专利摘要:
METHOD FOR OBTAINING 3-CHLORANILINE OR 3,5-DICHLOROANILINE Hydrogenation of nitrogen-containing polychloro derivatives of benzene in the presence of a palladium catalyst supported on coal, and hydrochloric acid under heating and elevated pressure, differing in that, in order to simplify the process, as the nitrogen-containing contents, it is also used as the nitrogen-containing gases, which are used for heating and elevated pressure, in order to simplify the process, in the case of nitrogen-containing gases, it is also used as a nitrogen-containing mixture of oxygen-containing carbon for heating and increased pressure. E kch 1.1Gt: h of benzene use a compound of the general formula K if№ J (B where K is hydrogen or oxygen and R2 is hydrogen, then R and R are chlorine, hydrogen or chlorine, Rb is hydrogen and, if chlorine, then RR, R and R are hydrogen or chlorine, and to it, R5 or chlorine, and the process is carried out in the presence of hydrobromic or hydroiodic acid i or bromides, or Cft of alkali metal iodides at a concentration of hydrogen ions of 0.8 to 12 g-ion / l, the concentration of bromide ions O, 1-6 g ion / l, iodide ion concentration 0.5-10 - 1 g-ion / l, temperature 130-210 ° C and pressure 8-36 bar oo with co
公开号:SU1103793A3
申请号:SU802880051
申请日:1980-02-12
公开日:1984-07-15
发明作者:Кордье Жорж
申请人:Рон-Пуленк Агрошими (Фирма);
IPC主号:
专利说明:

Example 3. The process is carried out under conditions similar to Example 1, but using 115 cm of an aqueous solution of hydrochloric acid (0.8 mol / l) instead of 106 cm of a solution containing 4 mol / l and 14.8 g of dry NaJ (instead of 13.3 cm HJ solution. Get 3,5-dichloroaniline containing 5.8% trichloroaniline and 0.3% meta-chloroalkyl. The output of dichloraniline 93,6%. Conversion of tetrachloroaniline 100%. Example 4. The process is carried out under conditions analogous to example 1, but using 120 cm of an aqueous solution of hydrochloric acid (instead of 106 cm) and 0.4 cm of an aqueous solution of hydrogen iodide (concentration of the solution is 0.01 mol / l) instead of 13, 3 cm of a solution with a concentration of 7.6 mol / l. The duration of the process is 5 minutes (instead of 1 hour). Get 3,5-dichloroaniline containing 3.5% metachloroaniline. The yield of 3,5-dichloroaniline 96%. Conversion, tetrachloroaniline 100%. Example 5. The process is carried out under conditions analogous to example 1, but load 0.42 g of tetrachloroaniline (instead of 1.67 g), 120 cm of an aqueous solution of hydrochloric acid (concentration 2.5 mol / l) instead of 106 cm of solution concentration of 4 mol / l and 0.11 g KJ dry (instead of 13.3 cm HJ solution). The reaction time is 2 hours and 40 minutes (instead of 1 hour), the temperature is 150 ° C (instead of 190 ° C), the pressure is 10 bar, of which 5 bar is the fractional pressure of hydrogen .... 3.5-dichloroaniline is obtained containing 2 , 5% aniline and 2.5% metachloroaniline. The yield of 3,5-dichloroaniline 86%. Conversion of tetrachloroaniline 100%. Example 6. The process is carried out under conditions analogous to example 1, but using 1.17 g of 2,3-dichloroaniline (instead of tetrachloroaniline), 0.56 g of catalyst based on pall. di (instead of 0.07 g), 12b cm of an aqueous solution of HCl, the concentration of which is 2.5 mol / l (instead of 106 cm HCl concentration. 4 mod / l). Introduced 0.2 KJ (instead of hydrogen iodide). Heating is carried out to a temperature of 160 ° C, the total pressure is 13 bar, of which 6 bar is par 34. Hydrogen pressure., process duration 3h. 2,3-dichloroaniline conversion 98.2%. The output of metachlororanyl 95.6% relative to the converted dichloraniline. Example 7. The process is carried out under conditions similar to example t, but 3,4-dichloroaniline (instead of 2,3-dichloraniline), hydrochloric acid with a concentration of 1 mol / l (instead of 2.5 mol / l), 0, is evaporated; 04gKL (instead of 0.2 g). The duration of the process is only 45 minutes. 