• 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. Method of 2-cyano-6-hydroxybenzthiazole irradiation using 2-chloro-6-methoxybenzthiazole, potassium cyanide and an organic solvent, characterized in that in order to increase the chain yield of the product, 2-chloro-6-methoxybenzthiazole interaction with iodotrimethylsipane, the obtained three non-silyl derivative is hydrolyzed and the resulting mixture of 2-chloro-6-hydroxybenzethiazbl and 2-iodo-6-hydroxybenzthiazole is treated with potassium cyanide in an organic solvent, preferably dimethylsulfoxide. 2. A method for preparing 2-cyano-6-oxybenzthiazole using 2-chloro-6-methoxybenzthiazop, total potassium cyanium and an organic solvent, which, in order to increase the yield of the target product, 2-chloro-6-methoxybenzthiazole is subjected to the reaction of C with iodotrimethylsilane, the obtained methyl, the methylsilyl derivative is treated with potassium cyanide in a medium of organic solvent, preferably dimethylsufine, and the sample is hydrolyzed. 3 "2-cyano-6 halfway method (L-oxybenzthiazole using 2-chloro-6-methoxybenzthiazole, potassium cyanide and organic solids, characterized in that, in order to increase the yield of the target product, 2-chloro-6-methoxybenzthiazole is subjected interaction with potassium cyanide in the medium of an organic solvent, preferably di-methylsulfoxide, the resulting product is reacted with iodine, methylsilane and the resulting trimethylsilyl derivative is subjected to ihydrolysis
    公开号:SU1055332A3
    申请号:SU802937845
    申请日:1980-06-20
    公开日:1983-11-15
    发明作者:Батц Ханс-Георг；Вульфф Карл
    申请人:Берингер Маннхайм Гмбх (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the preparation of 2-cyamoxybenzthiazole and its variants, which finds use in the synthesis of luciferin. A known method for the preparation of 2-cyano-6-hydroxybenzthiazole, which consists in the fact that 2-chloro-6-methoxybenzthiazole is reacted with pyridine hydrochloride followed by DMTA by reacting the resulting 2-chloro-6-hydroxybenzthiazole with potassium cyanide in dimethylsulfoxide. The yield of the target product lj The disadvantage of this method is the low yield of the target product. The purpose of the invention is to increase the yield of the target product. The objective is achieved in that according to the process for the preparation of 2-cyano-6-hydroxybenzthiazole, comprising the fact that 2-chloro-6-methoxybenzthiazole is reacted with iodotrimethylsilane, the trimethylsilyl derivative formed is subjected to hydrolysis and the formation of JC variant 1) (CH3) 3b. about. optionally a mixture of 2-hl6p-6-hydroxybenzthiazole and 2-iodo-6-hydroxy-phenethiazdle is treated with potassium cyanide in an organic solvent medium, preferably dimethyl sulfoxide. According to the second embodiment, 2-chloro-6-methoxybenzthiazole is reacted with iodotrimethyl silane, the trimethylsilyl derivative formed is treated with potassium cyanide in an organic solvent medium, preferably dimethyl sulfoxide, and the resulting product is hydrolyzed. According to the third variant, 2-chloro-b-methoxybenzthiazole is reacted with potassium cyanide in an organic solvent medium, preferably dimethyl sulfoxide, the resulting product is reacted with iodotrimethylsilane and the trimethylsilyl derivative is hydrolyzed. . The proposed method allows to obtain the target product with a yield of 5-52%. Process J CFCJ)
    (CHj} jeiJ
    (CH.j) Qi option
    P 2)
    / V
    / U
