• 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:
    1,3-dichloroacetone oxime is prepared from 1,3-dichloropropanone by reaction with a hydroxylamine salt in a strongly acidic medium in the presence of a base selected from the group consisting of tertiary amines, lower alkyl amides, alkali metal bicarbonates, alkali metal carbonates and alkaline earth metal carbonates. 1,3-dichloroacetone oxime acetate is advantageously prepared by reaction of the oxime with acetic anhydride. The acetate is obtained in high purity.
    公开号:SU837320A3
    申请号:SU772445206
    申请日:1977-01-28
    公开日:1981-06-07
    发明作者:Эдвард Мацумото Кент；Хуа-Хин Чан Джимми；Роберт Бэйкер Дон
    申请人:Стауффер Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR EXTRACTING ACETATE 1,3-DICHLOROCETONOXIME
    This invention relates to an improved process for the preparation of 1,3-dichloroacetoneoxime acetate, which has biological activity and therefore can be used in agriculture in the fight against fungi and bacteria. One two-step process is known for the preparation of 1,3-dichloroacetoneoxime, concluding in that 1,3-dichloro propanone is reacted with hydroxylamine hydrochloride in the presence of ethanol and water at boiling and the oxime obtained in this way is acylated with acetic acid in benzene and in the presence of pyridine as a base at 10-20 0. The process uses a twofold excess of the hydroxylamine hydrochloride salt. As a rule, the target product obtained by this method turns black either in the separation process or during the subsequent storage ij. The disadvantage of this method is the poor quality of the target product. The aim of the invention is to improve the quality of the target product. The goal is achieved by the fact that 1,3-dichloropropanone is reacted with a hydroxylamine salt in the presence of a base at a pH of 0.5-2.0 and a temperature, followed by acylation of 1,3-dichloroacetone oxime with acetic anhydride. Calcium carbonate, pyridine or sodium carbonate is preferably used as the base. The process (both stages) is advantageously carried out in an inert organic solvent such as toluene. A relatively stable AND staining color is obtained when the desired product is standing. Distinctive features of the proposed method are the following: the process of interaction of 1,3-dichloropropanone with α-hydroxylamine salt in the presence of a base with a pI of 0.5 g-2.0, and the use of acetic anhydride as acyl-uhhadhe. In the method according to the invention, any hydroxylamine salt can be used, for example hydrochloric acid and sulfuric acid, which can be used in equimolar amounts with respect to 1,3-dichloropropanone. Any suitable base can be used in the process, provided that it can be easily dispersed throughout the reaction medium without occurrence of undesirably high pH values in certain areas. Preferred bases for this process are carboxates and bicarbates of alkali metals, and especially calcium carbonate. The carbonates and bicarbonates of other metals of these groups are also used, for example sodium carbonates of magnesium, barium and strontium, as well as sodium and potassium bicarbonates. Tertiary amines, for example triethylamine, pyridine, substitutable pyridines, for example lutidines, and dimethylaniline can also be used. In addition, lower alkylamides are also taken for this reaction, for example, acetamide formamide and dihydrogenformamide. However, they are less preferable, since, although both of them produce oximes in good yields, the reaction product may contain unreacted 1,3-dichloropropanone in such an amount that additional difficulties arise due to its irritating effect. Therefore, this compound must be separated from the obtained oxime, for which an additional purification step and appropriate equipment are necessary. . The use of strong bases for this reaction, for example, sodium and potassium hydroxides, is undesirable, since their addition can lead to the formation of sections with pH values greater than 2. A pH of 2 and-pi less can be established in different ways as active, and passive. Typically, the pH of the starting reaction mixture of 1,3-dichloropropanone and the hydroxylamine salt is approximately in the range of 3.7-4.0. As the reaction proceeds, the pH decreases due to the formation of hydrogen ions in the resultant reaction of the hydroxyl salt on the salt. Thus, for example, in one of the embodiments of the process according to the inventive method, 1, 3-dichloropropano1 and a hydroxylamine salt are reacted and, when the pH is reduced to a value of less than about 2 (usually, it takes 15–45 minutes), from add base. Then the pH of the reaction mixture is controlled and the addition of the base is adjusted so that the pH value does not exceed 2. As a rule, the total reaction time is approximately 2-4 hours and the fact that the pH of the system exceeds 2 to the first 15-45 minutes does not adversely affect the course of reactions. in some cases (example 2), the initial pH of the reaction medium may actually be less than 3.7-4.0. This can be explained by the content of acidic impurities used: 1x reagents or solvents, especially in hydroxylamine pain. In such a case, the base