• 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:
    1. A method of producing 2,3-dichloro-5-trichloromethylpirvdine by chlorinating 2-chloro-5-trichloromethylpyridine with chlorine in the presence of a catalyst at 170-200 ° C and atmospheric pressure, characterized in that, in order to increase the yield of the desired product, As a catalyst, a compound of molybdenum or tungsten or ruthenium is used. 2. The method of Claim 1, from which it is used that tungsten hexachloride is used as a catalyst is molybdenum pentachloride, molybdenum hexacarbonyl, molybdenum oxytetrachloride or ruthenium chloride. WITH
    公开号:SU1151202A3
    申请号:SU823407196
    申请日:1982-03-11
    公开日:1985-04-15
    发明作者:Арнольд Вернер Джон；Артур Вилсон Чарльз；Эдвард Миксан Крейг
    申请人:Дзе Дау Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a process for preparing 2,3-dichloro-5-trichloromethyl pyridine, which is an intermediate compound for the preparation of herbicides. A known method for the preparation of 2,3-dichloro-5-trichloromethane 1 Pyridine by chlorination with chlorine 2-chloro-5-trichlorome methyl pyridine 170-200 C and atmospheric pressure with a catalyst FeCIjtl. As a result of the low selectivity of the process, a mixture of products is formed and the target product is obtained with a low yield (25% AO). The purpose of the invention is to improve the output and purity of the target product. The goal is achieved by the fact that according to the method of obtaining 2,3-dichloro-5-trich. Pormethylpyridine by chlorination of 2-chloro-5-trichloromethylpyridine with chlorine at atmospheric pressure in the presence of a catalyst, a molybdenum or tungsten compound or a precursor is used as catalyst As a catalyst, use tungsten hexachloride, molybdenum pentachloride, molybdenum hexacarbonyl, an oxytetra molybdenum chloride or ruthenium chloride. The initial 2-chloro-5-trichloromethylpyridine in the liquid state is brought into contact with chlorine at 170–200 ° C and atmospheric pressure or pressure up to 1,480.3 kPa (according to the manometer) and above in the presence of 1.0110 wt.% (Preferably 25 wt.% .%) catalyst. The proposed method is expediently carried out under anhydrous conditions continuously, cyclically although, if necessary, a batch process can be used. Chlorine gas is passed into liquid 2-chloro-5-trichloromethylpyridine used as a starting material, in the presence of a catalyst with at least an equimolar amount of gaseous reactant (it is desirable that an excess of chlorine is 0.3-10 mol / h mole source material). The uninterrupted transmission of excess chlorine gas through the reaction mixture not only provides a large yield of reagent, but also displaces by-products such as carbon tetrachloride or hydrogen chloride. The optimal chlorine gas feed rate depends on the temperature and pressure of the reaction, the volume of the reaction mixture, etc. An excess of chlorine of 0.35 mol / h per 1 mol of 2-chloro-5-trichloromethylpyridine is usually used. The catalysts can be used with inert supports such as, for example, aluminum, silicon, silicon aluminum, various clays and molecular sieves. Increasing the temperature from 10 to 15 ° C increases the reaction rate by about two times, and the pressure from 790.8 to 1480.3 kPa (according to the manometer) also contributes to this. Example 1. A mixture of 23.1 g (0.1 mol) 2 -chloro-5-trichloromesh1pyridine and 2.0 g (0, OL5 mol) of tungsten hexachloride are heated at 120 ° C, chlorine is passed into this mixture for 42.5 hours. Chromatography of the vapor phase showed the presence of 18% 2, 3-dichloro-5 -trichloromethylpyridine. Then the reaction mixture is heated to 170-175 ° C for 7 hours with the addition of chlorine. After this, the content of 2, 3-dichloro-5-trichloromethylpyridine is set to 95% by chromatography on the vapor phase. The reaction mixture is diluted with hexane and washed with water, the organic layer is separated, dried over MgSO4 and the solvent is removed by evaporation. 26.7 g of a yellow liquid are obtained. During distillation, 24.9 g of 95.6% 2, 3-dichloro-5-trichloromethylpyridine are obtained (yield 89.7%), b.p. (1 mm Hg). The analysis showed the presence of the following impurities,%: 2,3,5,6-Tetrachloropyridin1, 6 2-Chloro-5-trichloromethylpyridine 1,6 2,3,6-Trichloro-5-trichloromethylpyridine1, 2 Example 2. Chlorine is slowly blown into the mixture 5773 g (25 mol) of 2-chloro-5-trichloromethyl. Pyridine and 496 g (1.25 mol, 5 mol.%) Of tungsten hexachloride.
