• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention is directed to a process for reducing the concentration of nitrosamines in dinitroanilines, which comprises treating a nitrosamine-containing dinitroaniline with PCl3, PCl5, PBr3, POCl3, SCl2, SOCl2, SO2Cl2, SOBr2, or TiCl4.
    公开号:SU833156A3
    申请号:SU782654652
    申请日:1978-08-31
    公开日:1981-05-23
    发明作者:Фрэнк Эйземберг Ричард；Роза Воглер Катлин
    申请人:Эли Лилли Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a method for purifying dinitroanilines from nitrosamines. . . The known reaction of nitrosamines with hapoidating inorganic agents is l. The purpose of the invention is to increase the purity of the target product. The goal is achieved. It contains a nitrosamine dinitroan LIN, selected from the group of 4-trifluoromethyl-2, 6-dinitro-N, N-di-n-propylaniline; 4-isopropyl-2,6-dinitro-N, N-di-n-propylaniline; 4-trifluoro-2, 6-dinitro-Mn-butyl-M-ethylan. Pin 4-trifluoromethyl-2,6-dinitro-M-ethyl-S-metal allylaniline; 4-tert.-butyl-2,6 dknitro-N-BTOp.butylanilina; 3,4-dimethyl-2, 6-dinitro-N- (1-ethylpropyl) -aniline, 4-trifluoromethyl-2,6-dinitro-M-propyl-H- (2-chloroethyl) -aniline; 4-trifluoromethyl-2,6-dinitr-M-propyl-M- (cyclopropyl methyl) -aniline; 4-trifluoromethyl-2,6-dinitro-Zamino-N, N-diethylaniline; 4-trifluoromethyl-2, b-dinitro-3-chloro-N, N-diethyl aniline; 4-methyl-2,6-dinitro-1, N-bis- (2-chloroethyl) -aniline; 4-sulfamoyl-2, b-dinitro-N, N-di-n-propylaniline and 4-methylsulfonyl-2,6-dinitro-N, N-di-n-propylaniline are treated in the liquid phase with a reagent such as PCSS, PCe, Phg, POCej, SCea, SoCE, 502.022 .. and TiCe4 at a temperature from room temperature to 140 ° C, preferably at 70-90 ° C. In addition, dinitroaniline can be used in molten form. Example 1. The extraction of nitro3amine from 4-treifluoromethyl-2,6-dinitro-M N-di-n-propylaniline using Mix 30 g of the sample 4-trifluoromethyl-2, b-dinitro-N / N-di-n-propylaniline, containing 6B thousand shares of nitrosamine, and 0.5 g of PCe and heated to 70 ° C. The reaction mixture was kept at this temperature for 1 hour while stirring the mixture. Samples are taken after 30 minutes and 1 hour and analyzed for the content of nitrosamine. In a sample taken after 30 minutes, the concentration of nitrosamine is 1.2 ppm. Then the reaction mass is neutralized with 2 ml of 10% sodium carbonate solution; the layers are separated. The aqueous layer is extracted with an equal amount of h.porous methylene. Chloromethylene extract is also analyzed for nitrosamine content. Example 2. The extraction of nitrosamine from 4-trifluoromethyl-2,6-dinitro-N, M-di-n-propylaniline was carried out as described in Example 1, however, 0.2 g of PCEE was used, the reaction was carried out and completed in 30 minutes. The sample is analyzed for the content of nitrosamine, which is 0.9 ppm. Example 3, Extraction of nitrosamine from 4-trifluoromethyl-2, b-dinitro-N M-di-n-propylanilpna using PC. Only 0.02 g of PCSJ-Pro were analyzed for content as in Example 2 /. nitrosamine. Nitrosamine was not detected in the sample. Example 4. The extraction of nitrosamine from 4-trifluoromethyl-2,2-dinitro-N, N-di-n-propylaniline using PC. The procedure was the same as Example 3, but the reaction temperature was not equal to Nitrosamine. Example 5. Extraction of nitrosine mine from 4-trifluoromethyl-2,6-dinitro-M-ethyl-M-metalalaniline using 30 g of 4-trifluoromethyl-2, b-dinitro-M-ethish-I-metalaniline, containing 8.6 part per million of nitrosamine, heated to 90 ° C, 0.2 g of PCA is added and the reaction mixture is stirred at this temperature for. 1h 5 ml of a 10% sodium carbonate solution are added and the layers are separated. Select a sample from a layer of 4-trifluoromethyl-2, b-dinitpo-N-ethyl-N-metalaniline