• 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:
    N-di-n.propyl-2,6-dinitro-4-trifluoromethylaniline (Trifluralin) with a low content in nitrosamines (less than 1 ppm) is prepared by reacting 4-trifluoro-2,6-dinitro-chlorobenzene with di-n.propylamine under the following critical conditions:… - feeding to the chlorobenzoderivative the di-n.propylamine containing a hydrate or an alkaline carbonate so that the pH value be comprised between 7 and 7.5;… - by regulating the temperature in such a way that it will not exceed 70 DEG C;… - by operating in the presence of at least 50% by weight of water in the reaction mass.
    公开号:SU1003750A3
    申请号:SU813285558
    申请日:1981-05-12
    公开日:1983-03-07
    发明作者:Борненго Марио；Бассиарелли Серджо
    申请人:Монтэдисон С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved method for producing M-di-C-propyl-2,6-dinitro-4-trifluoromethylaniline, a herbicide known as Trifloralin. 5
    According to a known method, said compound is prepared from 4-trifluoromethyl-2,6-dinitrochlorobenzene by heating it at 90 ° C with di-C’ propylamine. Under such conditions, significant quantities of nitrosoamines are formed as by-products (their content can reach 250 parts per million), which are considered substances hazardous to warm-blooded animals. According to the known method, the content of nitrosoamines in the final product can be reduced by treating it with 20% HC 1! and ethanol £ 1]. 20
    The purpose of the invention is to reduce the content of nitrosoamine in the target product and simplify the process.
    The goal is achieved according to the method for producing N-di-H-pro2 pil-2,6-dinitro-4-trifluoromethylaniline, namely, that 4-trifluoro · methyl-2,6-dinitrochlorobenzene is reacted with di-n-propylamine at the simultaneous introduction into the process of alkali metal hydroxide at pH 7'7.5 at 70 ° C and in the presence in the reaction mass of 50 wt. % water.
    It is assumed that under such conditions di-C-propylamine hydrochloride will not be formed (lower pH 4.3-4.5 is needed to form di-H-propylamine hydrochloride); low temperature prevents the loss of di-) 1-propylamine, and all these conditions lead to the fact that the content of nitrosoamines in the final product will at most reach 1 fraction per million.
    The alkali metal chloride reaction is exothermic and must therefore be controlled by a suitable cooling system. The presence of water, in addition, is necessary to maintain the sodium chloride present in the solution and to remove it.
    The amount of nitrosoamine found in the herbicide obtained by the above procedure varies from 0.1 to 1 ppm. To achieve such results, it is necessary to strictly adhere to the specified conditions of the process; a shift in the pH value to the acidic side (region) can lead to the fact that the content of nitrosoamine exceeds 1 millionth of a share; an increase in temperature in an alkaline environment above 70 ° C leads to the loss of N-propylamine; an increase in pH above 7.5 gives unsatisfactory yields due to an increase in secondary reactions.
    Example 1. 1200 g of 4-trifluoromethyl-2,6-20-di-nitrochlorobenzene ^, 2 liters of water are charged into a 4-liter vessel, after which they are heated to 55 ° C with stirring.
    Then simultaneously through two elongated taps add 450 g of 99% Di-25-n-propylamine and 355 g of 40 weight. % NaOH; by means of the introduced electrode, the flow is regulated so that the pH remains constant within the range of 7'7.5 · - zo
    During the addition, the vessel is cooled with water so that the temperature inside does not exceed 55 ° C.
    After complete addition, the reaction mass is heated to 70 ° C for 3 hours, all the while maintaining the pH value of 7.2 (possible the addition of a few drops of 40 wt.% NaOH).
    The mixture is washed twice with a liter of teppa water (55 ° C), each time with stirring, until a neutral medium is reached.