can be added earlier during the reaction, while controlling the pH and adjusting the addition of the base, as described above. : In accordance with one embodiment of the method, a part of the base is added at the reaction stage. In this case, a sufficient amount of mineral acid, for example hydrochloric, sulfuric, phosphoric or nitric acid, is also added at the same time in order to lower the pH of the reaction medium to an initial value of 2 or less. The oxime production step is preferably carried out in the presence of an inert organic solvent, for example benzene, toluene, xylene, chlorination of hydrocarbons, in particular chloroform, methylene chloride, perchlorethylene or 1-2 of dichloroethane. Typically, the oxime production step is carried out at a temperature of 58 ° C, depending on the base and solvent used (if a solvent is used). When using a tertiary amine, lower temperatures are preferred: 540 ° C, especially 15-25 ° C. When an alkaline earth or alkali metal carbonate is used, the reaction proceeds best at 35-45 ° C, although it can be carried out at higher temperatures, up to about 85 ° C, depending on the boiling point of the solvent. . . The reaction between 1,3-dichloroacetone oxime and acetic anhydride is carried out in the presence of an inert solvent, for example, in the presence of the listed solvents .. Minor amounts of water are permissible, provided that a separate aqueous phase does not form in the reaction medium, since there is no reaction in the two-phase system. will flow to the end. This is preferably carried out at. To complete the reaction, a slight excess of acetic anhydride should be used, for example: measures of 1.4-1.5 mol per mole of oxime. A smaller excess can be taken if the organic oxime solution is dried prior to use in the acetate preparation step. The oxime can be separated from the reaction mixture prior to reaction with acetic anhydride. However, it is preferable to both reactions — the preparation of oxime and the preparation of acetate are carried out in the presence of the same inert solvent. Since, in the first reaction, the oxime is contained in the organic layer, this layer is used in the next reaction as a solution of the oxime in a solvent. The separation of the organic phase from the aqueous phase during the oxime production step should be carried out very carefully to avoid the ingress of undesirable amount of water into the acetate formation system.
    When the pH is more than 3 or during prolonged standing, the oxime may decompose.
    In accordance with another example of carrying out the process according to the proposed method, the starting 1,3-dichloropropanone can be obtained by oxidizing 1,3-dichloropropanol with an oxidizing agent, such as sodium dichromate and concentrated sulfuric acid. The 1,3-dichloropropanone can be separated from the reaction products by extraction with toluene or another suitable solvent, and the solution of this compound can be used as one of the starting materials in the oxime reaction without separating the ketone. At all stages of the process, the separation of the solvent from the reaction product by distilling off the solvent should be carried out very carefully, since all the products are very volatile and significant amounts of them can volatilize with the solvents.
    Example. 2.5 kg (8.8 mol) of sodium dichromate dihydrate and 1 l of water are placed in a 12 l bottle. The mixture is stirred to dissolve the salt. Then, successively .1.94 kg (15.0 mol) of 1,3-dichloro-2-propanol and 2.95 kg (30 mol) of concentrated sulfuric acid dissolved in 0.75 l of water are added. The temperature during the reaction is maintained; approximately at a level of 20 s and continued to be mixed at a moderate rate. Precautions must be taken as the reaction becomes strongly exothermic when sulfuric acid is added to the reaction mixture. At the end of the reaction, the reaction mixture becomes viscous and black. ,
    Then, 3.3 l of water and 5.2 l of toluene are added to the reaction mixture and the resulting mixture is separated in phase. The lower aqueous layer is again extracted with toluene, and the combined toluene solutions are washed with a small amount of water. The yield of 1,3-dichloropropanone is about 98%.
    A solution of 1,3-dichloropropanone in toluene, obtained in the previous stage, 1.43 kg (8.7 mol) of hydroxylamine sulfate dissolved in 3 l of water, and 48 ml of concentrated hydrochloric acid is placed in a 12 l bottle. 1.19 kg (15 mol) pyridine is then slowly added with stirring while monitoring the pH. Reaction temperature
    live at the level of 20-25C. During the entire process of adding the base, the pH is maintained at 2. The addition of the base is completed in approximately 2-2.5 hours, after which the reaction mixture is stirred for an additional 0.5 hour. According to gas chromatographic analysis, the ketone is completely converted into the corresponding oxime. The reaction products are divided into phases, with the oxime contained in the toluene layer.
    The solution of oxime in toluene, obtained in the preceding stage, is placed in a 12-liter bottle and 2.2 kg (21.6 mol) are slowly added to it.