and analyze it for nitrosamine content. The content of nitrosagus in the sample is 4 ppm. Example 6. Removal of nitrosam on 4-isopropyl-2,6-dinitro-M, N-di-n-propylaniline using PCE- ,. A 50 MP solution of 4-isopropyl-2,6-dinitro-NiN-di-n-propylaniline in xylene (35 l of isopropylin from 33.5 hr of a million of nitrosamine) is distilled off on a rotary evaporator for 20 minutes at 90 ° C. 0.5 ml of PC & 7 is added and the reaction mixture is stirred for 30 minutes. Then, 20 ml of a 5% sodium carbonate solution is added and the mixture is stirred for 10 minutes, then distilled on a rotary evaporator for 15 minutes at 100 ° C and analyzed for nitrosamine content, which is 1.9 parts million. Examples 7-9. Remove nitro rosamin from 4-trifluoromethyl-2, b-di-po-N, N-di-n-propylaniline with SoCCi. In each experiment, 30 g of 4-trifluoromethyl-2, 6-dinitro-N, N-di-n-propylanyl a, containing 68 parts per million of nitosamine, are mixed with SOCEj and heated to the reaction temperature, and maintained for a certain period of time. for a period of time, then it is neutralized with 2 ml of a 10% sodium arbonate solution. The layers are separated, and in the first experiment, the organic layer is extracted with an equal amount of methylene chloride. Samples analyzed for the possession of nitrosamine. The results of naliz presented in table. 1. Table 1 Example 10. Removal of nitrosamine from 4-trifluoromethyl-2,6-dinitro. M-ethyl-M-methyllylaniline with soce. 30 g of 4-trifluoromethyl-2, b-dinitro-M-ethyl-I-metalaniline, containing 8.6-4. per million nitrosamine, heated to 90 ° C, 0.2 g added. and the reaction mass is stirred at 90 ° C. in t: 1 hour h. Add 5 ml of 10%: about sodium carbonate solution and separate the layers. Analysis of the organic layer indicates that the nitrosamine content is 0.44 ppm. Examples 11-13. Removal of nitrosamine from 4-trifluoromethyl-2,6-dinitro-NjN-di-n-propylaniline using RVhz. 30 g of 4-trifluoromethyl-2,6-dinitro-N, N-di-n-propylaniline, containing 68 ppm of nitrosamine, are heated before and 0.5 g of PBG is added. The reaction mass is held at 70 ° C for 30 minutes, then neutralized with a dilute sodium carbonate solution and the layers are separated. The organic layer is analyzed for nitrosamine content. The nitrosamine concentration is 1.1 thousand. Repeat the reaction under the same conditions, however, the reaction temperature is maintained at 90 ° C, only 0.1 g of PBG is added. the nitrosamine content is reduced to 2.3 ppm. The reaction is repeated again under the same conditions. But the reaction temperature is 120 ° C and the number of PBH is equal to Nitrosamine analysis is not detected, 1 g is roughened. Example 14. Removal of nitrosamine from 4-trifluoromethyl-2,6-dinitro -N, H-di-n-propylaniline using TiCe4. 30 g of 4-trifluoromethyl-2, b-dinitro-N; N-di-n-propylaniline, containing 68 parts per million of nitrosamine, is heated before and OD of ml of TiCC is added. The reaction is carried out at the same temperature. Samples are taken periodically and analyzed for nitrosamine content. When sampling after 15 minutes, the content of nitrosamine is 59 hours per million, when sampling after 30 minutes 16 hours per million, sampling at 1 hour - 21 hours per million, after 2 hours - 3.8 hours million. Example 15. Removal of nitrosis mine from 4-trifluoromethyl-2,6-dinitro-NIN-di-n-propylaniline using SCEa. To 100 g of molten 4-trifluoromethyl-2, 6-dinitpo-N | N-di-n-propylaniline, containing 50 parts per milliliter of nitrosamine, 0.2 g of SCtj is added and the reaction mass is stirred for 1 h at. Samples are taken and analyzed for the content of nitrosam on without treatment. When sampling after 30 minutes, the content of nitrosamine is 7.4 per million, after 1 