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    • 专利摘要:
    There is described a process for the preparation of amines of the type RNH2, wherein R represents a hydrocarbon radical containing up to 18 carbon atoms, in particular an aliphatic, arylaliphatic, cycloaliphatic or aromatic radical, the said process being characterized by the fact that an amide having the formula RCONH2, wherein R has the aforesaid meaning, is reacted, at a pH less than or equal to 7, firstly with gaseous chlorine, in the absence or in the presence of a diluent, and the N-chloroamide thus formed is subsequently reacted with an alkali hydroxide and/or an earth alkali hydroxide.
    公开号:SU902661A3
    申请号:SU782627808
    申请日:1978-06-14
    公开日:1982-01-30
    发明作者:Бертини Франко；Альберто Паури Карло
    申请人:Сниа Вискоза Сочиета Национале Индустриа Аппликационе Вискоза С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    in a solution of 127 g of hexahydrobenzamide (1 mol) in 600 ml. . The initial pH is 6.5. 78 g of chlorine 1, 099 mol, with controlled weighing, is absorbed in 78 minutes. The chlorinated product thus obtained is poured into 500 g of fine ice, the chloroform solution is separated and washed with water until it is neutral. The remaining 161 g of N-chlorohex in hydrobenzamide (quantitative yield), the active chlorine content of which is 22% (theoretically 21.93%) is obtained by evaporation of the solvent. 64.64 g (0.4 mol) of N-chlorohexahydrobenzamide (100% purity), prepared as described above, are added over 1 hour to a solution of 32.32 g (0.8 mol) of sodium hydroxide (purity 99%) dissolved 400 ml of water and maintained at 20-22 ° C. The resulting mixture is kept stirring for 1 hour at 20, then heated for 1 hour at. and the azeotropic cyclohexylamine / water death thus obtained is distilled (distillation temperature 9b s), the content of cyclohexylamine in the azeotropic mixture kk ,. Thus, 188 g of cyclohexylamine is obtained, which corresponds to a theoretical yield. Example 2 Chlorine gas was introduced at a rate of 66 g / h into a suspension of 25b g (2 mol) of hexahydrobenzamide in 1700 ml of water at 20 ° C while stirring. The initial pH is 6.5. After 2 hours and 28 minutes, 1b 3 g of chlorine is absorbed, which corresponds to 2.3 mol. After separation of the N-chloro hexahydrobenzamide from the suspension by filtration, it is washed with water. Thus, a sludge g of N chlorohexahydrobenzamide is obtained (yield 95.75% with a chlorine content of 21.11 (theoretical value 21.93%). 67.18 g (0.4 mol) N-chlorohexahyrobenzamide prepared as described above are added over a period of 1 hour to a suspension of 6.79 g (0.6 mol) purity of 95% calcium hydroxide in 2500 ml of water, which is maintained at 20-25 C. The mixture is stirred at 20-25 0 until the active chlorine disappears, it is heated for another 30 min. 9 C 1 80 C, then cyclohexylamine is distilled in an azeotropic mixture with water at 96-99 C, resulting in 68 g of a solution, containing 7.79 cyclohexylamine, which corresponds to a yield of 92 from theory. Example 3. 33 g (0.2 mol) of N-chlorohexahydrobenzamide (purity 98) are added slowly with stirring, to the suspension 8.1 g (0.2 mol) of NaOH (purity 98.5) and 15.6 g (0.2 mol) of calcium hydroxide (purity 95%) in 2300 ml of water at. The mixture is then stirred for several hours at 20 ° C until all the active chlorine in solution will not disappear, then heated for 30 minutes at Bo C and cyclohexylamine is distilled in an azeotropic mixture with water, resulting in a solution of 186 g containing 10 qi clohexylamine, which corresponds to the output of 93.6 from theory. PRI mme r it. +3.24 g (0.2 mol) of N-chlorohexahydrobenzamide (purity 97.17) is added over 30 minutes at 20 ° C to a mixture of 8.1 g (0.2 mol) of NaOH (purity 98.5%) and b5 g (0.2 mol) Ba (OH) 2 8HrO (purity 97%) dissolved in 1200 ml of Hoe. After stirring for 30 minutes at 20 ° C, the mass is heated at 80 ° C for 30 minutes and the azeotropic water / cyclohexylamine mixture is distilled and a total of 50 g of alkaline water is collected. The content of cyclohexylamine in water is determined to be 4.3%, which corresponds to a yield of 97.7%. Example 5. 33.2 g of N-chlorohexahydrobenzamide (purity 97.17%) are added with stirring over 30 minutes at 20 ° C to a mixture of 8.1 g (0.2 mol) of NaOH and a solution of 97 g (0.3 mol) Ba (OH) 2 ZNaO (purity 97.5%) in 850 ml of water. The reaction mass is slowly heated at 60 ° C and maintained at the indicated temperature for 30 minutes, then the temperature is raised to 80 ° C for 30 minutes and the azeotropic water / cyclohexylamine mixture is distilled. 