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    • 专利摘要:
    THE METHOD OF OBTAINING O-TRIFTOROMETHANILINE using trifluoromethylbenzene, nitration with a mixture of nitric and sulfuric acids and reduction, is characterized in that, in order to simplify the process, trifluoromethylbenzene is chlorinated with chlorine gas in the presence of a chlorine catalyst, namely, SbCf, with a hydrochloric acid or chloro-chlorine, and chloro-chlorine in the presence of a purity catalyst, such as SbCf, and a hydrogen or chlorofluoromethyl benzene is chlorinated by chlorine in the presence of a chlorine catalyst; Sb, or S1 in the amount of 7 x 0.1 to 10–10 wt.% With respect to taken trifluoromethylbenzene at 0–100 ° C before the conversion of trifluoromethylbenzene to 95–99 wt.% With prom, followed by nitration of the resulting crude reaction product at a mass ratio For each acid to chlorotrifluoromethylbenzenes contained in the reaction medium, 0.5-5, until chlorotrifluoromethylbenzenes completely disappear when hydrogenating the organic phase obtained after decanting and washing in the presence of a hydrogenation catalyst — Rene nickel and / or Rene nickel with the addition of 0.75 3.5% by weight of chromium in the amount of 3-10% by weight relative to chloronitrotrifluoromethylbenzenes in methanol medium at a pressure of 10-50 bar and i 20-100 ° C and secondary hydrogenation of the reaction products in the presence of an additional amount of catalysis of a hydrogenation torus equal to 8–20 wt.% with respect to the initial content of chlorine trotrifluoromethyl behes at a pressure of 10–50 bar and SO-lOffC in the presence of alkali, followed by distillation of the desired product from the reaction mixture with 00.
    公开号:SU1138019A3
    申请号:SU813362295
    申请日:1981-12-11
    公开日:1985-01-30
    发明作者:Дисдье Камилл；Мартино Жак-Пьер；Салливан Джон
    申请人:Рон-Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved method for obtaining ortho-trifluoromethylanine, which is used as an intermediate in the synthesis of dyes and compounds with phytosanitary activity. A known method of obtaining the desired product by nitrating trifluoromethylbenzene in order to obtain m-nitrotrifluoromethylbenzene, which is then converted by m-trifluoromethylpylin. Acetylation of this compound with acetic acid gives m-acetylaminotrifluoromethylbenzene, the nitration of which allows to obtain 2-nitro-5-acetylaminotrifluoromethylbenzene. From the latter, by hydrolysis, 2-nitro-5-amy1trifluoromethylbenzene is obtained. The amino group is removed by reductive diazotization, which allows to obtain o-nitrotrifluoromethylbenzene, the reduction of which leads to the formation of o-trifluoromethylaniline 1. The disadvantage of this method is the long duration of the process. So to obtain the desired product from trifluoromethylbenzene, seven steps are required. It is difficult to carry out the diazotization reaction; in addition, after the majority of stages, purification of the products obtained is necessary. At the same time, the target product is low yield. There is also known a method for preparing the target product, which consists in treating o-trifluoromethylbenzamide with sodium hypobromite by the Hoffmann decomposition reaction. 2. The disadvantage of this type of reaction lies in the possibility of the formation during the reaction of decomposition of N-bromo-amines, which are unstable compounds. In addition, the original substance used according to this method is not widely available on an industrial scale. The closest to yes to this is the method of obtaining o-trifluoromethylaniline, which consists in nitrating trifluoromethyl benzene, reducing the last m-trifluoromethyl nitrobenzene, acetylizing the resulting product with acetic acid, nitrating m-acetylaminotrifluoromethyl benzene with a mixture of sulfuric nitric acid, hydrolysis of the resulting product by a product of the resulting product and a product of the product of the resulting product. aminotrifluoromethylbenzene and reduction of the o-nitrotrifluoromethylbenzoyl obtained. 