3,4-Dichloroaniline was completely converted to methachloraniline, the yield of which was 97.1%. Example 8. Into an autoclave with a capacity of 225 cm, 139 g of 3,4-dichlorophenol dioxide, 0.56 g / catalyst (palladium on activated carbon, palladium content is 10%), 120 cm of an aqueous solution of hydrochloric acid at a concentration of 1 mole / l), 0.04 g KJ. The autoclave is first flushed with argon gas and then with hydrogen, after which hydrogen is introduced into the autoclave until a pressure of 4 bar is reached. Adjust the temperature in the autoclave to. The pressure is now 13 bar, of which 6 bar is the partial pressure of hydrogen. The reaction mixture is held under these conditions for 1 hour and 40 minutes, and then cooled. Conversion of dichloronitrobenzene 100%. The output of the obtained metachloraniline 92.9%. Example 9. In an autoclave with a capacity of 250 cm covered with tantalum from the inside, 120 cm of aqueous 4N are introduced. hydrochloric acid solution, 0.354 g of 3,4,5-trichloroaniline, 0.14 g of a palladium-based catalyst, similar to that indicated in Example 1, 0.011 g of KJ. The autoclave is flushed with argon, then with hydrogen, and then closed. Heating is carried out for 2 hours and 30 minutes at a total pressure of 8 bar and a hydrogen partial pressure of 5 bar. During the process, trichloroaniline is completely transformed, and 3.5-dichloroaniline is obtained in a yield of 99%, Example 10. In a 250-cm autoclave coated with tantalum from the inside, 120 cm of aqueous 4 Hi HC1 solution is added, 3.5.4 g 2, 4.5 S-trichloroaniline, 1.4 g of a palladium-based catalyst, similar to the one mentioned in the previous examples (palladium is applied on activated carbon, the content of palladium is 10%), 0.011 g of iodide of feces Autoclave is rinsed with argon, then hydrogen, after what the autoclave is closed. Heating is carried out for 240 MHHj, at a temperature of 160 at a total pressure of 18 bar and a partial pressure of hydrogen of 13 bar. A complete conversion of the starting α-compound is observed, 3-chloranium lines are obtained with a code of 98.2%. For example 11. Process wire in conditions similar to the preceding example, but load 120 cm of water 4 n. a solution of HC1, 0.354 g of 2,3,4-trichloroaniline, 0.140 g of catalyst based on palladium (palladium in an amount of 10% applied to activated carbon), 0.011 g of potassium iodide. Heating is carried out for 160 minutes at a temperature of 160 ° C and a total pressure of 18 bar, of which 13 bar is the partial pressure of hydrogen. With complete conversion of the starting compound, 3,5-dichloraniline is obtained with a yield of 96.8%. Example 12, a process under conditions analogous to the example, but loading 120 cm of an aqueous solution of hydrochloric acid at a concentration of 4 mol / l, 1.67 g of 2,3,4,5-tetrachloroaniline, g of the catalyst used in example 1; 7.14 g potassium bromide. Heating is carried out for 170 minutes at a temperature of 190 ° C and a total pressure of 20 bar, of which 6 bar / is the partial pressure of hydrogen. A complete conversion of the starting compound is observed. Get 3W-dichlo aniline with a yield of 90%. Example 13. The process was conducted under conditions similar to example 1, however, 120 ml of aqueous 4N hydrochloric acid solution, 420 mg 2,3,4, 3-tetrachloroaniline, 140 mg of catalyst, similar to that used in example 1j 1.1 mg, were charged potassium iodide (or the concentration of this compound in the reaction medium is 5.5-i; b.) 3. The reaction medium is heated for 220 minutes at a temperature of 160 ° C and a total pressure of 9 bar, of which 4 j5 bar is the partial pressure of hydrogen Complete conversion of tetrachloroaniline is observed. 