    ir (CHy) ySi7 aKHjOH / HgO jp 1. 2-Xno i-6-hydroxybenzPrim e thiazole; V 10 g (0.0 mol), 2-chloro-6-methoxy benzthiazole is dissolved in 30 ml of abs. ..ThiftTHoro chloroform, add 2 Tg (about 0.1 mol t "to the floor of 1 {en1 solution). 15 ml) iodotrimethylsilane and stir the mixture at a bath temperature of 80 ° C and without access of moisture to a reflux condenser. After 70 hours, another k ml of iodotrimethylsilane is added and stirring is continued for another 0 hours at the boiling point of the mixture. The reaction mixture is then suspended in 00 ml of chloroform, LLP in ml of methanol is added, and the mixture is shaken for a short time, resulting in a clear solution. 300 ml of a 10% aqueous solution of sodium thiosulfate are immediately added to it and the mixture is shaken in a separating funnel. Chloroform phase. is separated and the chloroform is extracted twice from the aqueous phase. The combined extracts are dried with sodium sulfate, mixed with carbon, carbon, filtered off after stirring and the filtrate evaporated in vacuo. 310 As a result, the semi-B, k g of the crude product, which is suspended in 300 nl of water, mix the suspension with 20 ml 2 and. sodium hydroxide solution and shake. After some time, a small amount of the undissolved product is sucked off on the filter and washed with water. My filtrate is mixed with charcoal, which after agitation is sucked off on the filter, and the filtrate is acidified with 2N. hydrochloric acid. The precipitated product is washed with water and dried in a desiccator. The result is 6.28 g of a mixture consisting of 2-chloro-6-hydroxybenzthiazole and 2-iodine-6 - hydroxybenzthiazole, which corresponds to 67.7 of the theoretical yield (when the indicated compound is obtained by the described methods, the yield is only) . The product obtained is melted at a temperature of 1 O-1b ° C, is chromatographically pure, and according to its properties it corresponds to the literature data. EXAMPLE 2. 2-Cyano-6-hydroxy6enz tigzol. To a suspension heated to 120 ° C with 3 g of potassium cyanide and 100 mg of l8-crown-6 in 150 ml of dimethyl sulfoxide, are added g obtained by the method of VII with example 1 of a mixture of 2-chloro-6-hydroxy benzthiazole and 2-iodine-6 -oxybenzthia-1zola and mix the mixture at a bath temperature of 120 ° C. After 3 hours, the reaction mixture is poured into 1 liter of ice water and the resulting solution is acidified with dilute hydrochloric acid. It is then extracted twice with 500 ml portions of diethyl ether, the extracts are washed with water, dried over sodium sulfate, mixed with coal, which is filtered off after balancing, and the filtrate is evaporated in vacuo. The result is 2.5 g of crude 2-cyano-6-oxybenzthiazole. The resulting crude is suspended in 100 ml of water and mixed with .1 n. sodium hydroxide solution. However, after a short time, the product is dissolved and a small amount of insoluble residue remains. Charcoal is added to the solution, after being stirred up, it is filtered off, the filtrate is acidified with dilute strong acid, the precipitated crystals are sucked off and dried in a desiccator. The resulting product is dissolved in 150 ml of 32 diethyl ether, the solution is washed with 100 ml of ligroin to precipitate impurities), the solution is mixed with coal and after stirring it is sucked off. After evaporation of the filtrate in vacuo, 2.0 g of 2-yano-6-oxybenzthiazole are obtained, which corresponds to 52% of the theoretical yield. The resulting compound melts at 150-200 ° C with decomposition. Froze 2-Cyano-6; hydroxybenathiazole .- 4 j ;; (0.02 mol) 2-chloro-6-methoxybenzthiazole and 2.6 g (0.04 mol}; potassium cyanide in ISO ml of dimethyl sulfoxide is stirred for 3 m at. Then the cooled solution is poured into 1 l of water, carried out twice extract with diethyl ether, wash the ether extract with water, dry with sodium sulfate and evaporate. The residue after evaporation is dissolved in 5 ml of chloroform, the resulting solution is mixed with 6 ml of tridylmethylsilane and the mixture is stirred for 100 hours at the bath temperature. Then the solution is diluted with chloroform add a small amount of meta Shake the mixture in a separatory funnel with a no-thiosulfate solution; ri, separate the mixing phase, and extract from the aqueous phase with chloroform. Combined chloroform) the extracts are dried with sodium sulfate and evaporated. The product obtained is purified on a column filled with silica gel, using as a eluent a mixture of tetrahydrofuran and and propyl ether in a ratio of t: 4. 