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    • 专利摘要:
    METHOD OF OBTAINING 1- (OR 2-) NAPTOIC ACID OR 2,6-NAPHTAPINDICARBONIC ACID, OR ANTHRAHINON by oxidizing methyl- or dimethylnaphthapine or anthracene at a temperature of 125-130 C and a pressure of 2-4 atm in acetic acid in the presence of an acetic acid - . cobalt and manganese bromide with the subsequent isolation of the target product and catalyst recovery by distilling the water formed during the reaction, so that, in order to increase the Process efficiency, before the water formed during the reaction the reaction mixture is treated with potassium permanganate at a temperature of 80-100s, used in an amount of 9.1-25% by weight of the catalyst and 2-5% by weight of the feedstock. When orientating with respect to the indica m: (L 04.04.81 - the method of obtaining anthrac quinone; 03.03.82 - the method of obtaining 1- (or 2-) naphthoic acid or 2,6-naphthalene dicarboxylic acid.
    公开号:SU1176828A3
    申请号:SU823529501
    申请日:1982-12-20
    公开日:1985-08-30
    发明作者:Книпс Ульрих；Бемер Бертрам；Херцберг Роланд
    申请人:Рютгерсверке Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to organic chemistry, in particular, to an improved method for the preparation of 1- (or 2-) naphthoic acid or 2,6-naphthalene dicarboxylic acid or anthraquinone, products widely used in organic chemistry.
    The aim of the invention is to increase the efficiency of the process by treating the reaction mass with potassium permanganate.
    Example 1: A 0.2 l autoclave with a capacity of 0.2 l is heated and supplied with a 10 g 2-methylnaphthalene solution and a solution consisting of 50 g of acetic acid, 1.5 g of Co () –4H20 and 0.5 g, then the autoclave close, oxygen is supplied with a pressure of 2 atm and heated to 130 ° C. The process is carried out at a constant pressure of 2 atm. After the reaction time has expired (90 min), it is cooled to 80 ° C and the pressure is brought to atmospheric pressure. Then, 0.5 g (25% by weight of the catalyst and 5% by weight of 2-methylnaphthalene) of solid potassium permanganate and 15 ml of glacial acetic acid are added, after which the reaction water is azeotroped off. The distillation is stopped after 15 MP of the head product is obtained, 10 g of 2-methylnaphthalene is added again to the second cycle, 10 mg of oxygen is supplied and the mixture is heated to 150 g for 150 min. Then the catalyst is treated with 0.5 g of potassium permanganate for 150 min. and the reaction solution is used again. At the end of the third cycle after oxidation under pressure, the mixture is cooled to room temperature, the crystal mass is filtered on a putsch and after adding 0.5 g of Co (cH5COO) -4 H-jO the solution is dehydrated and the river era tio catalyst. A total of five cycles were carried out with the same catalyst. Then the reaction mixture is cooled and the naphthoic acid that has been filtered is filtered off, 500 ml of cold water is added to the filtrate, and the naphthoic acid that is separated out is filtered, washed with water and dried.
    Yield: 46.2 g of 2-naphthoic acid with a pure 85%, which corresponds to the yield, g vnsmu 65% of the theoretical.
    After recrystallization from alcohol, the product has so pl. (according to the literature, high-purity product has t. g. 185,).
    Comparative example. Example 1 is repeated with the difference that potassium permanganate is not added to the reaction mixture before the second and third cycles.
    After the end of the second cycle, the yield of 85% 2-naphthoic acid is 8.8 g, 59% of the theoretical, and after the end of the third cycle, the yield of the target product decreases sharply and amounts to 4.6 g (32.4% of the theoretical). In addition, the purity of the target product is reduced to 72%.
    Comparison of the results of example 1 and its comparative example suggests that without treatment with potassium permanganate, the recovered catalyst exhibits less activity, which negatively affects the efficiency of the process, as this reduces the yield of the target product,
    Example 2, In an autoclave with a capacity of 1 l of 100 g of I-methyl naphthalene in 250 g of acetic acid containing in solution 25 g of Co (cH5COO) 2-4 of HzO and 2.5 g are subjected to oxidation with oxygen under a pressure of 2 atm for 6 h at 125 ° C. After depressurization, the slurry of crisp t tall crude naphthoic acid slurry is cooled to room temperature and sucked off. After adding to the reaction solution 2.5 g (9.1% by weight of the catalyst and 2.5% by weight of 1-methyl naphthalene) solid potassium permanganate is heated to 100 ° C and the reaction water together with a small amount of acetic acid (20 g in total ) is removed by distillation. To the solution thus obtained, 100 g of methylnaphthalene and acetic acid are added again to replenish the amount of dehydrated) and then it is subjected to re-oxidation.