1. However, this method is very long (7 stages), t udoemkim (diazotization step) after each stage of purification of the products obtained is required. The purpose of the method is to simplify the process. The HANDLING goal is achieved in that according to the method of obtaining o-trifluoromethylaniline using trifluoromethylbenzene, nitration with a mixture of nitric and sulfuric acids and reduction, trifluoromethylbenzene is chlorinated with gaseous chlorine in the presence of a chlorination catalyst, namely SbCt or FeCf + Fe, or Sb, or SbCF or FeCf + Fe, or Sb, or SbCt or FeCf + Fe, or Sb, or SbCt or Fecf +. , 1 - 10 wt.% With respect to taken trifluoromethylbenzene at 0-100 G before the conversion of trifluoromethylbenzene to 95-99 wt.%, Followed by nitration of the obtained crude reaction product at a mass ratio of each This acid to chlorotrifluoromethylbenzenes contained in the reaction medium is 0.5-5 until chlorotrifluoromethylbenzenes completely disappear by O-80 ° C by hydrogenation. Obtained after decanting and washing the organic phase in the presence of a hydrogenation catalyst — Rene nickel and / or Rene nickel with the addition of 0.75–3.5 wt.% Chromium in an amount of 3-10 wt.% With respect to chloronitrotrifluoromethylbenzenes in methanol at 10 -50 bar and 20100 ° C and the secondary hydrogenation of the reaction products in the presence of an additional amount of hydrogenation catalyst equal to 8-20 wt.% With respect to the initial content of chlorine ornaterotrifluoromethylbenzenes at a pressure of 10-50 bar and 20-100 ° C in the presence of whole, followed by distillate c and the desired product from the reaction mixture. Example 1. To a reactor equipped with a stirrer, an injector for gas injection and a hydrochloric acid absorber, 29.2 kg of trifluoromethylbenzene and 292 g of antimony pentachloride are charged. Then inject chlorine gas at 20 ° C for 8 hours. After washing with water, 35.340 kg of the mixture is obtained, the analysis of which by vapor chromatography shows the following composition,%: three: fluoromethylbenzene 4, m-chlorotrifluoromethylbenzene 70.6, p-chlorotrifluoromethylbenzene 5, 8, O-chlorortrfluoromethylbenzo a 3, dichlorotrifluoromethylbenzenes (3 isomers) 16.6. The conversion level of trifluoromethylbenzene is 95%; overall yield of 96%. 15.940 kg of concentrated (97%) sulfuric acid and 15.940 kg of fuming nitric acid are loaded into the reactor with a working mixer. The mixture is cooled to 10 ° C and introduced under stirring at the same temperature for 1 hour, 18.05 kg of the previously obtained crude mixture of trifluoromethylbenzene, chlorotrifluoromethylbenzenes and dichlorotrifluoromethylbenzenes. At the beginning of the inlet, the mixture is heated to 50 ° C and kept at this temperature for 6 hours. The organic phase is decanted, washed with water, 10% sodium hydroxide, again with water. Thus, 21.62 kg of a mixture is obtained, the analysis of which by the method of chromatography in the vapor phase shows the following composition,%: chlorotrifluor methylbenzenes cannot be quantitatively determined by nitrotrifluoromethylbenzene 3.9, chloronitrotrifluoromethylbenzenes 82.2 (4 isomers), dichloronitrotrifluoromethylbenzenes 13.9 (4 isomers )., The degree of conversion of chlorotrifluoromethylbenzenes is 100%, the total yield is 96%. In the autoclave with a working mixer load 1,400 l of methanol and 50 g of Rene nickel. Heat to 20 ° C under a hydrogen pressure of 20 bar and move for 15 minutes. Then, 1.46 L of metaiol and 1 kg of the previously obtained organic phase are introduced. The hydrogenation is carried out at 80 ° C and a pressure of 20 bar. After 1.5 hours, it was noted using chromatography in the vapor phase that the entire amount of chloronitrotrifluoromethylbenzenes was consumed. Cooled to 50 ° C and 622 g of 30.8% HaiTpOBoro lye were introduced. Mix over 15 minutes at a hydrogen pressure of 20 bar. Then 50 g of Rene nickel are introduced and hydrated at a pressure of 20 bar and for 2 hours, after which 50 g of Reie nickel are introduced. Continue the hydrogenation for another 2 hours. Then the reaction is complete. After filtration, concentration and washing with water, 684 g of a mixture of amines of the following composition are obtained,%: O-trifluoromethylaniline 77.2, M-trifluoromethylaniline 20.5, G | - trifluoromethylaniline 2,3. This mixture is distilled on a column with 20 plates with a reflux condenser with 29 plates at a pressure of 50 mm Hg. Art. 522 g