    5 acetic anhydride. The temperature of the reaction mixture is maintained at approximately 20 s. Addition of anhydride is completed in approximately 2 hours. At the end of the reaction with -.
    0 0.5 l of water is added, the solution is stirred and then divided into phases. The toluene layer is programed with a pure sodium bicarbonate solution, dried over magnesium sulfate, filtered and distilled. ; The liquid is concentrated in vacuo for 1.52 hours at a temperature of approximately 50 ° C. Get 2,041 g of acetate 1,3 dichloroacetone, t. Kip. 8082 ° C / 4 mmHg Art. Degree of purity
    0 product 95 wt.%; yield 74% (based on the initial 1, 3-dichloro-2-propa: NOL and intermediate ketone).
    Example2. in volume
    300 ml of solution of 12.7 g
    (0.10 mol) 1, 3-dichloro-2-propanone c. 29.5 ml of 1,2-dichloroethane and a solution of 9.5 g (0.058 mol) of hydroxylamine sulfate in 20 ml of water. The cell is placed in a water bath with a temperature of 40 s.
    0 The initial pH value is approximately 1.5. Tlo seems to be that. is explained by the content of acidic impurities in one of the reagents or in dichloroethane. After 60 minutes, the pH decreases to a negative value, 2.50 g (0.025 mol) of calcium carbonate is added to the reaction mixture, and after 30 minutes another 2.50 g is added (after which the pH rises to about 1.5).
    0 Total reaction time
    195 min, after which the pH is approximately 0.8. The reaction product is cooled, filtered and separated into phases. The organic phase is placed in
    A flask with a volume of 100 1 l is added to which 14.7 g (0.144 mol) of acetic anhydride is added. The temperature is maintained equal. After 180 minutes, the reaction ends at 96%; after which the mixture is allowed to cool and
    0 defend The resulting solution was distilled under vacuum at 50 ° C. 16.8 g of a light yellow liquid containing 95.2% by weight (yield 91.3%) of 1,3-dichloroacetone oxime acetate are obtained and
    5 1.3% 1, 3-dichloro-2-propanone.
    A primer, according to the method described in example 2, is prepared and expelled with oxime. Yield 98%; degree of purity is 85-89%.
    Example4. According to the method described in Example 2, an oxime is obtained. The reaction rate is maintained equal. The output of the oxime 80%; degree of purity is 85.1%.
    EXAMPLE 5 Oxime is prepared according to the method described in Example 2, but only with a single addition of 2.50 g (0.025 mol) of calcium carbonate (approximately 0.5 mol eq. Per 1 mol eq of hydroxylmethyl sulfate ;. The output of the oxime is 73%; the degree of purity is 74.1%.
    EXAMPLE 6 Oxime is prepared according to the method described in Example 2, but with the addition of only 7.50 g (0.075 mol of calcium carbonate (approximately | 1.5 mol-eq per 1 mol-eq of pdroxylamine sulfate). Yield oxime 74% / purity 79.4%.
    权利要求:
    Claims (4)
    [1]
    1. A method of producing 1,3-dichloroacetone oxime acetate by reacting 1,3-dichloropropanone with a hydroxylamine salt with a poseduchcy acylation of the obtained 1,3-dichloroacetone oxime with an acetic acid derivative using a base process, in order to improve the quality of the target product 1,3-dichloropropanone with a hydroxylamine salt is carried out in the presence of a base at a pH of 0.5-2.0, and as pro0. Acetic anhydride is used from acetic acid.
    [2]
    2. A method according to claim 1, characterized in that the reaction of 1,3-dichloropropanone with a salt
    5 hydroxylamine is carried out at.
    [3]
    3. Method according to paragraphs. 1-2-2, characterized in that calcium carbonate, pyridine or sodium carbonate is used as the base.
    Q
    [4]
    4. The method according to paragraphs. 1-3, characterized in that the process is carried out in an inert organic solvent such as toluene. . Information sources,
    f taken into account in the examination
    1. US patent number ,,
    cl. 424-327, published in 1973 (prototype).