    The yield of I-di-I-propyl ~ 2,6-dinitro-4-trifluoromethylaniline, calculated on 4-trifluoromethyl-2,6-dinitrochlorobenzene, reaches 97 weight. % With a product purity of up to 95 '%, the content of nitrosoamines is 0.1 ppm.
    EXAMPLE EXAMPLE 2 Under conditions analogous tech 50 Example 1, the reaction between 4 and 1,003,750
    with propylamine and 4-trifluoromethyl ~ 2,6-chlorobenzene as follows: sodium hydroxide solution is added after di-n-propylamine is fully charged. The yield of the final product is 95 weight. %, but the content of nitrosoamine is 250 ppm.
    Example 3. Under conditions similar to example 1, the reaction was carried out with the addition of di-n-pro-pilamine and sodium hydroxide solution, but the reaction temperature spontaneously increased during the addition of reagents, the purity of the product thus obtained decreased to 92%, and the content of nitrosoamines reached 10 ppm.
    Example ^. Under conditions analogous to example 1, 1200 g of 4-trifluoromethyl-2,6-dinitrochlorobenzene are charged into the reactor, which is then heated to 55 ° C in the presence of 40% water. After that, di-H-propylamine and sodium hydroxide solution are added at the same time, maintaining the pH still between 7.2 and 7.5. The nitrosoamine content in the final product increased to 10 ppm, while the yield reached 95 weight. % product showed 94% purity.
    权利要求:
    Claims (2)
    [1]
    This invention relates to an improved process for the preparation of M-di-C-propyl-2, 6-dinitro-trifluoromethylaniline, a herbicide known as Trifloralin. According to a known method, said compound is obtained from C-trifluoromethyl-2, 6-dinitrochlorobenzene by heating it with di-n-propylamine. Under such conditions, significant amounts of nitrosoamines are formed as by-products (their content can reach 250 ppm), which are considered dangerous for warm-blooded animals. According to a known method, the content of nitrosamines in the final product can be reduced by treating it with 2Q% HCt and ethanol 1. The purpose of the invention is to reduce the content of nitrosamine in the target product and simplify the process. The goal is achieved according to the method of producing N-di-I-propyl-2, 6-dinitro-C-trifluoromethylaniline, which consists in the fact that 4-trifluoromethyl-2, 6-dinitrochlorobenzene is reacted with di-n-propylamine with simultaneous administration in the process of alkali metal hydroxide at pH, 5 at 70s and in the presence in the reaction mass 50 weight. % water. It is assumed that, under such conditions, hydrochloride di-H-propylamine will not form (lower pH values of t, 3, 5 are necessary for the formation of hydrochloride di-propylamine; low temperatures prevent the loss of di-M-propylamine, and all of these conditions result in the nitrosamine content in the final product being at most 1 ppm. The formation of alkali metal chloride is exothermic and must therefore be controlled by a suitable cooling system. The presence of water is also necessary to maintain the sodium chloride present in the solution and to remove it. The amount of nitrosamine found in the herbicide prepared according to the above procedure ranges from 0.1 to 1 ppm. To achieve such results, it is necessary to strictly adhere to the specified conditions of the process; a shift in the pH value to the acidic side (region) may cause the nitrosoamine content to exceed 1 ppm; an increase in the temperature in an alkaline medium leads to a loss of i-propylamine; an increase in pH above 7.5 gives unsatisfactory yields due to an increase in secondary reactions. EXAMPLE 