26 g of a solution is collected which contains 4.6% of cyclohexylamine, which corresponds to a yield of 98.6%. Example 6. A stream of chlorine gas is introduced at a rate of approximately 33 g / h into a suspension of 111 g of 0.91 mol of benzamide (purity 99.5%) in 700 ml of 590 water at 15-20 ° C. After 2 hours and 15 minutes, 75 g of chlorine (1.05 mol) is consumed with controlled weighing. The mass is stirred for another 15 minutes at 20 ° C, then the resulting chlorinated product is filtered and washed. water until hydrochloric acid disappears. Get g Nchlorobenzamide (yield 98.9), containing 21, active chlorine, which corresponds to the title 9b. +8.6 g (0.3 mol) of N-chlorobenzamide (purity 9b) is added at 1b-20 ° C with good stirring for 15-20 MH to solution, 2 g (0.6 mol) of NaOH ( purity-99) in 95 ml of water. After several hours, when there is no active chlorine in the solution, the mixture is quickly heated to 80 ° C. This temperature is maintained for 30 minutes, after which the mixture is cooled and the reaction is reacted several times with chloroform. Receive 256 ml of chloroform extract having a titration of gas chromatography of 10.7% in aniline, which corresponds to a yield of 95.96% of theory. Example 7. 32.4 g (0.2 mol) of N-chlorobenzamide (purity 9b%) was added at 15–20 ° C with good stirring for minutes. in an aqueous suspension consisting of 15.6 g (0.2 mol) Ca (OH) 2 (purity 95%) and 8.1 g (0.2 mol) NaOH (purity 98.5%) in 2000 ml of water . The temperature is maintained for 2 hours, after which the mass is heated for 1 hour at, then the temperature is quickly adjusted and maintained at this level for about 30 minutes. When the reaction is complete, aniline is distilled in a stream of water vapor. 557 g of alkaline water are distilled and due to this, the separated aniline oil is separated. For analysis, the mass is adjusted to a volume of 1000 ml with ethyl alcohol and the aniline aqueous-alcoholic solution is chromatographed. The titer contains 1.73% aniline, which corresponds to a yield of 93%. Example 8. A suspension of 26.52 g (0.5 mol) of calcium oxide (purity 95%) in 1000 ml of water is stirred until all the oxide is converted to hydroxide. The suspension is cooled to and kE, S g (0.3 mol) of N-chlorobenzamide (purity 9.2%) is gradually added with stirring. Maintain a temperature of 20–25 ° C with stirring until active chlorine disappears from solution. The reaction is terminated by rapid heating to within 30 minutes and the resulting aniline is distilled in a stream of water vapor until neutral water is obtained. Thus, it receives 900 ml of aniline solution, in which the chromatography titer is 2.85%, which corresponds to a yield of 91.9. Example 9. Chlorine gas was introduced at a rate of 95 g / h into a suspension of 19 g (1.21 mol) of pelargonamide (purity 98.15) in TtOO ml of water. The introduction of chlorine is stopped after 60 minutes and the suspension is still left under stirring for 20-30 minutes at 20 ° C. The solid is filtered off, washed with water until all HC1 disappears (ZOO cm of water), and the chlorinated derivative is dried. Thus, 226 g of N-chlorpellargonamide is obtained (yield 97%), which has an active chlorine titer of 17.6% (theoretically 18.5%). 40.3 g (0.2 mol) of N-chlorpellargonamide (purity 95.15%) are gradually added over 30 minutes with stirring and at 10-T5C to a solution of 16.3 g 0, mol NaOH in ml1 H 0. After After the reaction mass is maintained for 2 hours at 20 ° C., the reaction is completed at 8 ° C for 30 minutes. The resulting amine is extracted from water, in which it is poorly soluble, with ethyl ether. The extract in the amount of 133 g contains 18.2% octylamine, which corresponds to a yield of 93.7%. Example 10. 