    At the end of the five cycles, most of the acetic acid is removed by distillation and the residue is extracted with water to recover the catalyst salts. The naphthoic acid 3 contained in the insoluble residue is extracted with water to recover the catalyst salts. The naphthalic acid contained in the insoluble residue is extracted with a dilute sodium hydroxide solution. 500 g of 1-naphthoic acid of 90% purity are obtained, which corresponds to a yield of 74% of the theoretical one. After recrystallization from alcohol, the product has a T. 160 ° С (according to the literature data, the high-purity product has mp 161 s). Comparative example. Example 2 is repeated with the difference that the catalyst is used in the second cycle without pretreatment with potassium permanganate. In the first cycle, the yield of 1-naphthoic acid with a 90% purity is 99 g (73.3% of the theoretical), and in the second cycle, the product yield is reduced to 48.5 g (35.9% of the theoretical ). In addition, the purity of the product is reduced to 80%. A comparison of the results of example 2 and its comparative example suggests that without treatment with potassium permanganate, the recovered catalyst shows less activity, which adversely affects the efficiency of the process. Froze The operation is analogous to example 2. For five cycles, the reaction of 50 g of 90% 2,6-dimep-yl naphthalene is subjected to oxidation. In this case, in each cycle, 10 g of aromatic carbon is subjected to oxidation with oxygen from 4 atm at 125 C in a mixture consisting of 50 g of glacial acetic acid, 2.5 g of Co (cH jCO (–4Н20, X. After each cycle, the catalyst is treated with 0.5 g (l6.6% by weight of the catalyst and 5% by weight of 2,6-dimethylnaphthal potassium permanganate. 58.6 g of naphthalene-2,6-dicarboxylic acid with a purity of 85% is obtained, which corresponds to the yield 72% of theoretical. After recrystallization from the alcohol, the product has a melting point of 300 ° C. According to laboratory data, the high-purity product has a melting point of 300 ° C. Comparative Example 3 is repeated, with the difference that before conducting the second and third cycles, potassium permanganate was not added to the reaction mixture. At the same time, the following was established. After the end of the second cycle, the yield is 85%, 2,6-naphthalene dicarboxylic acid is 11.1 g (68.2% of theoretical), and after the end of the third cycle, the yield of the target product decreases sharply and is 6.15 g (37.8% of theoretical). In addition, the purity of the target product is reduced to 74%. A comparison of the results of Example 3 and its comparative example suggests that without treatment with potassium permanganate, the recovered catalyst exhibits less activity, which negatively affects the efficiency of the process. Example4. 50 g of anthracene (95% water and a solution consisting of 150 g of acetic acid, 7.5 g of Co () and 1.3 g of MpW2-4H O are fed to an autoclave with a capacity of 1 l. Then the autoclave is closed and the reaction mixture is subjected to oxidation with oxygen at 130 ° C and a pressure of 4 atm. After 5 hours, it is cooled to 90 ° C and the pressure is brought to atmospheric. Then 1 g (ll, 4% by weight of the catalyst and 2% by weight of anthracene) of solid permanganate is added ka LIA and 25 ml of glacial acetic acid and the reaction water is distilled off. After obtaining the head product in an amount of 25 ml, the process is terminated. The mixture is then cooled The solution was subjected to reoxidation after the addition of 50 g of anthracene using eleven cycles, the results of which are shown in Table 1. The results of the eleventh cycle of the reaction show that the activity of the catalyst has not been exhausted. After crystallization from alcohol, the product of cycles 1-11 has a melting point of 284–285 ° С (according to the literature data, high-purity anthraquinonymous is of mp.286 s). Comparative example, Repeat example 4 with the difference that potassium permanganate was not added to the reaction mixture prior to the second and third cycles. In this case, the following is established.
    After the end of the second cycle, the yield of anthraquinone with 100% purity is 34.7 g (B2.4% of the theoretical, and after the end of the third cycle, the yield of the desired product sharply decreases and amounts to 16.5 g, 7% DT of the theoretical in terms of product with 100% purity).