1 A 1200 g β-trifluoromethyl-2,6-di-nitrochlorobenzene, 2 liters of water is charged into a liter vessel, then heated to 55 ° C with stirring. Then, 450 g of 99 di-n-propylamine and 355 g of 0 wt. % NaOH; through the input electrode, the flow is adjusted so that the pH remains constant within the limits of 5- During the addition, the vessel is cooled with water so that the temperature inside does not exceed 55 C. After the addition is completed, the reaction mass is heated to within XX hours while keeping the pH value equal (it is possible to add a few drops of ifO wt.% NaOH). The mixture is washed twice with a liter of warm water (55 ° C), each time with stirring, until it reaches a neutral medium. The yield of N-di-C-propyl-2,6-dinitro-4-trifluoromethylaniline, calculated on α-trifluoromethyl-2,6-dinitrochlorobenzene, reaches 37 wt. % When the purity of the product reaches 5%, the nitrosamine content is 0, 1 ppm. PRI me R
    [2]
    2. Under conditions similar to example 1, the reaction between H10 504-propylamine and-trifluoromethyl-2,6-chlorobenzene was carried out as follows: a solution of sodium hydroxide was added after the di-n-propylamine was completely charged. The yield of the final product is 95 wt. %, but the nitrosoamine content is 250 ppm. Froze Under conditions similar to example 1, the reaction was carried out while adding di-m-pro-t pilamine and sodium hydroxide solution, but the reaction temperature spontaneously increased during the addition of the reagents. the purity of the product thus obtained was reduced to 32%, and the content of nitrosamines reached 10 ppm. PRI me R t. Under conditions similar to example 1, 1200 g of α-trifluoromethyl-2,6-dinitrochlorobenzene are charged to the reactor, which is then heated to 55 ° C in the presence of kQ% water. After this, di-propylamine and sodium hydroxide solution are added simultaneously while maintaining the pH between 7.5 and 7.5. The nitrosoamine content in the final product has increased to 10 ppm, while the yield has reached 95 wt. % product showed purity. The method of obtaining M-di-H-propyl-2,6-dinitro-trifluoromethylaniline by reacting 4-trifluoromethyl-2,6-dinitrochlorobenzene with: di-n-propylamine, characterized in that, in order to reduce the nitrosoamine content in the final product, the process is carried out in the presence of an alkali metal hydroxide, which is added simultaneously with dipropylamine, at a pH of 7-7.5 and a temperature of 70 ° C in the presence of 50 wt. in the reaction mass. water. Sources of information taken into account during the examination 1. Belgian patent No. Cl. C 07 C, publ. 1968 (prototype).
    类似技术:
    公开号 | 公开日 | 专利标题
    US5107032A|1992-04-21|Process for the preparation of o-phthalaldehydes
    SU1003750A3|1983-03-07|Process for producing n-di-h-propyl-2,6-dinitro-4-trifluoromethyl aniline
    US3752841A|1973-08-14|Process for the preparation of carbamates of alkylthiolhydroxamates and intermediates
    US4486358A|1984-12-04|Process for producing N-phosphonomethylglycine
    US4308391A|1981-12-29|2-Amino-4-substituted-thiazolecarboxylic acids and their derivatives
    US4948909A|1990-08-14|Process for the preparation of iminodiacetonitrile and iminodiacetic acid
    US3857692A|1974-12-31|1,2-dimethyl-3,5-diphenylpyrazolium salts and 3,5-dibromo-4-hydroxybenzonitrile herbicidal compositions
    EP0237513A1|1987-09-16|Process for the preparation of iminodiacetonitrile
    US5359132A|1994-10-25|Process for the preparation of sodium salts of aromatic sulphinic acids containing nitro groups
