyl chloride, wherein the yield is 95% (calculated by diphenylamine) and the purity is more than or equal to 98% (HPLC). IR Spectrum (KBr, upsilon, cm)-1)：1722(-C＝O)，
1H NMR(DMSO-d6)δ：：7.37(s，2H)，7.46(s，4H)，7.51(s，4H)ppm
Elemental analysis C13H10NOCl(％)：
Calculated values: c67.39, N6.002, H4.320, Cl 15.33
Measured value: c67.29, N6.048, H4.241, Cl 15.29
Example 2
84.5g (0.5mol) of diphenylamine, 34.6g (0.5mol) of pyridine and 200mL (3.11mol) of methylene chloride were charged into a 1L flask equipped with a stirrer, condenser, dropping funnel and gas-absorbing device. At the temperature of 15-18 ℃, under stirring, 150mL (2.33mol) of dichloromethane solution containing 35.6g (0.12mol) of solid phosgene is dripped, and tail gas generated by the reaction is absorbed by sodium carbonate aqueous solution. After the dichloromethane solution containing the solid phosgene is dripped, the reaction is carried out for 4 hours at the temperature of between 15 and 18 ℃. The solid is removed by filtration, and the dichloromethane is removed by evaporation from the filtrate, thus obtaining 75.4g of diphenylamine-base carbonyl chloride, the yield is 65.2 percent (calculated by diphenylamine), and the purity is more than or equal to 98 percent (HPLC).
Example 3
84.5g (0.5mol) of diphenylamine, 34.6g (0.5mol) of pyridine and 200mL (3.11mol) of methylene chloride were charged into a 1L flask equipped with a stirrer, condenser, dropping funnel and gas-absorbing device. 150mL (2.33mol) of dichloromethane solution containing 59.4g (0.2mol) of solid phosgene is added dropwise at the temperature of 20-22 ℃ under stirring, and tail gas generated by the reaction is absorbed by sodium carbonate aqueous solution. After the dichloromethane solution containing the solid phosgene is dripped, the reaction is carried out for 4 hours at the temperature of 20-22 ℃. The solid is removed by filtration, and methylene dichloride is removed by evaporation from the filtrate, 104g of diphenylamine-base carbonyl chloride is obtained, the yield is 89.9 percent (calculated by diphenylamine), and the purity is more than or equal to 98 percent (HPLC).
Example 4
84.5g (0.5mol) of diphenylamine, 34.6g (0.5mol) of pyridine and 200mL (3.11mol) of methylene chloride were charged into a 1L flask equipped with a stirrer, condenser, dropping funnel and gas-absorbing device. At the temperature of 25-28 ℃, under stirring, 150mL (2.33mol) of dichloromethane solution containing 49.5g (0.167mol) of solid phosgene is added dropwise, and tail gas generated by the reaction is absorbed by sodium carbonate aqueous solution. After the dichloromethane solution containing the solid phosgene is dripped, the reaction is carried out for 4 hours at the temperature of between 25 and 28 ℃. The solid is removed by filtration, and methylene chloride is removed by evaporation from the filtrate, thus 106.5g of diphenylamine-base carbonyl chloride is obtained, the yield is 92 percent (calculated by diphenylamine), and the purity is more than or equal to 98 percent (HPLC).
Example 5
84.5g (0.5mol) of diphenylamine, 34.6g (0.5mol) of pyridine and 200mL (3.11mol) of methylene chloride were charged into a 1L flask equipped with a stirrer, condenser, dropping funnel and gas-absorbing device. At the temperature of 35-38 ℃, under stirring, 150mL (2.33mol) of dichloromethane solution containing 49.5g (0.25mol) of solid phosgene is added dropwise, and tail gas generated by the reaction is absorbed by sodium carbonate aqueous solution. After the dichloromethane solution containing the solid phosgene is dripped, the reaction is carried out for 4 hours at the temperature of between 35 and 38 ℃. The solid is removed by filtration, and dichloromethane is removed by evaporation from the filtrate to obtain 105.2g of diphenylamine-carbonyl chloride, the yield is 90.9 percent (calculated by diphenylamine), and the purity is more than or equal to 98 percent (HPLC).
