• 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:
    1,2,4-triazin-5-one compounds of the general formula (I) <IMAGE> (I) where R is <IMAGE> are prepared by reacting a compound of general formula (II) <IMAGE> (II) in which R is defined above with either (a) a tertiary alcohol of general formula (III) HO-R'(III) in which R' is a t-alkyl group having 4 to 18 carbon atoms, especially t-amyl or t-octyl or preferably t-butyl or (b) an alkene of general formula (IV) <IMAGE> (IV) in which R1 and R2 are the same or different and are hydrogen or an alkyl group and R3 and R4 are the same or different and wherein the alkyl groups in each case can be 1 to 15 carbon atoms and wherein preferably R1 and R2 are hydrogen and R3 and R4 each are methyl to form an alpha -ketocarboxylic acid amide of general formula (V) <IMAGE> (V) and this, in a given case after previous saponification to the free acid, condensed with thiocarbohydrazide <IMAGE> to form a 1,2,4-triazin-5-one compound of general formula (VI) <IMAGE> (VI) and then the mercapto group is methylated.
    公开号:SU791236A3
    申请号:SU782639548
    申请日:1978-07-20
    公开日:1980-12-23
    发明作者:Кленк Херберт；Шварце Вернер；Лейхтенбергер Вольфганг
    申请人:Дегусса (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for producing derivatives of 1,2,4-triazine · -5-one, which may find application in agriculture.
    Known methods for the preparation of derivatives of 1,2,4-triazin-5-one, for example, 3-methylmercapto-4-amino-b-tert. butyl-1,2,4-triazin-5-one, by reacting tert.butylglyoxylic acid with thiocarbohydrazide Yu
    II [2] or by reacting! -Digaloid-3,3-dimethylbutanoic acid with thiocarbohydrazide [h].
    A disadvantage of the known methods is the difficulty of obtaining the starting products associated with the use of toxic compounds.
    A known method for producing 3-methylmercapto-4-amino-6-tert.butyl-1,2,4-triazin-5-one by reacting 20 pivaloyl chloride with isonitriles, hydrolyzing the resulting imide chloride to 4-ketocarboxylic acid amide and subsequent interaction of the amide with thiocarbohydrazide in a polar solvent 25 and subsequent methylation of the 3-mercapto compound [4J The disadvantage of this method is the use of hard-to-reach and foul-smelling isonitriles and insufficiently high yield of the corresponding 3-mercapto compound (60% or 79%) ·
    The purpose of the invention is to simplify the process through the use of more affordable starting products, increasing the yield and expanding the assortment of the target products.
    This goal is achieved by the described method for producing derivatives of 1,2,4-triazin-5-one of the general formula I ft
    where R-CHj-e ’’ with the inclusion of the general formula or sn ^ 'group, is that the compound
    I-c-sc> where R has the indicated meanings, is reacted in the presence of an acid with a tertiary alcohol of the formula III
    0H-R4, where R is a tert. Alkyl residue, or with an alkene of formula IV where R 1 and R 2 are hydrogen, '
    R_ and Rj are the same or different • and mean a lower alkyl residue, and the resulting ci-ketocarboxylic acid amide of general formula V
    Rcc-nhO '' and k, l 0 0 'where R and R have the indicated meanings, directly or after preliminary saponification to free о £ -ketocarboxylic acid, they are condensed in a polar solvent with a thiocarbohydrazide of the formula HgN-NH-CS-NH- NHg followed by methylation of the obtained 3-mercapto-4-amino-1,2,4-triazin-5-one of the formula to
    The products are isolated by known methods, in general general form or
    The interaction of the acyl cyanides of the formula II with a tertiary alcohol of the formula hi or with an alkene of common base IV is carried out under the condition called the Ritter graph-Ritter reaction.
    The reaction can be carried out in the absence of a solvent, although it is better to carry out the reaction in the presence of an organic solvent, preferably. Use glacial acetic acid or dichloromethane. Other solvents that can be used are higher esters, such as diisopropyl dihydrogen, and alter. Preferred ~ -o n five are butyl ether ether.
    The temperature in a wide process is carried out from -20 and С to + 50 ° С.