3.5-dichloroaniline is obtained with yield 9 2.5%. Example 14. The process is carried out under conditions analogous to example 1, however, 120 ml of aqueous 4N hydrochloric acid solution, 420 mg of 2,3,4,5-tetrachloroaniline, 140 mg of catalyst, containing 1 , 1% palladium supported on activated carbon, 11 g of potassium iodide. The mixture is heated for 180 minutes at a temperature of 160 ° C and a total pressure of 18 bar, of which 13 bar is parietal hydrogen pressure. yield 98.1%. See the full conversion of tetrachlorine NIL and on. Example 15. The results are similar to those obtained in example 14, when using similar starting compounds and under conditions similar to those indicated, when replacing 140 mg of catalyst containing 1.1% palladium by 140 mg of catalyst containing 2.8% palladium, deposited on a substrate similar to that indicated, using the same methods. Example 16. An autoclave with a capacity of 3.6 liters, coated on the inside with tantalum, was charged with 2 kg of an aqueous 13.6% hydrochloric acid solution, 150 g of a catalyst containing palladium deposited on carbon black (1100 specific carbon specific surface area, weight content palladium 10%), 11.7 g of dry solid potassium iodide (or 0.5 ion / g of iodide ions per gram atom of palladium). The autoclave is flushed first with nitrogen, then with hydrogen, and then the autoclave is closed. Hydrogen is injected until pressure reaches 3 bar. The reaction mixture is heated to a temperature of 160 ° C, leaving autogenous pressure to increase. Hydrogen is reintroduced to a pressure setting of 15.5 bar, of which 10 bar is the hydrogen partial pressure. Then 1 mol of 2,3,4,5-tetrachloronitrobenzene is introduced over 2 hours and 30 minutes. The mixture was left under the above conditions with constant stirring for 2 hours. Then the reaction mixture was cooled to, after which it was removed from the reactor, the liquid reaction mixture was neutralized with an aqueous solution of sodium hydroxide, the catalyst was removed by filtration mainly 3, -5-dichloroaniline) is extracted with toluene. The solvent is evaporated under vacuum. Under these conditions, 2,3,4,5-tetrachlorobenzene conversion is 100%. The yield of 3,5-dichloroaniline 94%, II p and me s 17-19. A 250-ml autoclave with an internal coating of tantalum is charged with 120 ml of an aqueous solution of hydrochloric acid with a varying concentration of HC 1, 3.5 g of 2,3,5-trichloroaniline, 10.8 mg of dry potassium iodide, 0.14 g of catalyst in palladium deposited on activated carbon (specific surface of activated carbon 1100, weight content of palladium 10%). "- Heating is carried out for a certain time at a temperature of 160 ° C and a total pressure of 20 bar. 3,5-dichloroaniline is obtained. In tab. 1 shows the concentration of hydrogen ions in the ion-g / l, the duration of the heating and the yield with respect to the reacted 2,3,5-trichloroaniline. 3 T a fl l and c a 1 Prime 20-23. A 250-ml autoclave with an internal coating of tantalum is charged with 120 ml of hydrochloric acid solution at a concentration of 4 mol / l, 1.67 g of 2,3,4,5-tetrachlororaniline, 0.07 g of catalyst in the form of palladium deposited on activated carbon (specific surface of activated carbon 1100, weight content of palladium tO%), a variable amount of bromine ions in the form of a salt (bromide) or hydrobromic acid (120 ml). In the latter case, no hydrochloric acid is added. Heating is carried out for a certain time at 190 ° C at a total pressure of 26 bar. Conversion 100%. 3,5-dichloroaniline is obtained. In tab. 2 shows a view of the cation combined with the bromine ion, the concentration of bromine ions, the duration of heating and temperature of aniline chlorinated in the 3.5 position, i.e. the yield in moles of this compound relative to 2,3,4,5-tetrachloroaniline. table 2
Li N
Li N
Example 24. The process is carried out under the conditions of Example 1. 0.84 g of 2,3,5,6-tetrachloroaniline-55 is introduced into the autoclave; 0.07 g of Pd / C catalyst with 10% palladium; 106 ml of an aqueous solution of 4 N. hydrochloric acid; 13.3 ml of water; 5
60
94 91 0.3 100 0.1 120
90 98 4 180
a clear solution of 7.6 and. hydroiodic acid solution.