of 0-trift-6-methylaniline with a content of more than 99% is obtained as the head fraction, which corresponds to a yield of 99%. Example 2. In the reactor described in example 1, load 7.300 kg of trifluoromethylbenzene, 41 g of ferric chloride (111) and 20 g of iron. Chlorine is then injected for 6 hours. After washing with water, 9160 g of the mixture is obtained, the analysis of which by the method of chromatography in the parsvoy phase shows the following composition,%: trifluoromethylbenzene, 1.7, L-chlorotrifluoromethylbenzene, 66.4, p-chlorotrifto methylbenzene, 6.1 , O-chlorotrifluoromethylbenzene 2.6, dichlorotrifluoromethylbenzene 24.3. The conversion degree of trifluoromethylbenzene is 98%, the total yield is 98%. With stirring, 2.753 g of the previously obtained crude mixture is introduced with stirring. The mixture is cooled to GC and introduced for 1 hour with stirring at this temperature: fuming nitric acid (1700 g) and concentrated (97%) sulfuric acid (2350 g) ... Then the mixture is heated to 80 ° C and maintained within 6 hours. The organic phase is decanted, washed with water, 10% caustic soda, again with water. Thus, 3290 g of a mixture is obtained, the analysis of which shows the following composition,%: chlorotrifluor methylbenzene cannot be quantitatively determined, nitrotrifluoromethylbenzene 1.8, chloronitrotrifluoromethylbenzenes 74.8, dichloronitrotrifluoromethylbenzenes 23.4. The degree of conversion of chlorotrifluoromethylbenzenes is 100%, the total yield is 96%. With stirring, 2900 ml of methanol and 50 g of Repee nickel are introduced into the autoclave; with the addition of 0.75% chromium. Maintained at a hydrogen pressure of 12 bar and 50 ° C with stirring for 15 minutes. Then, under these conditions, for 1 hour and 45 minutes, 1000 g of the previously obtained nitration product is introduced. Then it is kept for another I h 30 min at 50 C and a hydrogen pressure of 12 bar with stirring. By this time, state the complete consumption of hpornitrotrifluoromethylbenzenes. 630 g of 31.1% sodium hydroxide is added and stirred for 15 minutes at 50 ° C and 12 bar of hydrogen pressure. Another 50 g of Rene nickel was added and the hydrogenation was continued for 3 hours under the indicated conditions. Then the reaction is complete. After filtering, concentrating and washing with water, 670 g of a mixture containing,%: O-trifluoromethylaniline 76.7, M-trifluoromethylaniline 21.2, and I-trifluoromethylaniline 2.1, are obtained. This mixture is distilled as described in Example 1. 498 g of O-trifluoromethylaniline are obtained with a content of more than 99%, which corresponds to a distillation yield of O-trifluoromethylaniline 97%. Example Z. In the reactor described in Example I, 7.300 kg of trifluoromethyl beisol, 62.4 g of antimony were introduced. Chlorine is then introduced at. 20 C for 3 h 30 min. After (washing with water, 9.170 g of a mixture which aializ chromatography in the vapor phase showed the following composition,%: -fiftormetilbenzol 0.7 A 65.6 -hlortriftormetsh1benzol T1-hlortriftormetilbeizol 5.2, about 1.5-hlortriftormetilbenzol, dihlbrtrifgormetilbeizoly 27.1. The conversion rate of trifluoromethylbenzene is 99.1%, the yield is 97%. 2.753 g of the previously obtained crude mixture is introduced into the reactor while mixing and cooled to and added with stirring at this temperature for 1 hour mixture: fuming nitric acid (1,700 g) and concentrated (97% ) sulfuric acid (2350 g). The mixture is then heated to 80 ° C for 6 hours. The organic phase is decanted, washed with water, 10% caustic soda and again with water. Thus, 3,200 g of mixture is obtained, the analysis of which shows the following composition ,%: (chlorotrifluoromethylbenzene cannot be quantified), nitrotrifluoromethylbenzene 0.7, chloronitrotrifluoromethylbenzenes 72.9, dichloronitrotrifluoromethylbenzenes 26.4. The degree of conversion of chlorotrifluoromethylbenzo. 100% fishing, total yield 94%. 