Example 6
84.5g (0.5mol) of diphenylamine, 34.6g (0.5mol) of pyridine and 200mL (3.11mol) of methylene chloride were charged into a 1L flask equipped with a stirrer, condenser, dropping funnel and gas-absorbing device. At the temperature of 30-32 ℃, under stirring, 150mL (2.33mol) of dichloromethane solution containing 44.6g (0.15mol) of solid phosgene is added dropwise, and tail gas generated by the reaction is absorbed by sodium carbonate aqueous solution. After the dichloromethane solution containing the solid phosgene is dripped, the reaction is carried out for 6 hours at the temperature of 30-32 ℃. The solid is removed by filtration, and methylene dichloride is removed by evaporation from the filtrate, thus obtaining 95.7g of diphenylamine-base carbonyl chloride, the yield is 82.6 percent (calculated by diphenylamine), and the purity is more than or equal to 98 percent (HPLC).
Example 7
84.5g (0.5mol) of diphenylamine, 34.6g (0.5mol) of pyridine and 150mL (2.33mol) of methylene chloride were charged into a 1L flask equipped with a stirrer, condenser, dropping funnel and gas-absorbing device. At the temperature of 30-32 ℃, under stirring, 150mL (2.33mol) of dichloromethane solution containing 49.5g (0.167mol) of solid phosgene is added dropwise, and tail gas generated by the reaction is absorbed by sodium carbonate aqueous solution. After the dichloromethane solution containing the solid phosgene is dripped, the reaction is carried out for 5 hours at the temperature of 30-32 ℃. The solid is removed by filtration, and dichloromethane is removed by evaporation from the filtrate to obtain 107g of diphenylamine-base carbonyl chloride, the yield is 92.4 percent (calculated by diphenylamine), and the purity is more than or equal to 98 percent (HPLC).
Example 8
84.5g (0.5mol) of diphenylamine, 34.6g (0.5mol) of pyridine and 300mL (4.66mol) of methylene chloride were charged into a 1L flask equipped with a stirrer, condenser, dropping funnel and gas-absorbing device. At the temperature of 30-32 ℃, under stirring, 150mL (2.33mol) of dichloromethane solution containing 49.5g (0.167mol) of solid phosgene is added dropwise, and tail gas generated by the reaction is absorbed by sodium carbonate aqueous solution. After the dichloromethane solution containing the solid phosgene is dripped, the reaction is carried out for 3 hours at the temperature of 30-32 ℃. The solid is removed by filtration, and dichloromethane is removed by evaporation from the filtrate to obtain 108g of diphenylamine-base carbonyl chloride, the yield is 93.3 percent (calculated by diphenylamine), and the purity is more than or equal to 98 percent (HPLC).
Example 9
84.5g (0.5mol) of diphenylamine, 34.6g (0.5mol) of pyridine and 200mL (3.11mol) of methylene chloride were charged into a 1L flask equipped with a stirrer, condenser, dropping funnel and gas-absorbing device. At the temperature of 30-32 ℃, under stirring, 150mL (2.33mol) of dichloromethane solution containing 49.5g (0.167mol) of solid phosgene is added dropwise, and tail gas generated by the reaction is absorbed by sodium carbonate aqueous solution. After the dichloromethane solution containing the solid phosgene is dripped, the reaction is carried out for 2 hours at the temperature of 30-32 ℃. The solid is removed by filtration, and dichloromethane is removed by evaporation from the filtrate to obtain 105.8g of diphenylamine-carbonyl chloride, the yield is 91.4 percent (calculated by diphenylamine), and the purity is more than or equal to 98 percent (HPLC).