The process time is 2 hours.
Upon conversion of the starting tetrachloroaniline tetra 100%, 3.5-dichloraniline is obtained in a yield of 96%.
9 110379310
Example 25. The process of provoa. In the conversion of the starting tetra3 conditions of example 1, starting from 100% chlorophyllinol, 3.54% of hydrochloride is added, 0.84 g of 2,3,5,6-tetra-chloroaniline in 97.3% yield, closor, 120 ml of aqueous solution
6 and. hydrobromic acid, 5 Technical and economic efficacy, 07 g of Pd / C catalyst with 10% Pd.
The process temperature, in general, simplifies the process, and then singing is 36 bar, from which 18 bar decreases pressure and temperature.
hydrogen pressure. Time process process.
权利要求:
Claims (1)
[1]
METHOD FOR PRODUCING 3-CHLOROANILINE OR 3,5-Dichloroaniline by hydrogenation of nitrogen-containing polychloro derivatives of benzene in the presence of a palladium catalyst supported on coal and hydrochloric acid under heating and elevated pressure, characterized in that, to simplify the process, as nitrogen-containing polychlor use a compound of general formula 2 to 3
B ”B 'where R 1 is hydrogen or oxygen and, if R2 is hydrogen, then R 3 and R 4 are chlorine, R 5 is hydrogen or chlorine, R b is hydrogen ·, and if R 2 is chlorine, then R 5 , R 4 , R b and R 6 are hydrogen or chlorine, with at least R 3 or R 5 being chlorine, and the process is carried out in the presence of hydrobromic or hydroiodic acids or bromides or alkali metal iodides at an ion concentration hydrogen 0.8 12 g-ion / l, concentration, bromidion 0.1-6 g-ion / l, concentration of iodide ions 0.5-10 4 - 1 g-ion / l, temperature 130-210 ° C and pressure 8-36 bar.
SU ".1103793
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同族专利:
公开号 | 公开日
CA1139314A|1983-01-11|
HU185215B|1984-12-28|
EP0015219B1|1981-10-28|
DK152667B|1988-04-11|
DD149062A5|1981-06-24|
YU42324B|1988-08-31|
US4351959A|1982-09-28|
IE49642B1|1985-11-13|
JPS5848541B2|1983-10-28|
FR2449075A1|1980-09-12|
IL59297D0|1980-05-30|
EP0015219A1|1980-09-03|
IL59297A|1983-06-15|
DK152667C|1988-08-22|
ES488571A1|1980-10-01|
JPS55149231A|1980-11-20|
GB2041375A|1980-09-10|
IE800275L|1980-08-15|
YU37980A|1983-01-21|
DK62680A|1980-08-16|
DE3060055D1|1982-01-07|
AT398T|1981-11-15|
BR8000918A|1980-10-29|
FR2449075B1|1983-03-11|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题

US3683025A|1969-05-06|1972-08-08|Henry W Pons|Hydrogenation of nitrobenzenes|
US3546297A|1969-07-01|1970-12-08|Du Pont|Process for preparation of aromatic chloroamines|
DE2503187C3|1975-01-27|1979-05-31|Bayer Ag, 5090 Leverkusen|Process for the preparation of chlorine-meta-substituted anilines|IL63297A|1980-08-01|1984-05-31|Rhone Poulenc Agrochimie|Selective preparation of meta-chloroanilines|
DE3042242A1|1980-11-08|1982-06-09|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING M-HALOGEN-SUBSTITUTED ANILINES|
DE3127026A1|1981-07-09|1983-01-20|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING M-CHLORINE-SUBSTITUTED ANILINE|
FR2521132B1|1982-02-05|1984-03-16|Rhone Poulenc Agrochimie|
FR2532305B1|1982-08-24|1984-12-07|Rhone Poulenc Agrochimie|
法律状态:
优先权:
申请号 | 申请日 | 专利标题
FR7904481A|FR2449075B1|1979-02-15|1979-02-15|
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