    3
    heated to 175-185 ° C. After 27.5 hours, the reaction mixture is heated and dissolved in carbon tetrachloride. The organic layer is washed with sodium carbonate solution and dried over anhydrous sodium carbonate. Upon evaporation of the solution, 6793 g of a yellow-orange liquid are obtained. During distillation, 6079 g of a workable product are obtained, t. Bale. 90 ° C (1 mm Hg). Vkod 91%. Analysis of the product by gas chromatography showed that it contained 94.2% of 2,3-dichloro-5-trichloromethylpyridine.
    Example 3. The process is carried out in a logical way for example 1 using 25 g (0.11 mol) of 2-chloro-5-trichloromethylpyridine and 1.25 g (5 wt.%) Of tungsten hexacarbonyl as a catalyst. After 14 h, the product is treated in the same way as Example 2. 18.0 g of orange-yellow liquid are obtained. After distillation, 15.4 g (yield, 53.4%) of the desired product of the following composition (internal gas chromatography) are obtained,%:
    2,3-Dichloro-5-trichloromethylpyridine 86.06
    2-Chloro-5-trichloromethylpyridine 2.32
    2,3,6-Trichloro-5-trichloromethylpyridine 5, 12
    Example 4. Example 1 was repeated using 1.37 (0.005 mol) molybdenum pentachloride as a catalyst at 170-175 ° C. After 13.5 hours, the product is processed and dried, as in Example 1.
    After distillation using a Vigre column, 23.5 g of a colorless liquid are obtained, by distilling which 22.2 g (83.7% of the desired product containing 94.5% of 2,3-dichloro-5-trichloromethylpyridine) can be obtained. the following impurities,%:
    2,3,5,6-tetrachloropyridin1, 7
    2-Chloro-5-trichloromethylpyridine 2.7
    2,3,6-Trichloro-5-trichloromethylpyridine 1,1
    Example 5. The process is carried out analogously to example 3 using 1
    molybdenum pentachloride as a catalyst. After 8.5 hours, the product is treated as in Example 2. 20.5 g of a yellow liquid are obtained. After distillation, 18.56 g (63.6%) of the desired product of the following composition (gas chromatography) are obtained,%:
    2, 3-Dichloro-5-trichloromethylpyridine, 95.3 2-Chloro-5-trichloromethylpyridine, 9
    2,3,6-Trichloromethylpyridin2, 0
    - Example 6. The process is carried out analogously to example 3 using molybdenum hexacarbonyl as a catalyst. After 24 hours, the product is treated analogously to example 2 to obtain 18 g of a liquid, after distillation of which 14.24 g (48.8%) of the desired product is obtained (gas chromatography),%: 2,3-Dichloro-5-trichloromethylpyridin83, 3
    2-Chloro-5-trichloromethylpyridine 2.5 2,3,6-Trichloro-5-trichloromethylpyridine 7.6 Example 7. The chlorine is slowly bubbled into a mixture of 23 g (0.1 mol) of 2-chloro-5-trichloromethylpyridine and 2, 5 g (10 wt.%) Of molybdenum oxytetrachloride (MoCP, vO), heated to within 12 hours. After distillation, 18.8 g (71%) of the desired product are obtained. The mixture of the reaction products has the following composition (gas chromatography),%: 2, 3-Dichloro-5-trichloromethylpyridine 76.5 2-Chloro-5-trichloromethylpyridine2, O
    2,3,6-Trichloro-5-trichloromethylpirtztsin 1,8 2,3,5,6-Tetrachloropyridin11, 8
    Pentachloropyridine 3,9 2,3,6-Trichloropyridin 3, 2
    Example 8. Chlorine is slowly bubbled into a mixture of 2-chloro-5-trichloromethylpyridine (23.1 g 0.1 mol) and ruthenium chloride (1.04 g, 0.005 mol) at 175-180 ° C for 29.5 hours. After cooling
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING 2,3-DICHLOR-5-TRICHLOROMETHYLPYRIDINE by chlorination of 2-chloro-5-trichloromethylpyridine with chlorine in the presence of a catalyst at 17O-2 ° C and atmospheric pressure, characterized in that, in order to increase the yield of the target product, as a catalyst A compound of molybdenum or tungsten or ruthenium is used.