    The components are reacted in such proportions that 1 mole of acyl cyanide accounts for an excess of stoichiometric amount of alcohol or alkene. For example, 1-20 moles, preferably 1.5-2 moles, of alcohol or alkene are added per 1 mol of acyl cyanide. Acid is also used in a small excess. For example, from 1 to 10 moles, preferably 1.1 to 1.5 moles, of an acid are used per mole of acyl cyanide.
    Sulfuric acid is preferably used, but other sulfonic acids such as benzenesulfonic acid can also be used.
    After hydrolysis of the reaction mixture, ketocarboxylic acid amides can be isolated by known methods, for example, crystallization or extraction followed by crystallization or distillation .:
    The acyl cyanide of general formula 111 is prepared by known methods or of carboxylic acid hydrogen halides by reaction with metal cyanides. .
    4G
    That is, the <Z-ketocarboxylic acid alkylamides obtained in the first step of the process according to the invention, which correspond to general formula V, can be introduced directly into the further reaction with thiocarbohydrazide in the presence of a polar solvent, such as alcohols, water, dimethyl sulfoxide, dimethylformamide, etc. d. or mixtures thereof and, if appropriate, in the presence of an acidic catalyst, preferably hydrochloric acid or sulfuric acid, in an amount which is at least equivalent to the amount of amide. In this case, temperatures that lie between 0 g, C and the boiling point of the solvent can be maintained.
    It is also possible tert-alkylamides of d-ketocarboxylic acids of the general formula V are first converted to free ol-ketocarboxylic acids, which is carried out by known methods, and then cyclized with thiocarbohydrazide.
    In both cases, the sulfur atom is then methylated by known methods, for example P, by treatment with a methylating agent such as methyl iodide, methyl bromide. or dimethyl sulfate in a basic medium.
    Example 1
    . sn ^ CH b
    CHj-c-CO-ch cn ^ - s - co-somn-s. - sn ^
    MF ^ MF- ^ MF ^
    111 g (1.0 mol) of pivalocyanide are added to a mixture of 148 g (2.0 mol) of tert.-butanol and 50 ml of methylene chloride. Then, with stirring at 0-5 ° C was added dropwise 150 g of 98% sulfuric acid, immediately thereafter the temperature was raised to 20 C. Stirring is continued minutes the reaction mixture for 4 hours, after which the mixture was poured into 400 g of ice and stirred current. 30 clays. Everything was diluted immediately afterwards with 300 ml of methylene chloride, the organic phase was separated and the methylene chloride solution was evaporated. There remains a white, crystalline precipitate, which is washed with approximately 500 ml of water on the filter. After that, the precipitate is dried. Remains 133 g (72%) of N-tert.-butylamide trimethylpyruvic acid with so pl. 63-65 ° C.
    Elemental analysis.
    Found,%; C 6-4.59, ’H 10.44, 'N7.32.
    Calculated,%: C 64.38, H 10.34, N7.56.
    io-butylene
    --------------> sn
    CH - C-C0CN
    1
    CH-J OC
    J-C - СО-СО - N4 - s.-Сл + b
    CH
    111 g (1.0 mol) of pivaloyl cyanide are added to a mixture consisting of 150 ml of glacial acetic acid and 150 g of 100% sulfuric acid. Then, 112 g (2.0 mol) of isobutylene are passed with stirring at a temperature of 0 ° C - 10 ° C for ς h.
    Immediately after this, the temperature was raised to 20 ° C and the reaction mixture was continued to stir for 2 hours. Then, 5 N were added dropwise with gentle cooling. aqueous sodium hydroxide solution until pH = 8. The mixture is stirred for another 30 minutes and the precipitated N-tert-butyl amide of trimethylpyruvic acid is suctioned off. Remains
    172 g (93%), counting on the entered 15 cyanide acid. Amide has a melting point of 63-65 ° С and is identical with the amide described in paragraph a).