hour - 7.3 hours per million. Examples 16-18. Removal of nitrosamine from 4-trifluoromethyl-2,6-dinitro-N N-di-n-propylaniline with POCe. 30 g of 4-trifluoromethyl-2,6-dinitro-N, N-di-n-propylaniline, containing 68 ppm of nitrosamine, are heated to the reaction temperature, a certain amount of POCt is added and the reaction mixture is kept at the reaction temperature for 30 The reaction mixture is neutralized with sodium carbonate, carbonate, and the organic layer is analyzed for nitrozamine. The conditions of the reaction and the results obtained are shown in Table. 2.:. Table. EXAMPLE 19 Removal of nitrosamine from 4-trifluoromethyl-2,6-dinitro 65
    权利要求:
    Claims (3)
    [1]
    Claims of the invention: -N) N-di-n-propylane using the base effect. 30g of 4-trifluoromethyl-2,6-dinitro-N N-di-n-propylaniline with an average sample breakdown for nitrosamine 68 hours. For a million, mix with 0.2 g of PCCs and 0.05 g., Reactionary). the mixture is heated to and kept at this temperature for 30 minutes. Then neutralize 2 ml of 10% solution, - ,,. Then, the layer of 4-trifluoromethyl-2,6-dinitro-Y, N-di-n-propylaniline is analyzed for the content of n-thosamine. Nitrosamine not detected. Example 20 Removal of nitrosamine from 4-trifluoromethyl-2,6-dinitpo-N N-di-n-propylaniline with the aid of time. A 30 g sample of the mass of 4-trifluoromethyl-2, N-dinitro-N N-di-n-propylaniline with a nitrosamine content of 68 ppm is heated to -9 ° C and 0.03 ml of PCfi is added. The reaction mass is maintained at for 2 h and periodically sampled and analyzed. When taking a sample after 15 minutes, the concentration of nitrosamine is 6.6 thousand parts. By sampling after 30 minutes - 21, with sampling after 1 h 4.9; in the selection after 2 h - 8.5. Example 21. Removal of nitpO3 uviHHa from 4-trifluoromethyl-2,6-dinitro-N, N-di-n-propylaniline with a 30 ml sample of 4-trifluoromethyl-2,6 dinitro-N, N-di-n-propylaniline with Nitrosamine 36 hours per million is heated before and 0.5 ml of SOiCe2 is added. The reaction mass is kept at the same temperature for 1 hour. Samples are taken after 0.5 and 1 hour. Each sample is washed with 1.0 ml of water, dried on a rotary evaporator for 15 min at and analyzed for the content of nitrosamine. When sampling after 30 min, the concentration of nitrosamine 4h. to MILLION; when selected after 1 h - 2. Example 22. Removal of nitroeamine from 4-: rifluoromethyl-2,6-dinitpo-N N-di-n-propylaniline using PC € 5-. Carried out analogously to example 21, but instead using 0.5 g of PCEU. When sampling after 30 minutes, the concentration of nitrosamine is 8 hours. in a million; when selected after 1 hour - 4 .. Method for purification of dinitroanines from nitrosamines, characterized in that, in order to increase the purity of the target product, containing nitroamine dinitroaniline selected from the group 4-trifluoromethyl-: 2,6-dinitro-N, N-di-n-propylaniline; 4-isopropyl-2, 6-dinitro-M / N-n-propylaniline, 4-trifluoromethyl-2, b-dinitrote — H-n-Outil-M-ethylaniline; 4-trifluoromethyl-2, b-dinitro-N-ethyl-N-metalaniline; 4-t-butyl-2,6-dinitro, -H-s-butylaniline; 3,4-dimethyl -2, 6-dinitro-N- (1-ethylpropyl) -aniline, 4-trifluoromethyl-2, b-dinitro-M-propyl-N- (2-chloroethyl) -aniline, 4-trichloromethyl- 2, b-dinitro-N-propyl-N- (cyclopropylmethyl) -aniline; 4-trifluoromethyl-2, b-dinitro-3-amino-N, N-diethylaniline 4-T; Ifluoromethyl-2, b Dinitro-3-chloro-M, N-diethylaniline; 4-methyl-2, b-dinitro-N, N-bis (2-chloroethyl) -aniline; 4-sulfamoyl-2,6-dinitro-N, N-di-n-propylaniline and 4- (methylsulfonyl) -2,6-M N-di-n-propylaniline, treated in the liquid phase with a reagent selected from the group
    rsse, RVhz, Rosez, soce,
     , Sce. and - Tice at a temperature from room temperature to 140C.