    [2]
    2. The method according to claim 1, characterized in that tungsten hexachloride, molybdenum pentachloride, molybdenum hexacarbonyl, molybdenum oxytetrachloride or ruthenium chloride are used as a catalyst.
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    同族专利:
    公开号 | 公开日
    IL64939A|1984-09-30|
    ZA82716B|1983-09-28|
    AR229175A1|1983-06-30|
    BR8201194A|1983-01-18|
    CA1162550A|1984-02-21|
    DE3261579D1|1985-01-31|
    AU8020182A|1982-09-16|
    KR830009026A|1983-12-17|
    ES8303339A1|1983-02-01|
    EP0060462A1|1982-09-22|
    YU52082A|1985-03-20|
    GB2094788A|1982-09-22|
    JPS6017788B2|1985-05-07|
    JPS57165367A|1982-10-12|
    AU549161B2|1986-01-16|
    HU186912B|1985-10-28|
    DK157855C|1990-07-30|
    EP0060462B1|1984-12-19|
    DK157855B|1990-02-26|
    IL64939D0|1982-04-30|
    KR860000584B1|1986-05-17|
    US4331811A|1982-05-25|
    GB2094788B|1984-10-31|
    ES510354A0|1983-02-01|
    DK107482A|1982-09-13|
    CS226444B2|1984-03-19|
    NZ199723A|1984-12-14|
    引用文献:
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    BE624800A|1961-11-15|
    US3186994A|1962-10-18|1965-06-01|Dow Chemical Co|Polychloropyridines|
    US3244722A|1964-01-28|1966-04-05|Dow Chemical Co|Certain ethers of pyridine compounds|
    US3420833A|1967-09-08|1969-01-07|Dow Chemical Co|Vapor phase production of polychlorinated compounds|
    US3538100A|1968-03-15|1970-11-03|Olin Corp|Process for preparing highly chlorinated pyridines|
    US3732230A|1970-12-07|1973-05-08|Dow Chemical Co|Liquid phase polychlorination of pyridine hydrochlorides|
    US4256894A|1978-04-24|1981-03-17|The Dow Chemical Company|Preparation of chlorinated pyridines|
    CA1089468A|1978-04-24|1980-11-11|The Dow Chemical Company|Process for preparing 2,3,5,6-tetrachloropyridine andpentachloropyridine|
    CA1084936A|1978-06-19|1980-09-02|Dow Chemical Company|Preparation of polychlorinated pyridines from 2,4- dichloro-6- pyridines|JPS6315271B2|1980-03-07|1988-04-04|Ishihara Sangyo Kaisha|
    JPS6346748B2|1981-11-04|1988-09-19|Ishihara Sangyo Kaisha|
    US4701532A|1983-03-25|1987-10-20|The Dow Chemical Company|Method of selectively chlorinating 2-chloro-5- pyridine in the 3-position|
    US4483993A|1983-04-08|1984-11-20|Kalama Chemical, Inc.|Production of polychlorinated pyridine mixtures by liquid phase chlorination of beta-picoline or beta-picoline hydrochloride|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/243,166|US4331811A|1981-03-12|1981-03-12|Preparation of 2,3-dichloro-5-trichloromethylpyridine|
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