    G h® / ^ 0
    CHj-C-cO-CO- NH-O-CH ^ --- snus S00I-C0-tai, s ex,
    185 g of N-tert.-butylamide trimethyl * pyruvic acid in 1 liter of 5 N. HC1 is heated for 10 hours to reflux. After cooling, it is shaken with methylene chloride and the methylene 3D phase is then extracted with a dilute NaOH solution. The aqueous chain solution is then acidified again with concentrated hydrochloric acid until pH = 1 and then shaken with ethyl acetate 35. The ethyl acetate extract was evaporated. Remains 97.7 g (75% of theory) of methyl pyruvic acid in the form of a light oil, which after some time begins to crystallize.
    d)
    Si. 5H. N '^ 1 / C = o · x N tm = g (0.5 mol) of thiocarbohydrazide is heated in 600 ml of water to a boil. With stirring, 65 g (0.5 mol) of trimethylpyruvic acid obtained in step c) in ethanol are added dropwise for about 2 hours. Then, another 4 hours are heated to reflux. The reaction mixture is cooled and crystals are suctioned off. After drying, they release 94 g (94% of theory) of 3-mercapto-4-amino-6-tert-butyl-1,2,4-triazin-5-one (mp. 212-214 ° C).
    e) Methylation of 3-mercapto-4-amino-6-tert-butyl-1,2,4-triazin-60-5-one.
    100 g obtained according to paragraph g) of the compound are dissolved in a mixture consisting of 250 ml of 2 N. NaOH and
    250 ml of methanol and then 65 are mixed with 75 g of methyl iodide. Immediately after this, the mixture was stirred for another 4 hours at 20 ° C. The crystallized reaction product is suctioned off, dried and recrystallized from benzene. Obtain 92 g (80% of theory) of 3-methylmercapto-4-amino-6-tert-butyl-1,2,4-triazin-5-one with so pl. 12b’s
    PRI me R 2.
    CH, -c-CO-CONri-c-OH. thiocarbohydrazide CMi, CMx
    To 53 g (0.5 mol) of thiocarbohydrazide in 500 mh 1 n. HCI is added dropwise with stirring and heating to reflux
    92.5 (0.5 mol) obtained in example 1 a). trimethylpyruvic acid tert-butylamide in 200 mp ethanol. Immediately after this, the reaction mixture is heated. 8 hours. After cooling, dilute 1 liter of water and suction the crystals. 72 g (72% of theory) of the desired triazinone are isolated (mp. 209-213 ^ 0). Methylation is carried out as described in example G d).
    Example 3. a) Obtaining (1-methyl-cyclopropyl) -glyoxyl-tert-butylamide.
    109 g (1 mol) of (1-methyl-cycdopropyl) -carboxylic acid cyanide are added to a mixture of 130 g of tert-butanol and 130 ml of methylene chloride. ' Then, with stirring, 100 g of 98% sulfuric acid are added dropwise at 0-5 ° C., the temperature is raised to 20 ° C. and stirred for another 4 hours, 18 ml of water are added and the reaction mixture is stirred for another 30 minutes. Then it is diluted with 500 ml of CH ^ C ^ and when cooled with an aqueous solution of NaOH, pH = 6. The solution of CH, C is then evaporated.
    181 g (98.9%) of (1-methyl-cyclopropyl) -glyoxyl-tert.-butylamide remained, mp. 80 ° C.
    Elemental analysis.
    Found,%: C 65.2; H 9.4, ’N 7.45. Calculated,%: C 65.5; H 9.3, *
    N, 7.65.
    b) Preparation of 4-amino-b- (1-methyl-cyclopropyl) -3-mercapto-1,2,4-triazin-5-one.
    183 g of (1-methyl-cyclopropyl) -glyoxylic acid tert.-butylamide and 112 g of thiocarbonylhydrazide are added to the mixture consisting of 1 liter of 1 N. hydrochloric acid and 1 l of ethanol. The reaction mixture is boiled for 8 hours at reflux boil, cooled, diluted with 1 L of water and the crystals are sucked off on a filter. Get white crystals with a yellow sheen, which are dried. Yield - 152.6 g (77.1 from theory), mp. 137-138 ° C.
    Elemental analysis.
    Found,%: C 42.2; H 5.1; N, 28.1; S 16.1.
    ' c 7 H <e N 4 0 2 . (M 198)
    Calculated,%: C 42.4; H 5.05;
    N, 28.3; S 16.16.
    c) Methylation to 4-amino-b- (1-methyl-cyclopropyl-3-methylthio-1,2,4-triazin-5-one.
