• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for making 5-mercapto-1,2,3-triazoles of the formula <IMAGE> I wherein R1 is hydrogen or a C1-C4-alkyl which may also be substituted, the said process comprising (1) as a first step reacting a solution of 1,2,3-thiadiazole-5-carbohydroxamic acid derivative of the formula <IMAGE> II wherein R1 has the meaning as above and R2 is hydrogen or a univalent metal equivalent in an inert organic solvent in the presence of an acid acceptor with a solution in an inert organic solvent of an acid halide of the formula R3-X so as to form an acylated 1,2,3-thiadiazole-5-carbohydroxamic acid derivative (2) reacting as a solution in an inert organic solvent the carbohydroxamic acid derivative just obtained with an alcohol or phenol of the formula H-O-R4 so as to form a (1,2,3-thiadiazole-5-yl)-carbamic acid ester (3) then treating the thus obtained carbamic acid ester with an acetic or basic catalyst to form the 5-amino-1,2,3-thiadiazole (4) whereupon the said amino thiadiazole is subject to a rearrangement in the presence of a base followed by isolation of the product of the reaction.
    公开号:SU1241991A3
    申请号:SU802912054
    申请日:1980-04-23
    公开日:1986-06-30
    发明作者:Крюгер Ханс-Рудольф
    申请人:Шеринг Аг (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the preparation of 5 mercapto-1,2,3-triazoles, starting products in the synthesis of plant protection products and pharmaceutical preparations.
    The purpose of the invention is to simplify the process of obtaining due to the use of no more affordable and safe reagents,
    Example 1. Getting 5-mercapto-, 2,3-three ash.
    In a three-neck 500 ml round-bottomed flask equipped with a stirrer, a thermometer, and a dryer tube, 14.5 g (0.1 mol) of 1,2,3-α-thiadiazole-5-carbohydroxamic acid are suspended in 200 ml of tetrahydrofuran and mixed with solution 19 , 7 g (0.1 mol) of p-toluenesulphonic acid chloride. And 50 ml of tetrahydrofuran. To this mixture, a mixture of kz, 27.8 ml (0.2 mol) of triethylamine and 9.4 g (0.1 mol) of phenol in 75 ml of tetrahydrofuran is added dropwise to one. The temperature inside the reactor is maintained. Stir for 1 hour at 4 ° C and 3 hours at room temperature.
    round, and the internal temperature quickly rises to. After overnight, a significant amount of the solvent is evaporated in vacuo at 40 ° C, the residue is treated with 400 ml of ice water, white crystals are obtained, which are filtered off with suction and washed. first with water and then with toluene. Yield 19.2 g of phenyl ester of (1,2,3-β-thiadiazolyl-5-yl) carbamic acid,. (decomposition).
    In a three-neck 500 ml round-bottomed flask with a stirrer, a thermometer and a reflux condenser, a mixture of 19.2 g of the above crude phenyl ester (1,2,3-thiadiazol-5-yl) carbamic acid 12 g (0.3 mol) of sodium roxide and 100 ml of water, drip in 1.5 hours. Then, the solution is cooled to 20 ° C and treated with 26.4 MJ: (concentrated hydrochloric acid. After saturing, 100 g of sodium chloride is extracted with portions of ethyl acetate 50 with 17, 6 ml of constricted hydrochloric acid (only 250 ml), the extracts are combined with acidic and again extracted with ethyl acetate and shaken with solution. om 20g hydrogencarbonate in 75 ml water. The aqueous phase was mixed with 17.6 ml of concentrated hydrochloric acid and then
    tatum (portions, total 250 ml). Light yellow crystals are obtained,. Yield 6.1 g (53.1% of theor.) 5- 55 mercapto-4 methyl-1,2,3 thiazole.
    250 ml of ethyl acetate (250 ml in total) are extracted again in portions. Light yellow crystals are obtained.
    0
    Output 6.8 g (67.1% of theor.). M.p. 59 ° C.
    Example 2, Preparation of 5-mercapto-4-methyl-, 2., 3-triazole.
    In a three-neck 500 ml round-bottomed flask with a stirrer, a thermometer, and a desiccant tube, suspend 15,1 g (0.1 mol) of 4-methyl-1,2,3-thiadiazole of 5-carbohydroxamic acid in 200 ml of tetra-idrofuran and mix with 27.8 ml (0.2 mol) of triethylamine.