2900 ml of methanol and 50 g of Rene Nickel with the addition of 3.5% chromium are loaded into the autoclave with stirring. Heat to 50 ° C under a hydrogen pressure of 12 bar and stirring for 15 minutes. Then, under these conditions, 1000 g of the previously obtained nitration product is introduced for 1 h 45 min. Even more live for 1 h 30 min under a hydrogen pressure of 12 bar with stirring. After that, it is noted that the entire amount of chloronitrotrifluoromethylbenzenes has been consumed. Then, 630 g of 31.1% sodium hydroxide is introduced and transferred at 50 ° C and 12 bar of hydrogen for 15 minutes. Then 50 g of Rene nickel are added and hydrogenated for 2 hours at 50 ° C and 12 bar of hydrogen pressure. Another 50 g of Rene nickel is added and the hydrogenation is continued for 3 hours under the conditions described above. The reaction is then completed. After filtration, concentration and washing with water, 660 g of a mixture of the following composition are obtained,%: o-trifluoromethylaniline 78.2; M-trifluoromethylaniline 19.7, L-trifluoromethylaniline 2.1. This mixture is distilled as in Example 1. 505 g of o-trifluoromethylaniline are obtained with a content of more than 99%, which corresponds to the distillation yield of o-trifluoromethylaniline & ... Example 4. A reactor equipped with a stirrer, a gas nozzle, a cooler and 29.2 g of trifluoromethylbenzene and 29.2 g of iron trichloride are placed in the hydrochloric acid scavenger. Chlorine gas is then introduced at 3 hours. After washing, 35.84 kg of the mixture is obtained, the chromatographic analysis of which in the vapor phase shows the following content,%: trifluoromethylbenzene 0.9, chlorotrifluoromethylbenzenes 71, dichlorotrifluoromethylbenzenes 28.1. The conversion of trifluoromethylbenzene is 98.9%, and the total yield is 95%. With stirring, 94.3 kg of concentrated sulfuric acid (97%) and 9.43 kg of fuming nitric acid are placed in the reactor. This mixture is cooled to 10 ° C and 18.86 kg of previously obtained crude mixture of trifluoromethylbenzene, chlorotrifluoromethylbenzenes and dichlorotrifluoromethylbenzenes are introduced with stirring at this temperature for 1 hour with stirring. After loading is complete, the mixture is heated to 80 ° C and maintained at this temperature for 6 hours. The organic phase is decanted, washed with water, 10% sodium hydroxide and then again with water. Thus, 21.73 kg of the mixture is obtained, the chromatographic analysis of which in the vapor phase shows the following composition,%; chlorotrifluoromethylbenzenes are not detected nitrotrifluoromethylbenzene 0.9, chloronitrotrifluoromethylbenzenes 71.6, dichloronitrotrifluoromethylbenzenes 27.5. The degree of conversion of chlorotrifluoromethylbenzenes is 100%, and the total yield is 93%. With stirring, 6.5 liters of methanol and 7Q g of Rene nickel added with chromium (2%) are placed under stirring. Bring to 10 bar of hydrogen at 100 ° C with stirring for 15 minutes. Then under these conditions for. 1 h 45 min. 2336 g of the previously prepared nitration product are introduced. This mixture is then kept under stirring for 30 minutes at 10 bar of hydrogen. In this case, the consumption of the total amount of chloronitrotrifluoromethylbenzenes is noted. Then, 1736 g of 30% sodium hydroxide is added and stirred for 15 minutes at 100 ° C and 10 bar of hydrogen. Then, 187 g of Rene nickel with the addition of chromium (2%) are added and hydrogenation is carried out for 3 hours at 100 ° C and 10 bar of hydrogen. After this, the reaction is complete. After filtration, concentration and washing with water, 1546 g of a mixture are obtained, containing,%: orthotrifluoromethylaniline 66, metatrifluoromethylaniline 29.4, paratrifluoromethylaniline 4.6. This mixture is distilled as in Example 1. 989 g of orthotrifluoromethylaniline are obtained with a purity higher than 99%, which corresponds to a yield of distilled orthotrifluoromethylaniline in the order of 97%. Example 5. In the reactor of example 1 is placed 14.6 kg of trifluoromethylbenzene and 1.46 kg of antimony trichloride. Chlorine is then introduced at 0 ° C for 9 hours. After washing with water, a receive. 