    类似技术:
    公开号 | 公开日 | 专利标题
    SU837320A3|1981-06-07|Method of preparing 1,3-dichloroacetonoxime acetate
    EP3166611B1|2020-09-16|Process for the preparation of 4-alkoxy-3-hydroxypicolinic acids
    SU1582988A3|1990-07-30|Method of producing potassium salt of 6-methyld-3,4-dihydro-1,2,3-oxathiazine-4-on-2,2-dioxide
    CA1083828A|1980-08-19|Extraction of copper values from aqueous solutions with hydroxy-oximes
    CA1052823A|1979-04-17|Process for the preparation of cyclohexanediones-|
    SU1342419A3|1987-09-30|Method of producing 6-methyl-3,4-dihydro-1,2,3-oxathiazine-4-on-2,2-dioxide as potassium salt thereof
    KR100381133B1|2003-04-23|An energetic placitizer comprising a eutetic mixture of bis|formal, 2,2-dinitropropyl 2,2-dinitrobutyl formal and bis|formal, and a preparation method thereof
    EP0158159B1|1988-10-05|Process for the synthesis of o-substituted oxime compounds and the conversion thereof into the corresponding hydroxylamine o-substituted
    US4476322A|1984-10-09|Synthesis of dimethylmethylene dinitramine
    CN109574913B|2020-08-18|Method for preparing geminal dinitro compound by nitrate hydrate
    SU799652A3|1981-01-23|Method of preparing benzoyl cyanide
    SU516341A3|1976-05-30|Method for preparing substituted benzophenones
    KR100193108B1|1999-06-15|Process for preparing N-monosubstituted hydroxylamine
    JP4102465B2|2008-06-18|A method for removing water and ammonia from a benzophenone imine reactor effluent.
    US5393874A|1995-02-28|Preparation of N-hydroxy-N'-diazenium oxides
    KR100365648B1|2002-12-26|An energetic plasticizer comprising bis|formal and bis|diformal, and a preparative method thereof
    EP0872473A2|1998-10-21|Process for the preparation of chloroketoamines using carbamates
    KR800001175B1|1980-10-20|Process for the production of 1,3-dichloro acetone oxime its acetate derivatives
    US4167522A|1979-09-11|Guanidine pantoate
    CN113233998B|2021-12-28|Preparation method of mesotrione
    US3960915A|1976-06-01|Process for the preparation of isopropenyl isocyanate
    JP6865135B2|2021-04-28|How to treat the composition
    US4128579A|1978-12-05|Process for the manufacture of α,β-unsaturated cycloaliphatic ketoximes
    US3026328A|1962-03-20|Processes for converting l-threo-5-amino-6-phenyl dioxane to the corresponding l-erythro dioxane
    SU1330134A1|1987-08-15|Method of producing 5-phenylethynylfurfural
    同族专利:
    公开号 | 公开日
    US4128580A|1978-12-05|
    BE850789A|1977-07-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CH399823A|1959-04-28|1965-09-30|Philips Nv|Preparations for influencing the growth of plants|
    US3117987A|1959-09-04|1964-01-14|Abbott Lab|Dicyclopropylketoxime derivatives|
    US3169989A|1962-05-31|1965-02-16|Shell Oil Co|Trihalo-substituted aldoxime esters|
    US3592920A|1968-07-22|1971-07-13|Stauffer Chemical Co|Method of controlling bacteria and fungi with certain oxime esters|US4237069A|1979-07-02|1980-12-02|Allied Chemical Corporation|Production of alpha-hydroxy oximes|
    US4894461A|1981-04-27|1990-01-16|Hoechst-Roussel Pharmaceuticals, Inc.|3--6-fluoro-1,2-benzisoxazole|
    US4536578A|1982-04-09|1985-08-20|Hoechst-Roussel Pharmaceuticals Inc.|1-[3-propyl]-4-piperazines|
    US4610988A|1982-04-09|1986-09-09|Hoechst-Roussel Pharmaceuticals Inc.|1-[3-propyl]-4-piperazines useful for alleviating pain|
    US4609658A|1982-04-09|1986-09-02|Hoechst-Roussel Pharmaceuticals Inc.|1-[3-propyl]-4- piperazines useful for reducing blood pressure|
    US4420485A|1982-09-29|1983-12-13|Hoechst-Roussel Pharmaceuticals Inc.|1'-[3- proply]spiro[benzofuran-2,3' or 4'-piperidines or 3'-pyrrolidines]|
    WO1991018867A1|1990-06-06|1991-12-12|Eastman Kodak Company|Process for the preparation of ketoximes|
    US5300689A|1992-03-20|1994-04-05|Henkel Corporation|Oximation process|
    US5488161A|1992-03-20|1996-01-30|Henkel Corporation|Oximation process|
    EP2551261B1|2010-03-24|2016-11-02|Ube Industries, Ltd.|Method for producing oxime|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US65379776A| true| 1976-01-30|1976-01-30|
    [返回顶部]