    [2]
    2. Method, pop, 1, characterized in that the process is carried out at 70-90 s.
    [3]
    3. A method of pop 1, characterized in that dinitroaniline is used in molten form.
    Sources of information taken into account in the examination
    1. Definition of nitrosamines and. nitrosamides in microgram amounts, Ala, Lett, 1973, 6 (4), p. 369-72.
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    DE482795C|1927-02-06|1929-09-20|Chem Fab Gruenau Landshoff & M|Process for the preparation of secondary amines from the corresponding N-nitroso derivatives and their core substitution products|
    DE2035796A1|1970-07-18|1972-01-27|Bayer Ag|Procedure for replacing N nitroso|DE2918023A1|1979-05-04|1980-11-13|Bayer Ag|METHOD FOR PRODUCING N-ALKYLATED AROMATIC AMINES|
    DE2926947C2|1979-07-04|1982-03-18|Hoechst Ag, 6000 Frankfurt|Process for removing nitrosating agentfrom nitrated aromatic compounds|
    US4391992A|1979-08-24|1983-07-05|American Cyanamid Company|N-Denitration of N,2,6-trinitroanilines with phase transfer catalysts|
    EP0024503B1|1979-08-24|1983-06-15|American Cyanamid Company|N-denitration of n,2,6-trinitroanilines with phase transfer catalysts|
    IT1131182B|1980-05-15|1986-06-18|Montedison Spa|PREPARATION PROCESS OF N-DI-N-PROPIL-2,6-DINITRO-4-TRIFLUOROMETILANILINA WITH LOW NITROSAMINE CONTENT|
    IL67948A|1983-02-18|1988-05-31|Agan Chemical Manufacturers|Method for removal of nitrosoamine impurities from herbicides|
    DE3345157A1|1983-12-14|1985-06-27|Hoechst Ag, 6230 Frankfurt|METHOD FOR PRODUCING NITROSAMINE-FREE N, N-DISUBSTITUTED NITROAROMATIC AMINES AND THEIR STABILIZATION AGAINST NITROSAMINE FORMATION|
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    AU594850B2|1987-12-29|1990-03-15|Finchimica S.P.A.|A method for the treatment of dinitroanilines to reduce their nitrosamine content and/or to stabilise them against the formation of nitrosamines|
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    US5922915A|1998-05-11|1999-07-13|Srm Chemical, Ltd., Co.|Process for removing N-nitroso compounds from organo-amine compositions including dinitroaniline herbicides|
    CN102766056B|2012-08-13|2014-07-02|江西盾牌化工有限责任公司|Method for preparing chemical herbicide with butralin technical material content reaching 90+/-1%|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US83026177A| true| 1977-09-02|1977-09-02|
    US05/878,843|US4185035A|1977-09-02|1978-02-17|Dinitroaniline purification with inorganic acid halides|
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