    198 g obtained according to paragraph b) of the compound are dissolved in 500 ml of 2 N. NaOH solution and add 500 ml of methanol and 150 methyl iodide. The reaction mixture is stirred for 6 hours at 20-30 <> C. The resulting crystals are suctioned off, washed and dried. Receive 174.5 g of the final product (at 40 ° C is sown in vacuum) in the form of white crystals, so pl. 115116 ° C.
    The yield is 82.3% of theory.
    Elemental analysis.
    Found,%: C 45.3; H, 5.8; N, 26.1; S, 15.3.
    Calculated,%: from 45.3; H, 5.7; N, 26.4; S, 15.1.
    权利要求:
    Claims (4)
    [1]
    where “and R is hydrogen; are the same or different and mean a lower alkyl residue, and the resulting amide with α-ketocarboxylic acid of the general formula Y Rcc-ny, and 00, where R and R have the indicated values directly or after pre-saponification to the free α-carboxylic acid, condense in a polar solvent with with a thiocarbohydrazide of the formula H2N-NH-CS NH-MH2 followed by methylation of the 3-mercapto-4-amino-1 2,4-triazin-5-one formula obtained. The products are isolated using known methods. The interaction of the acylcyanides of the general formula II with the tertiary alcohol of the general formula 1 (one Whether it is carried out with an alkene of general formula IV under the condition of the so-called Ritter reaction or a graph-Ritter reaction. The reaction can be carried out in the absence of a solvent, although it is better to carry out the reaction in the presence of an organic solvent, it is preferable to use glacial acetic acid or dichloromethane. solvents that can be consumed are higher esters, like dibutyl ether or diisopropyl ether. The reaction temperature varies over wide ranges. Preferably the process is carried out from. The components are reacted in such ratios that the stoichiometric amount of the alcohol or alkene is greater than 1 mole of acyl cyanide. For example, 1 to 20 moles, preferably 1.5 to 2 moles, of an alcohol or alkene are added per mole of acyl cyanide. Acid is also used in a small excess amount. For example, from 1 to 10 mol, preferably 1.1-1.5-mol, acid is used per 1 mol of acyl cyanide. Sulfuric acid is preferably used, but other sulfonic acids, such as -benzenesulfonic acid, can also be used. After hydrolysis of the reaction mixture, the amides of ketocarboxylic acids can be isolated by known α-methods, for example, crystallization or extraction, followed by crystallization or distillation: Acyl cyanides of general formula U1 are prepared using known methods, or hIlogen anhydrides of carboxylic acids in the resultant of interaction with cyanide methanol. . - alkylamides of ot-ketocarboxylic acids, obtained in the first stage of the process according to the invention, which correspond to the general formula V, can be introduced directly into further interaction with the thiocarbohydrazide in the presence of a polar solvent, such as alcohols, water, dimethyl sulfoxide, dimethylformamide, etc. . or mixtures thereof, in accordance with the case, in the presence of an acidic catalyst, preferably hydrochloric acid or sulfuric acid in an amount that is at least equivalent to the amount of amide. In this case, it is possible to keep the temperature between the and the boiling point of the solvent. It is also possible to transfer tert.-alkylamides with (.