    JPH0649666B2|1994-06-29|Process for producing 2,4,6-tribromophenyl acrylate
    US2477869A|1949-08-02|Nitro sulfonates from beta-nitro alkanols
    US5043442A|1991-08-27|Process of preparing an isothiocyanate intermediate used in the preparation of xylazine
    US2287285A|1942-06-23|Preparation of potassium thiocarbonate
    JPH0649667B2|1994-06-29|Process for producing 2,2-bis | propane
    EP0003374B1|1981-08-12|Process for the preparation of a substituted triazine
    US3946071A|1976-03-23|Substituted alpha-chloro-methane-sulfenyl chlorides
    US4994561A|1991-02-19|Process for the preparation of metallizable azo dyes carrying out coupling in an inert gas atmosphere in the presence of an ammonium salt
    US4334911A|1982-06-15|Herbicidal compositions and methods
    US3681335A|1972-08-01|SUPPRESSION OF TRIS|-S-TRIAZINE FORMATION IN THE PRODUCTION OF CHLORO-BIS|-S-TRIAZINES THROUGH ADJUSTMENT OF pH
    SU1004365A1|1983-03-15|Process for producing naphthalenethioles
    US4232153A|1980-11-04|Process for the production of chloro-di |-s-triazines
    US2913484A|1959-11-17|Diphenylmethyl 3, 4-dichlorobenzoate
    SU1310389A1|1987-05-15|Method for producing n,n-di|-s-2,3,3-trichlorallyl-tricarbamate
    DE1568646A1|1970-04-02|Process for the preparation of N-hydroxyimidothiocarboxylic acid esters
    US3266882A|1966-08-16|Herbicidal compositions and their use
    同族专利:
    公开号 | 公开日
    AU7041681A|1981-11-26|
    JPS579745A|1982-01-19|
    IL62842A|1984-06-29|
    AU545206B2|1985-07-04|
    CA1168661A|1984-06-05|
    DE3163170D1|1984-05-24|
    HU188669B|1986-05-28|
    IL62842D0|1981-07-31|
    IT1131182B|1986-06-18|
    IT8022073D0|1980-05-15|
    ES8207132A1|1982-09-01|
    MX160038A|1989-11-09|
    JPH0127057B2|1989-05-26|
    EP0040762B1|1984-04-18|
    ZA813154B|1982-05-26|
    US4335260A|1982-06-15|
    BR8103009A|1982-02-09|
    EP0040762A1|1981-12-02|
    ES502212A0|1982-09-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US1401631A|1921-12-27|A cobpobation of |
    AT305241B|1969-06-28|1973-02-12|I Pi Ci S P A Ind Prodotti Chi|Process for the preparation of derivatives of o, o'-dinitro-N, N-dialkylaniline|
    DE2161879B2|1971-12-14|1974-07-04|Basf Ag, 6700 Ludwigshafen|Process for the preparation of 2,6-dinitroaniline derivatives|
    US4134917A|1977-04-25|1979-01-16|American Cyanamid Company|Method for the denitrosation of organic nitrosamines|
    BE869042A|1977-07-18|1979-01-17|Lilly Co Eli|PURIFICATION OF DINITROANILINES BY ELIMINATION OF NITROSAMINES|
    GB2003148B|1977-08-17|1982-02-10|Lilly Co Eli|Dinitroaniline purification with bromine and chlorine|
    US4185035A|1977-09-02|1980-01-22|Eli Lilly And Company|Dinitroaniline purification with inorganic acid halides|
    US4120905A|1977-09-21|1978-10-17|Eli Lilly And Company|Removal of nitrosating agents|
    EP0019281B1|1979-05-21|1982-12-29|Hoechst Aktiengesellschaft|Process for the removal of nitrozation agents from nitrated aromatic compounds|US5160530A|1989-01-24|1992-11-03|Griffin Corporation|Microencapsulated polymorphic agriculturally active material|
    US5461027A|1989-01-24|1995-10-24|Griffin Corporation|Microencapsulated pendimethalin and method of making and using same|
    DE4141369A1|1991-12-14|1993-06-17|Cassella Ag|METHOD FOR PRODUCING N-SUBSTITUTED NITRO-P-PHENYLENEDIAMINES|
    US5728881A|1997-03-05|1998-03-17|Srm Chemical, Ltd. Co.|Process for preparing trifluralin|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT22073/80A|IT1131182B|1980-05-15|1980-05-15|PREPARATION PROCESS OF N-DI-N-PROPIL-2,6-DINITRO-4-TRIFLUOROMETILANILINA WITH LOW NITROSAMINE CONTENT|
    [返回顶部]