17.91 kg of a mixture whose chromatographic analysis in the vapor phase shows the following content,%; trifluoromethylbenzene 3.9, chlorotrifluoromethylbenzene 82.5, dichlorotrifluoromethylbenzene 13.6. The conversion of trifluoromethylbenzene is 95%, and the total yield is 98%. When moving, 1828 tons of previously obtained crude mixture are placed in the reactor. The mixture is cooled to 0 ° C and the following mixture is introduced at this temperature for 1 hour: 9140 g of fuming nitric acid and 914 g of concentrated i sulfuric acid (97%). The mixture is then kept at 0 ° C for 6 hours. The organic phase is decanted, washed with water, 10% sodium hydroxide and then again with water. Thus, 2210 g of a mixture is obtained, the analysis of which shows the following composition,%: chlorotrifluoromethylbenzene is undefined, nitrotrifluoromethylbenzene 4.1, chloronitrotrifluoromethylbenzenes 82.7, dichloronitrotrifluoromethylbenzenes 13.2. The degree of conversion of chlorotrifluoromethylbenzenes is 100%, and the total yield is 3.2 liters of methanol and 114 g of Rene nickel supplemented with chromium (2%) are placed in the autoclave with stirring. When moving for 15 minutes, it is brought to 10 bar of hydrogen at 20 ° C. Then, under these conditions, 1139 g of the previously obtained nitriding product is introduced in I h 45 min. Then it is kept for another 1 h 30 min at 2CRP and 50 bar of hydrogen with displacement. After that, the consumption of the total amount of chloronitrotrifluoromethylbeizol is noted. Then 681 g of 33% sodium hydroxide are introduced and mixed for 15 minutes at 20 ° C and 50 bar of hydrogen. Then 228 g of Rene nickel are added and hydrogenation is carried out for 9 hours at 20 ° C and 50 bar of hydrogen. After this, the reaction is complete. After filtration, concentrate. washing with water gives 773 g of a mixture containing,%: orthotrifluoromethylaniline 71.8, metatrifluoromethylaniline 23.0, paratrifluoromethylaniline 4.7. This mixture was distilled as in Example I. 533 g of orthotrifluoromethylaniline were obtained with a purity higher than 99%, which corresponds to a yield of 96% distilled orthotrifluoromethylaniline. The physicochemical characteristics of the starting trifluoromethylbenzene (TFMB) and orthotrifluoroethyl aniline (O-TFMA) are presented in the table. Thus, the advantage of this method compared with the method of the prototype is a smaller number of stages and a better implementation of the method. In addition, about this method there is no need to purify the resulting mixture before each stage.
    权利要求:
    Claims (2)
    [1]
    METHOD FOR PRODUCING O-TRIFLUOROMETHYLANILINE using trifluoromethylbenzene, nitration with a mixture of nitric and sulfuric acids and reduction, characterized in that, in order to simplify the process, trifluoromethylbenzene is chlorinated with chlorine gas in the presence of a chlorination catalyst, namely SbCf g or FeCf + Sb, or SbC ^ In the amount of G | 0.1-10 wt.% In relation to> trifluoromethylbenzene taken at 0-100 ° С until trifluoromethylbenzene conversion is 95-99 wt.% Followed by nitration of the obtained crude reaction product with a mass ratio of each acid to chlorotrifluoromethylbenzenes contained in the reaction medium equal to 0.5-5, to the complete disappearance of chlorotrifluoromethylbenzenes at 0-80 ° C, by hydrogenation of the organic phase obtained after decantation and washing in the presence of a hydrogenation catalyst — Raney nickel and / or Raney nickel with the addition of 0.75—
    [2]
    3.5 wt.% Chromium in an amount of 3-10 wt.% With respect to chloronitrotrifluoromethylbenzenes in methanol at a pressure of 10-50 bar and 20-100 ° C and secondary hydrogenation of the reaction products in the presence of an additional amount of hydrogenation catalyst equal to 8-20 wt.% with respect to the initial content of chloronitrotrifluoromethylbenzene 1 at a pressure of 10-50 bar and 10-10 ° C in the presence of alkali, followed by distillation of the target product from the reaction mixture.
    SU. „, 1138019>
    ♦
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    同族专利:
    公开号 | 公开日
    IE51947B1|1987-04-29|
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    AT10360T|1984-12-15|
    MX7107E|1987-06-26|
    NO150359B|1984-06-25|
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    JPS594414B2|1984-01-30|
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    EP0038465A1|1980-04-17|1981-10-28|Hoechst Aktiengesellschaft|Process for the preparation of 2-trifluoromethyl aniline|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8026367A|FR2496098B1|1980-12-12|1980-12-12|
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