- ketocarboxylic acids of general formula V first into free o1-ketocarboxylic acids, which is carried out by known methods, and then carry out cyclization with thiocarbohydrazide. In both cases, the sulfur atom is methylated by known methods For example, as a result of treating with a methylating agent, such as methyl iodide, methyl bromide, or dimethyl sulfate in the basic medium. Example 1. CHj. CH CH Cvu-c-co-SI 1Ret-b thio | Ln, -c-co-e-NH- c - cn, 111 g (1.0 mol) of pivalocyanide was added to a mixture of 148 g (2.0 mol) of tert-b utanola and 50 ml of methylene chloride. Then, with stirring at a temperature of 0-5 ° C, 150 g of 98% sulfuric acid are added dropwise, immediately after this the temperature is raised to 4 hours. The mixture is then stirred for 4 h, then the mixture is poured onto 400 g of ice and stirred for 30 clays. All is diluted immediately after this with 300 mp of methylene chloride, the organic phase is separated and the methylene chloride solution is evaporated. A white, crystalline precipitate remains, which is washed on the filter with approximately 500 ml of water. After that, the precipitate is dried. 133 g (72%) of N-tert.-butylamide of trimethylpyruvic acid remained, with a mp. 63-65 C. Elemental analysis. Found,%: C 6-4,59; H 10.44, N7.32. Calculated,%: C 64.38, H 10.34, N 7.56. Ybc-butylene CHj-C-CO-CO-NH-CCH CHt, -C-COCM CHgI HI 3 J CHL 111 g (1.0 mol) pivaloyl cyancide is added to a mixture of 150 ml of glacial acetic acid and 150 g 100% sulfuric acid. Z. then pass with stirring at a temperature - for 1 h, 112 g (2.0 mol) of isobutylene. Immediately thereafter, the temperature is raised to and continue to stir the reaction mixture for 2 hours. Then drift with a slight cooling of 5 and. aqueous solution of sodium hydroxide until the pH is adjusted. Stir for another 30 minutes and the precipitated N-tert-butylamine trimethyl pyruvic acid is sucked off. 172 g (93%) remain, counting on the introduced cyanide acid. The amide has a melting point of b3-65 ° C and is ideal with amide, described in a). . t. h® / i, o'.CO-CO-MI-C-CH "i liii -.- CH-C-CO-C 185 g M-tert.-butyl.tida trimethylpyruvic acid in 1 liter 5 n . The HCI is heated for 10 hours to reflux temperature. After cooling, shake with 5-ethyl chloride and then extract the methylene chloride phase with a diluted NaOH solution. The alkaline aqueous solution is then acidified again with concentrated hydrochloric acid to a pH of 1 and then shaken with ethyl acetate. Ethyl acetate extract evaporates. 97.7 g (75% of theory) remains with tilpyruvic acid as a light oil, which after some time begins to crystallize. D) Sy-G-SOSOOI 1UO RBOGU.DIRyZ, IL Ism ...., S ./3 G (0.5 mol) thiocarbohydrazide are aggravated in 600 ml of water until boiling. While stirring, 65 g (0.5 mol) obtained under a point of trimethyl pyruvic acid in ethanol for about 2 are added dropwise. Then another 4 hours is heated to reflux temperature. The reaction mixture is cooled and the crystals are sucked off. After drying them, S4 g (94% of theory) of 3-mercapto-4-amino-6-tert-butyl-1, 2,4-triazin-5-one is isolated (mp 212-214c). e) Methylation of 3-mercapto-4-amino-6-tert-butyl-1, 2,4-triazin-5-one. 100 g of the compound obtained according to d) is dissolved in a mixture consisting of 250 ml of 2N. -NaOH and 250 ml of methanol and then 75 g of methyl iodide are mixed. Immediately after this, the mixture is stirred for another 4 hours at. The crystallized reaction product is filtered off with suction, dried and recrystallized from benol. Obtain 92 g of f80% of the theory-methyl mercapto-4-amino-b-tert-butyl 1, 2,4-triazin-5-one with t, pl. 126 C. Example 2. -CHj 9 "1 SI, -c-CO-COMN-CN. thiocarbohydrazide 3 I10. to 53 g (0.5 mol) of a thiocarbohydrazide at 500 mch 1 n. HCi with stirring and heating to reflux temperature is added dropwise 92.5 (0.5 mol) of tert-butylamide trimethyl pyruvic acid of 3,200 MP of ethanol prepared by measure 1 a). Immediately thereafter, the reaction mixture is heated, 8 hours. After cooling, the mixture is diluted with 1 l of water and the crystals are sucked off. 72 g (72% of theory) of the desired triazinone are isolated (mp. 209-213 s). Methylation is carried out as described in Example D (d). Example 3. a) Preparation of (1-1 "5-methyl-cyclopropyl) -glyoxyl-tert-butylamide. 