(2) Synthesis of AK-II
Example 10
115.8g (0.5mol) of diphenylaminocarbonyl chloride, 50.5g (0.5mol) of triethylamine and 400mL (6.21mol) of dichloromethane were charged into a reaction flask with stirring, gas port and gas take-up. At the temperature of 25-27 ℃, 17.1g (0.55mol) of methylamine gas is introduced, and after the methylamine gas is introduced, the heat preservation reaction is continued for 3 hours. Through the steps of filtering, washing filter cakes and ethanol recrystallization, 101g of 1-methyl-3, 3-diphenyl urea is obtained. The yield is 89.4 percent (calculated by diphenylamine-base carbonyl chloride) and the purity is more than or equal to 99 percent (HPLC).
IR Spectrum (KBr, upsilon, cm)-1)：3340(-NH)，2939(-CH3)，1655(-C＝O)
1H NMR(DMSO-d6)δ：2.58(s，3H)，5.9(s，1H)，7.19(d，6H)，7.34(d，4H)ppm
13C NMR(DMSO-d6)δ：27.35(-CH3)，125.48(p-Ph)，127.30(m-Ph)，129.10(o-Ph)143.35(-N-Ph)，156.39(-C＝O)
Elemental analysis C14H14N2O(％)：
Calculated values: c74.34, N12.39, H6.195
Measured value: c74.28, N12.32, H6.109.
Example 11
115.8g (0.5mol) of diphenylaminocarbonyl chloride, 50.5g (0.5mol) of triethylamine and 500mL (7.76mol) of methylene chloride were charged into a 1L flask with stirring, gas port and gas absorption. At the temperature of 20-22 ℃, 17.1g (0.55mol) of methylamine gas is introduced, and after the methylamine gas is introduced, the heat preservation is continued for 3 hours. Filtering, washing filter cake, and recrystallizing with ethanol to obtain 99g of 1-methyl-3, 3-diphenyl urea. The yield is 87.6 percent (calculated by diphenylamine-base carbonyl chloride) and the purity is more than or equal to 99 percent (HPLC).
Example 12
115.8g (0.5mol) of diphenylaminocarbonyl chloride, 40.4g (0.4mol) of triethylamine and 400mL (6.21mol) of dichloromethane were charged into a 1L flask with stirring, gas port and gas take-up. 15.5g (0.5.mol) of methylamine gas is introduced at the temperature of 15-17 ℃, and after the methylamine gas is introduced, the heat preservation reaction is continued for 3 hours. After filtering, washing filter cake and ethanol recrystallization, 97.3g of 1-methyl-3, 3-diphenyl urea is obtained. The yield is 86.1 percent (calculated by diphenylamine-base carbonyl chloride) and the purity is more than or equal to 99 percent (HPLC).
Example 13
115.8g (0.5mol) of diphenylaminocarbonyl chloride, 50.5g (0.5mol) of triethylamine and 300mL (4.66mol) of methylene chloride were charged into a 1L flask with stirring, gas port and gas absorption. At the temperature of 15-17 ℃, 17.1g (0.55mol) of methylamine gas is introduced, and after the methylamine gas is introduced, the heat preservation reaction is continued for 3 hours. Filtering, washing filter cake, and recrystallizing with ethanol to obtain 98.2g of 1-methyl-3, 3-diphenyl urea. The yield is 86.9 percent (calculated by diphenylamine-carbonyl chloride) and the purity is more than or equal to 99 percent (HPLC).
Example 14
115.8g (0.5mol) of diphenylaminocarbonyl chloride, 60.6g (0.6mol) of triethylamine and 400mL (6.21mol) of dichloromethane were charged into a 1L flask with stirring, gas port and gas take-up. At the temperature of 30-33 ℃, 17.1g (0.55mol) of methylamine gas is introduced, and after the methylamine gas is introduced, the heat preservation reaction is continued for 3 hours. Filtering, washing filter cake, and recrystallizing with ethanol to obtain 100.1g of 1-methyl-3, 3-diphenyl urea. The yield is 88.6 percent (calculated by diphenylamine-base carbonyl chloride) and the purity is more than or equal to 99 percent (HPLC).