    Then, a solution of I9, i (0.1 mol) of acid chloride and toluene sulfonic acid in 75 ml of tetrahydrofuranium is added dropwise to this mixture over 30 minutes, while the temperature inside the reactor is kept at 4-6 ° C. dropwise for 0 minutes a solution of g (0.1 mol) of phenol in 50 ml of tetrahydrofuran while maintaining the indicated temperature inside. Stir for another 1 hour at 40 s and 3 hours at room temperature.
    After this significant part
    five
    the solvent is evaporated in vacuo at 40 C5 the residue is treated with 400 ml
    0
    ice crystals, white crystals are obtained, which are sucked off, washed first with soda and then with toluene. Yield 12 ,, 7 g of phenyl ester of (4-methyl-; 1 ;: 2 5 C-thiadiazol-5-yl) carbamic acid. M.p. 153-155 0 (decomposition). In a three-neck 500 ml round bottom
    5 flask with stirrer, thermometer and about-. A mixture of 12.7 g of the crude phenyl ester (4-methyl-1,2,3-thiadiazol-5-yl) carbamic acid in
     - 12 g (0.3 mol) of sodium hydroxide and 100 UI of water for 1.5 hours. Then the solution is cooled and treated with 24.4 ml of concentrated hydrochloric acid. After saturation, 100 g of sodium chloride is extracted with ethyl acetate (portions, 250 ml total). The extracts are combined, shaken with a solution of 20 g of potassium bicarbonate in 75 ml of water. The aqueous phase is mixed.
    five
    0 with 17.6 ml of constricted hydrochloric acid and again extracted with ethyl acetate.
    tatum (portions, total 250 ml). Light yellow crystals are obtained,. Yield 6.1 g (53.1% of theor.) 5- 55 mercapto-4 methyl-1,2,3 thiazole.
    M.p. PZ-P4 S,
    1,2,3-thiadiazole-5-carbohydr 312419914 used as starting material
    oxamic acid is obtained as follows; the solution is evaporated in a vacuum. mind with a yellow wet residue.
    A three-necked 1 liter round-bottomed count is, for further purification, dissolved in a blender with a stirrer, a thermometer and inverse 300 ml of water at, then at
    5 for 45 min slowly pass carbon dioxide. After that, light yellow crystals are filtered off and dried in vacuum under a bowl, 55.6 g (0.8 mol) of hydroxyl-, amine hydrochloride are dissolved in 400 ml of methanol by refrigerator and mixed with a methanol solution of potassium hydroxide, obtained from 42, 0
    temperature up to constant
    (0.75 mol) of potassium hydroxide and 100 ml Jules.
    methanol. Stirred for 30 minutes at Yield of 59.6 C82.1% of theory.). M.p.
    room temperature, then filter-145 about With decomposition. from the precipitated potassium chloride and the filtrate is mixed in the described AnyYogichno get 4-metsh1-1,2,3 above the reactor with 79.1 g (0.4 mol) 15-thiadiazole 5-carbohydroxyamide
    ethyl ester 1, 2,3-thiadiazole-5-acid (mp. 105-1), decomposition of carboxylic acid at 4-methyl-1,2,3 ethyl ester temperature. After two hours, thiadiazole-5-carboxylic acid with a VU your delivery at room temperature is 86.4% of theory.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING 5-MERCAPTO — 1, 2,3-TRIAZOLES of the general formula
    HS to M
    N.
    where R is hydrogen or methyl based on a 1,2,3-thiadiazole-5-carboxylic acid derivative, characterized in that, in order to simplify the process, 1,2,3-thiadiazole-5 carbohydroxamic acid of the general formula
    N s ^ C0NH0H where R has the indicated meanings, is reacted with I-tolu. with sulfonyl chloride in the presence of triethylamine in tetrahydrofuran at room temperature, the resulting acylated derivative of 1,2,3-thiadiazole-5-hydroxamic acid of the general formula
    N— N ^ CONHOSO ^ CeHs where R has the indicated meanings, is treated with phenol in tetrahydrofu.rane at 4-40 ° С at an equimolar g ratio of the reactants for the obtained ester (1,2,3-thiadiazole) of carbamic acid of the general formula.
    N— <R O
    N ^ NHCOOC 6 H 5 o
    where R has the indicated meanings, act with aqueous alkali, and then with acid.
    SU <„, 1241991 AZ
    1 124 IS
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    法律状态:
    优先权:
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