109 g (1 mol) of cyanide (1-methyl-diclopropyl) -carboxylic acid are added to a mixture of 130 g of tert-butanol and 130 ml of methylene chloride. Then, with stirring, 100 g of 98% sulfuric acid are added dropwise at 0-5 ° C, the temperature is raised to and stirred for another 4 hours, 18 ml of water are added and the reaction mixture is stirred for 30 minutes. Then it is diluted with 500 ml of CH2Cl2 and, with cooling with an aqueous solution of NaOH, the value. The solution is then evaporated. 181 g (98.9%) of (1-methyl-cyclopropyl) -glyoxyl-tert remains. - butylamide, so pl. 80 C. Elemental analysis. Found,%: C 65.2; H 9.4, N 7.45. Calculated,%: C 65.5; H 9.3, S 7.65. b) Preparation of 4-amino-6- (1-methyl-cyclopropyl} -3-mercapto-1, 2,4-triazin-5-one. 183 g of (1-methyl-cyclopropyl) -glyoxylic acid tert-butylamide and 112 g of thiocarbonyl hydrazide is added to a mixture of 1 l of 1N hydrochloric acid and 1 l of ethanol. The reaction mixture is boiled for 8 hours at reflux temperature, cooled, diluted with 1 l of water, and the crystals are sucked off on a filter White crystals with a yellow luster are obtained, which are dried. The yield is 152.6 g (77.1 from theory), mp 137-138 pp. Elemental analysis Found:%: C 42.2 / H 5.1 ; N 28 S 16.1. (M 198) Calculated,%: C 42.4; H 5.05; N 28.3; S 16.16. C) Methylation to 4-a.mino-b- (1-methyl-cyclopropyl-3-methylthio-1, 2,4-triazin-5-one. 198 g of the compound obtained according to point b) are dissolved in 500 2 N, solution of NaOH and 500 ml of methanol and 150 methyl iodide are added. The reaction mixture is stirred 6 at 20 ° C. The formed crista is filtered off with suction, washed and dried. 174.5 g of final product are obtained (as dried under vacuum) as white crystals. m.p. 115116 C. Output - 82.3% of theory. Elemental analysis. Found,%: C 45, H; H 5.8, N 26 S, 15.3. Calculated,%: from 45.3 / H 5.7 / N 26.4, S 15.1. The invention The method of obtaining 1,2,4-triazin-5-one derivatives of the general formula .. ANCH where or. which includes the interaction of the production of s.-ketocarboxylic acids with thiocarb hydrazide in a polar solvent, followed by methylation of the 3-mercapto-4-amino-1, 2,4-triazine, which has been developed, which, in order to simplify the process, increase the yield and expanding the range of desired products, the compound of general formula II -c-cv, where R has the indicated meanings, is reacted in the presence of an acid or with a tertiary alcohol of general formula IJ (HO, -RR is a alkyl tertiary residue. or with an alkene of general formula IV R where R and R are. hydrogen, and R is one are different or mean a lower alkyl residue, and the resulting amide with β-ketarboxylic acid of general formula VR-CC-NHR is NO r -f00 where R and R have the indicated meanings, directly njyi after pre-saponification to free C-ketocarboxylic acid, is condensed with thiocarbohydrazide formula N2H-NH-CS-NH-NH2. Sources of information taken into account in the examination 1. England patent 1464810, class C 2 C, 16.02.77.
    [2]
    2. US patent 3671523, cl. 260-248,1972.
    [3]
    3. US patent number 4013649, cl. 260-248, 03.22.77.
    [4]
    4. Forward Germany No. 2165554, cl. 12 p 10/05, 1973 (prototype).
    类似技术:
    公开号 | 公开日 | 专利标题
    SU791236A3|1980-12-23|Method of preparing 1,2,4-triazin-5-one derivatives
    KR840001612B1|1984-10-11|Process for preparing 4 - quinolinones
    FI74279C|1988-01-11|TRANSMISSION OF A THERAPEUTIC PRODUCT THERAPEUTIC TRANSFORMATION OF TRANS-3- | -2-PROPENSYRADERIVAT.