    A comparison of the results of example 4 and its comparative example suggests that without treatment with potassium permanganate, the recovered catalyst shows less activity, which adversely affects the efficiency of the process.
    权利要求:
    Claims (2)
    [1]
    METHOD FOR PRODUCING 1- (OR 2-) NAPHTOIC ACID OR 2,6-NAPHTHALINEDICARBOXYLIC ACID, OR ANTHRAHINON by oxidation of methyl or dimethylnaphthalene or anthracene at a temperature of 125-130 ° С and a pressure of 2-4 atm in an acetic acid medium in the presence of a catalyst cobalt acetate and manganese bromide, followed by isolation of the target product and recovery of the catalyst by distillation of the water formed during the reaction, characterized in that, in order to increase the efficiency of the process, the reaction mixture formed before the water is distilled off during the reaction treated with potassium permanganate at a temperature of 80-100 ° C, used in an amount of 9.1-25% by weight of the catalyst and 2-5% by weight of the feedstock.
    Priority ”by recognition of:
    04/22/81 · - a method for producing anthraquinone;
    03.03.82 - a method for producing 1- (or 2-) naphthoic acid or
    [2]
    2,6-naphthapindicarboxylic acid.
    SU „„ 1176828
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    同族专利:
    公开号 | 公开日
    CS226447B2|1984-03-19|
    BR8207232A|1983-03-01|
    JPH0237903B2|1990-08-28|
    FI824371L|1982-12-20|
    ES8303275A1|1983-02-16|
    DE3261337D1|1985-01-10|
    JPS58500525A|1983-04-07|
    EP0077334B1|1984-11-28|
    AT10485T|1984-12-15|
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    WO1982003625A1|1982-10-28|
    US4477380A|1984-10-16|
    IT1148157B|1986-11-26|
    IT8248149D0|1982-04-01|
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    CA1169056A|1984-06-12|
    IN157294B|1986-02-22|
    FI71119C|1986-11-24|
    FI824371A0|1982-12-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB642459A|1948-06-25|1950-09-06|Robert Leslie Mcginty|Improvements in or relating to organic oxidation reactions|
    US3519684A|1966-12-27|1970-07-07|Enrique Roberto Witt|Preparation of aromatic disubstituted carboxylic acids|
    DE1940051C3|1969-08-06|1979-05-03|Ashland Oil & Refining Co., Ashland, Ky. |Process for the production of anthraquinone|
    US3969405A|1969-12-11|1976-07-13|Ostrowick Pierre M J G De Radz|Oxidation of alkylaromatics|
    US3856855A|1970-02-17|1974-12-24|Teijin Ltd|Process for preparation of naphthalene monocarboxylic acid or naphthalene dicarboxylic acid|
    JPS5541143B2|1976-02-23|1980-10-22|
    JPS52133942A|1976-05-04|1977-11-09|Kuraray Yuka Kk|Treatment of reaction mother liquor|US4556964A|1981-12-21|1985-12-03|Burroughs Corporation|Technique for monitoring galvo angle|
    CA2050866A1|1990-09-10|1992-03-11|George F. Schaefer|Oxidation of dialkyl polyaromatics to dicarboxypolyaromatics|
    WO1999040058A1|1998-02-09|1999-08-12|Rpc, Inc.|Process for treating cobalt catalyst in oxidation mixtures of hydrocarbons to dibasic acids|
    BR9907998A|1998-02-19|2000-10-24|Rpc Inc|Processes and devices for catalyst separation from oxidation mixtures|
    US6218573B1|1998-07-02|2001-04-17|Rpc Inc.|Methods of recovering catalyst in solution in the oxidation of cyclohexane to adipic acid|
    US6340420B1|1998-07-06|2002-01-22|Rpc Inc.|Methods of treating the oxidation mixture of hydrocarbons to respective dibasic acids|
    WO2000063147A1|1999-04-20|2000-10-26|Rpc Inc.|Methods of replacing water and cyclohexanone with acetic acid in aqueous solutions of catalyst|
    US6657067B2|2002-03-22|2003-12-02|General Electric Company|Method for the manufacture of chlorophthalic anhydride|
    US6649773B2|2002-03-22|2003-11-18|General Electric Company|Method for the manufacture of halophthalic acids and anhydrides|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE3115971|1981-04-22|
    DE19823207572|DE3207572A1|1981-04-22|1982-03-03|METHOD FOR THE OXIDATION OF REACTIVE AROMATES|
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