220 g (2.5 mol) of butyramide (purity 99%) is dissolved in 1000 ml of water (16% solution at 15 ° C), a stream of gaseous chlorine is introduced into the solution at a rate of 62 g / h at 15 -20 ° C. The pH of the solution, which is 6.5 before the introduction of chlorine (depending on the water used), gradually decreases as the reaction proceeds. After 1 h when entered. about 1/3 of the total amount of chlorine, the pH is 1.5, decreasing to 0, nq after 3 hours and 10 minutes, when chlorination is complete. The mixture is stirred for an additional 30 min. P (and then, with methylene chloride, the N-chloro79 tiramide is extracted from water. After evaporation of the solvent, 308 g of a pale yellow oil, N-chlorobutyramide, containing 28.15 active chlorine ( theoretically 29.16), which corresponds to exit 97) 8. To a solution of 32.6 g (0.8 mol) of NaOH in 130 ml of water is gradually added with stirring at 15 ° C for 35 minutes, 50.39 g (0.1 mol) of N-chloro-butyramide (purity 96.5 ). The mixture is stirred for another 8 hours at 20-22 ° C, then heated at 75-80 ° C for 25-30 minutes. The resulting amine is extracted from water or ethyl ether (chloroform, or by distillation. Thus, 375 g of a 5.9% aqueous solution of n-propylamine is obtained (the titer is determined by gas chromatography), which corresponds to yield 93. Example 11. Chlorine gas are introduced at a rate of 45 g / h into a suspension of 175 g (1.51 mol of caproamide (H-hexanamide) in 1200 ml of water with stirring and at C. The pH of the suspension was up to 6.9 before the chlorine was added, during the chlorination (first quickly, then more slowly) to a final value of 0.3. The pH is 1.1. After 2 hours and 37 minutes, 118 g (1.66 mol) of chlorine is absorbed. After separating the solid from the acidic water by filtering, the K-chloro-I-caproamide is washed with ice-water. the content of active chlorine is 23.211 (theoretical 23, b9), which corresponds to the output 5.8 g (0.3 mol) is gradually added to a solution of 24.5 g (0.6 mol) NaCH (purity 98) in 150 ml of water N-chloro-caproMida (purity 98. o) with stirring for 25 minutes with After keeping the mixture with stirring for 2 hours at 18-20 0 r. The action is completed by heating at 75 for 30 minutes, during which complete removal of chlorine from the solution is achieved. . The amine thus obtained is extracted from water with ethyl ether to obtain g of a solution containing 7.19% of H-pentylamine (or namylamine), which corresponds to yield 9 ,. Example 1 2.Gas-like chlorine is introduced at a rate of 30 g / h into a suspension of 75 g (0.51 mol) of adipic acid diamide (purity 981) in 650 ml of water with stirring at 18-20 ° C. The pH before the introduction of chlorine is 6.5, after 50 minutes, when about 1/3 of the total chlorine reacted - 1.5, at the end of the reaction after 2 hours and 25 minutes - 0, C At the end of the reaction, 175 f is absorbed (1 mol) chlorine. The suspension is kept under stirring for another 1 h, and then filtered. The solid product N, N-dichloro-diamide adipic acid is washed with water. Thus, 106.5 g of N, N-dichloroepipamide with active chlorine content of 31.6 (theoretically 33.28) are obtained. 22.44 g (0.1 mol) of dichloradipamide; (purity 94.95%) are suspended in 100 ml of water at 15–20 ° C and 1b, 32 g (0.4 mol) of NaOH (98% purity) diluted in a g of water is added with (N9 dropping funnel) 4 hours. The mixture is stirred for another 4 hours at 20 ° C, and then slowly heated to 5060 ° C for 3 hours. After that, the mixture is cooled to, acidified with HCE at 20 ° C, adjusted to pH 10 with NaOH, then several extracts are extracted with ethyl ether and 725 g of a solution containing 1.11% tetramethylenediamine are obtained (yield 91.3%). Example 13 - Chlorine gas is introduced at a rate of 45 g / h into suspension 150 g (1.1 mol) phenylacetamide a (purity 99%) in 850 ml of water with stirring. The initial pH is 6.8 and decreases after 45 minutes to 1.7, and after 1 hour 53 minutes - the time required for the reaction to 0 25. I After 1 h 53 min, 85 g of chlorine (1.2 mol) is absorbed. The mixture is stirred for 1 h at 20 ° C, then the solid is separated from the acidic solution by filtration and washed with water until neutral .
    9, 90
    I8l, 3, r N-chlorophenylacetamide (yield -93.9%), theoretically 20.9% of active chlorine contains 20.9%
    87.7 g (0.5 mol) of N-chlorophenylacetamide (purity) are added in portions over 30 minutes to a mechanically stirred solution obtained by dissolving in water with a temperature of 18–20 ° C, i) 0.8 g (1 mol ) NaOH (purity 9B).
    After adding the reagent, the mixture is stirred for another 1 h 30 min at 20 ° C, then heated for 30 min to and kept at this temperature for another 30 min with stirring.
    The solution is cooled and extracted in several stages with (cyclohexane) hlrform, resulting in 950 g of a solution containing 5.5 benzylamine, which corresponds to a yield of 91.3.
    权利要求:
    Claims (1)
    [1]
    1. Carrer P. The course of organic chemistry. L., Goskhimizdat, I960, p. 1b2 (prototype).
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