    SU433681A3|1974-06-25|METHOD OF OBTAINING 1,2.4 ^ TRIAZIN-5-ONOV
    DK161966B|1991-09-02|PROCESS FOR THE PREPARATION OF 5-AROYLED 1,2-DIHYDRO-3H-PYRROLOOE1,2-AAAPYRROL-1-CARBOXYLIC ACID OR ESTERS OR PHARMACEUTICAL ACCEPTABLE SALTS THEREOF
    RU2335497C2|2008-10-10|Method of obtaining 3,5-diamino-6-|-1,2,4-triazine of high purity grade
    HU178302B|1982-04-28|Process for producing n-amidino-3,5-diamino-6-substituted-2-piperazine-carboxamides
    IE49541B1|1985-10-30|4,5-dihydro-1-|-3-phenyl-1h-pyrazole-5-carboxylic acid and derivatives thereof
    HU229420B1|2013-12-30|Dibenzo [b,f]azepine derivatives and process for their preparation
    EP0009384A1|1980-04-02|Processes for the preparation of triazinones and condensed triazinones, and compounds so obtained
    US5498711A|1996-03-12|Synthesis of 4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazatetracyclo[5.5.0.05,903,11]dodecane
    IL116384A|1996-10-16|Ylidene compounds and their preparation
    SU428607A3|1974-05-15|
    IE52164B1|1987-07-22|Aroyl amino acids
    SU950188A3|1982-08-07|Process for producing derivatives of 4|-mercaptomethylimidazoles
    US6329521B2|2001-12-11|Process for preparing substituted benzoyl cyanide amidinohydrazones
    US2235638A|1941-03-18|Process of preparing derivatives of pyrimidine
    US6683182B2|2004-01-27|Method for producing lamotrigine from α-oxo-2,3-dichlorophenyl acetamidino-aminoguanidino hydrazone by ring closure reaction
    HU225271B1|2006-08-28|Process for producing 5-chloro-imidazol-4-carbaldehyde derivatives substituted at the 2-position
    KR100273823B1|2000-12-15|Process for the preparation of 5-substituted cytosines and other 4,5-disubstituted pyrimidine-2|-ones
    HU212611B|1996-09-30|Process for the preparation of 2-substituted 4,6-dialkoxy-pyrimidine derivatives
    JPH0670013B2|1994-09-07|3-nitro-dihydropyridines
    EP0015631A1|1980-09-17|thio)acetic acid and its salts
    US4421756A|1983-12-20|Quinolinoneimine carboxylic acid anti-inflammatory and analgesic composition containing the compound
    SU437294A1|1974-07-25|The method of obtaining derivatives of 2-amino-dihydro-benzodiazepinone
    同族专利:
    公开号 | 公开日
    DE2733180A1|1979-01-25|
    DE2733180C3|1983-04-14|
    GB2002361B|1982-01-13|
    NL7807432A|1979-01-24|
    BR7804679A|1979-04-10|
    IL55177D0|1978-09-29|
    PL114263B1|1981-01-31|
    YU160678A|1983-01-21|
    DE2733180B2|1979-12-13|
    IT7850401D0|1978-07-20|
    ES471951A1|1979-02-01|
    JPS5424886A|1979-02-24|
    SE444436B|1986-04-14|
    ATA530978A|1981-03-15|
    SE7808059L|1979-01-23|
    AT364368B|1981-10-12|
    FR2398065B1|1983-05-06|
    HU175069B|1980-05-28|
    IL55177A|1982-04-30|
    ES471958A1|1979-02-01|
    CH635085A5|1983-03-15|
    BE869139A|1979-01-19|
    FR2398065A1|1979-02-16|
    IT1156873B|1987-02-04|
    DD137225A5|1979-08-22|
    GB2002361A|1979-02-21|
    CA1082705A|1980-07-29|
    PL208544A1|1979-05-07|
    US4175188A|1979-11-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE1542873C3|1966-04-16|1978-07-13|Bayer Ag, 5090 Leverkusen|Herbicidal agent based on 4-amino-1,2,4-triazin-5-ones|
    US3905801A|1966-11-28|1975-09-16|Du Pont|Substituted 1,2,4-triazine-5-ones as herbicides|
    DE2165554A1|1971-12-30|1973-07-05|Bayer Ag|3,4,6-substd 1,2,4-triazin-5-ones - with herbicidal activity prepd from acid halides,isonitriles and hydrazine derivs|