1.5 g of 2-cyano-6-hydroxybenzthiazole are obtained as a result. which corresponds to kS% of the theoretical yield. The resulting compound melts at 190-200 ° C with decomposition. From the above examples it can be seen that using the proposed method results in a significantly cleaner product with a significantly higher yield. Thus, significant technical progress is achieved. P D and mere-C. 2-Cyano-6-hydroxybenzthiazole .. (0.015 mol): 2-chloro-6-methoxybenzthiazole is dissolved in 9 ml of absolute chloroform and mixed with 6 g of 4.5 ml (0.03 mol) iodotrimethyl5. 1055332. 6
    ilana The solution is stirred at ten-millimeters. After 3 m, the reaction mixture from a bath with a Hoper reverse is taken in approximately 800 ml of ice-cold water.
    by acid. 2 and. NA) and conducted from
    After 25 hours, an additional 3 g are added in portions of 500 and 300 ml. Extrat about ". 2.1 ml of iodotrimethylsilane and continue with water, dried with sulphate
    they stir by stirring at temperature and evaporate,
    boiling mixture. After 30 h, a solution containing a small amount
    evaporation in vacuo, the residue of solution impurities, the product is purified on silica gel in 100 ml of dimethyl sulfoxide and -O; gel 60, using 3 g of KCN as eluent (three times mixture of isopropyl ether and tetramol amount). Slurry suspension: hydrofuran, taken in ratio
    Then sew at 100®С. Output k2%.
    double extraction with chloroform
    权利要求:
    Claims (3)
    [1]
    one . Method for the preparation of 2-cyano-6-hydroxybenzothiazole using 2-chloro-b-methoxybenzothiazole, a cyanide of potassium and an organic solvent, characterized in that, in order to increase the yield of the desired product, 2-chloro-b-methoxybenzothiazole they are reacted with iodotrimethylsilane, the resulting trimethylsilyl derivative is hydrolyzed, and the resulting mixture of 2-chloro-6-hydroxybenzothiazole and 2-iodo-6-hydroxybenzothiazole is treated with potassium cyanide in an organic solvent, preferably dimethyl sulfoxide.
    [2]
    2. A method of obtaining 2-cyano-6 ’-hydroxybenzothiazole using
    2-chloro-6-methoxybenzothiazole, cyanide of potassium and an organic solvent, characterized in that, in order to increase the yield of the target product, 2-chloro ~ 6-methoxybenzothiazole is reacted with iodotrimethylsilane, the resulting tri 'methylsilyl derivative is treated with potassium cyanide in an organic solvent medium, preferably dimethyl sulfoxide, and the resulting product is hydrolyzed.
    [3]
    3. The method of producing 2-cyano-6-hydroxybenzothiazole using 2-chloro-6-methoxybenzothiazole, potassium cyanide and an organic solvent, characterized in that, in order to increase the yield of the target product, 2-chloro-6-methoxybenzothiazole is reacted with cyanide potassium in an organic solvent medium, preferably di. methyl sulfoxide, the resulting product is reacted with iodotri-; methylsilanone and the resulting trimethyl silyl derivative are subjected to 1 hydrolysis *
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    同族专利:
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    引用文献:
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    CN109456281A|2018-12-26|2019-03-12|安徽工大化工科技有限公司|A kind of preparation method of the chloro- 6- methoxybenzothiazole of 2-|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19792929115|DE2929115A1|1979-07-18|1979-07-18|METHOD FOR PRODUCING LUCIFERIN|
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