Example 15
115.8g (0.5mol) of diphenylaminocarbonyl chloride, 50.5g (0.5mol) of triethylamine and 400mL (6.21mol) of dichloromethane were charged into a 1L flask with stirring, gas port and gas take-up. 15.5g (0.5mol) of methylamine gas is introduced at the temperature of 25-27 ℃, and heat preservation is continued for 4 hours after the methylamine gas is introduced. Filtering, washing filter cake, and recrystallizing with ethanol to obtain 100.6g of 1-methyl-3, 3-diphenyl urea. The yield is 89.1 percent (calculated by diphenylamine-base carbonyl chloride) and the purity is more than or equal to 99 percent (HPLC).
Example 16
115.8g (0.5mol) of diphenylaminocarbonyl chloride, 50.5g (0.5mol) of triethylamine and 400mL (6.21mol) of dichloromethane were charged into a 1L flask with stirring, gas port and gas take-up. At the temperature of 25-27 ℃, 17.1g (0.55mol) of methylamine gas is introduced, and after the methylamine gas is introduced, the heat preservation reaction is continued for 2 hours. After filtration, washing of filter cake and recrystallization with ethanol, 99.5g of 1-methyl-3, 3-diphenyl urea is obtained. The yield is 88.1 percent (calculated by diphenylamine-base carbonyl chloride) and the purity is more than or equal to 99 percent (HPLC).
Example 17
115.8g (0.5mol) of diphenylaminocarbonyl chloride, 50.5g (0.5mol) of triethylamine and 400mL (6.21mol) of dichloromethane were charged into a 1L flask with stirring, gas port and gas take-up. Introducing 21.7g (0.7mol) of methylamine gas at the temperature of 25-27 ℃, and continuing the heat preservation reaction for 1h after the methylamine gas is introduced. Filtering, washing filter cake, and recrystallizing with ethanol to obtain 80g of 1-methyl-3, 3-diphenyl urea. The yield is 70.8 percent (calculated by diphenylamine-base carbonyl chloride) and the purity is more than or equal to 99 percent (HPLC).
Claims (2)
1. A synthesis method of 1-methyl-3, 3-diphenylurea comprises the following steps of adding solvents of dichloromethane, pyridine and diphenylamine into an ① reaction bottle, dropwise adding a solid phosgene-dichloromethane solution at the temperature of 10-45 ℃ under stirring, reacting for 2-6 h at the temperature of 10-45 ℃ after dropwise adding the solid phosgene-dichloromethane solution, filtering out solids, and evaporating dichloromethane to obtain diphenylenecarbonyl chloride, wherein the molar ratio of the solvents of dichloromethane, diphenylamine, pyridine and solid phosgene is 4-8: 0.37-0.74: 0.12-0.25, adding the diphenylenecarbonyl chloride, dichloromethane and triethylamine obtained in the step ① into the reaction bottle at the temperature of 20-45 ℃, introducing methylamine gas, continuing to perform heat preservation reaction for 0.5-4 h, filtering, washing filter cakes, and performing ethanol recrystallization to obtain the 1-methyl-3, 3-diphenyleneurea, wherein the molar ratio of the solvents of dichloromethane to triethylamine to dichloromethane is 0.37-0.74: 0.12-0.25.
2. The method for synthesizing 1-methyl-3, 3-diphenylurea according to claim 1 comprises the following steps of adding 3.11mol of dichloromethane, 0.5mol of pyridine and 0.5mol of diphenylamine as solvents into an ① reaction bottle, dropwise adding 2.33mol of dichloromethane solution containing 0.167mol of solid phosgene at the temperature of 30-32 ℃ under stirring, reacting for 4 hours at the temperature of 30-32 ℃ after dropwise adding, filtering to remove solids, evaporating dichloromethane from filtrate to obtain 110g of diphenylenecarbonyl chloride, adding ② mol of diphenylenecarbonyl chloride obtained in the step ① into the reaction bottle, adding 6.21mol of dichloromethane and 0.5mol of triethylamine, introducing 0.55mol of methylamine gas at the temperature of 25-27 ℃, continuing to perform heat preservation reaction for 3 hours after the methylamine gas is introduced, filtering, washing filter cakes, and performing ethanol recrystallization to obtain 101g of 1-methyl-3, 3-diphenylurea.
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