    US4013649A|1973-08-06|1977-03-22|E. I. Du Pont De Nemours And Company|Method of making 4-amino-6-t-butyl-3-mercapto-1,2,4-triazin-5-one|
    DE2417511A1|1974-04-10|1975-10-30|Bayer Ag|6-SEC.-BUTYL-1,2,4-TRIAZIN-5 -ONE, METHOD FOR THEIR PRODUCTION AND THEIR USE AS HERBICIDES|
    DE2460889C2|1974-12-21|1983-06-09|Bayer Ag, 5090 Leverkusen|Process for the preparation of 6-tert-butyl-3-mercapto-4-amino-1.2.4-triazin-5 -one|
    DE2517654A1|1975-04-22|1976-11-04|Bayer Ag|4-AMINO-5-THIONE-1,2,4-TRIAZINE, METHOD FOR THEIR PRODUCTION AND USE AS HERBICIDES|
    US4058526A|1976-05-11|1977-11-15|Bayer Aktiengesellschaft|Treatment of waste water from the preparation of 6-substituted 3-mercapto-4-amino-1,2,4-triazine-5-ones|
    GR65206B|1977-07-20|1980-07-29|Ciba Geigy Ag|Herbicidal derivative of 1,2,4-briazin-5-ons|DE2733181B2|1977-07-22|1979-08-30|Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt|Process for the preparation of N-substituted α-ketocarboxamides|
    DE3002203A1|1980-01-22|1981-07-23|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING-KETOCARBONIC ACID-N-TERT.-BUTYLAMIDES|
    US4309538A|1980-01-31|1982-01-05|Bayer Aktiengesellschaft|Preparation of 4-amino-6-tert.-butyl-3-alkylthio-1,2,4-triazin-5-ones|
    DE3003541A1|1980-01-31|1981-08-06|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING 4-AMINO-6-TERT.-BUTYL-3-METHYLTHIO-1,2,4-TRIAZINE-5-ON|
    DE3009044A1|1980-03-08|1981-09-24|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCINGKETOCARBON-N-ACYLAMIDES|
    DE3009043A1|1980-03-08|1981-09-24|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING 4-AMINO-6-TERT.-BUTYL-3-METHYLTHIO-1,2,4-TRIAZINE-5-ON|
    DE3008921A1|1980-03-08|1981-09-24|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING 4-AMINO-6-TERT.-BUTYL-3-METHYLTHIO-1,2,4, -TRIAZIN-5-ON|
    DE3020370C2|1980-05-29|1982-09-16|Degussa Ag, 6000 Frankfurt|Process for the preparation of 4-amino-6-tert-butyl-3-mercapto-1,2,4-triazin-5-one|
    DE3102318A1|1981-01-24|1982-08-26|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING 3,6-DISUBSTITUTED 4-AMINO-1,2,4-TRIAZINE-5-ONES|
    DE3106707A1|1981-02-23|1982-09-09|Degussa Ag, 6000 Frankfurt|HERBICIDE EFFECTIVE 1,2,4-TRIAZINE-5-ON DERIVATIVE|
    DE3115970A1|1981-04-22|1982-11-11|Bayer Ag, 5090 Leverkusen|"5-ACYLOXY-4-OXAZOLONIUM SALTS, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF AS INTERMEDIATE PRODUCTS FOR THE SYNTHESIS OF HERBICIDALLY ACTIVE TRIAZINONES"|
    DE3339858A1|1983-11-04|1985-05-15|Bayer Ag, 5090 Leverkusen|METHOD FOR PRODUCING PRACTICALLY ISOMERIC-FREE 4-AMINO-3-ETHYLTHIO-6-TERT.-BUTYL-1,2,4-TRIAZINE-5-ON|
    EP0549531A1|1991-12-20|1993-06-30|Säurefabrik Schweizerhall|Process for preparing acid anhydrides|
    US5440038A|1993-12-07|1995-08-08|Miles Inc.|Process for the purification of substituted 4-amino-1,2,4-triazine-5-ones|
    US6274766B1|1999-05-19|2001-08-14|Bayer Corporation|Process for purifying α-keto acids|
    US6852857B2|2002-05-16|2005-02-08|Bayer Materialscience Llc|Method of preparing substituted 4-amino-3-alkylthio-1,2,4-triazine-5-ones|
    CN109206379A|2018-11-01|2019-01-15|江苏七洲绿色化工股份有限公司|A kind of synthetic method of metribuzin|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE2733180A|DE2733180C3|1977-07-22|1977-07-22|Process for the preparation of 4-amino-3-methylmercapto-1,2,4-triazin-5-one derivatives|
    [返回顶部]