- Crystal structure, mosquito larvicidal & antifungal activity of 3?tert?butyl?7-(2,3,4-trimethoxyphenyl)-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one
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The title compound 3?tert?butyl?7-(2,3,4-trimethoxyphenyl)-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one was prepared and characterized using single crystal X-ray diffraction, thermal & Uv-Vis analysis, FTIR, NMR (1H, 13C) and Mas
- J, Chandraprabha V.,Dasappa, Jagadeesh Prasad,H, Gayathri B.,S, Madan Kumar,Shivarama Holla,Kamble, Ravindra R.,Naik, Prashantha
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- Novel synthesis method of metribuzin intermediate
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The invention discloses a novel synthesis method of a metribuzin intermediate, wherein the intermediate triazinone of metribuzin is produced by using pinacolone (methyl tert-butyl ketone) as an initial raw material through reaction steps of chlorination, hydrolysis, oxidation, condensation and the like. According to the invention, the reaction conditions are mild, and the total yield reaches 92.4%; hydrogen peroxide is used as an oxidizing agent for replacing sodium hypochlorite, and the oxidation reaction is carried out at a room temperature, so that the operation is convenient, and the byproduct is water so as to avoid the discharge of pollutants such as salt-containing wastewater and the like in the production process; and after the reaction is finished, the intermediate and the catalyst are subjected to chromatographic separation so as to recycle the water phase containing the catalyst.
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- Triazinone preparation method
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The invention relates to a triazinone preparation method, which comprises: carrying out a hydrolysis reaction on 1-chloropinacolone at a temperature of 80-140 DEG C under the actions of a solvent andan alkali to obtain a compound I, wherein the solvent is water; carrying out an oxidation reaction on the compound I in the presence of oxygen by using Pt as a catalyst under a neutral or weakly basiccondition to obtain a compound II; and carrying out a ring closure reaction on the compound II and thiocarbohydrazide under the catalysis of an acid to obtain triazinone, wherein the structure formula of the compound I is defined in the specification, and the structure formula of the compound II is defined in the specification. According to the present invention, 1-chloropinacolone is used as theraw material, and the water is used as the solvent, such that the generation of high salt wastewater can be avoided; Pt is used as the catalyst, and oxygen is used as the oxidant, such that the use of hydrogen peroxide can be avoided, and the catalyst can be recycled so as to reduce the raw material cost; and the production method is simple, meets the environmentally friendly requirement, and issuitable for industrial production, and the yield and the content of the final product are high.
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- Method for preparing a triazones (by machine translation)
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The invention discloses a method for preparing a triazones of: the two chlorine frequency alkone in the organic solvent and in the presence of the catalyst, in the 80 °C -140 ° C reaction under 1-3 hours, then post-processed to obtain compound I, compound I in the presence of an oxidizing agent and solvent, in 0 °C -40 ° C the oxidation reaction under 1-4 hours, a solution of trimethyl pyruvic acid obtained, the trimethyl pyruvic acid solution and sulfur under catalysis of carbazide in acid , in the 70 °C -90 ° C a cyclization reaction under 2-5 hours, then post-processed to obtain the triazones. The preparation method of this invention simple step, the raw materials are easy to obtain, the cost is low, does not produce high salt waste water, more consistent with the requirements of environmental protection, is suitable for industrial production, and, ultimately, to the yield of the product and the content is relatively high. (by machine translation)
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- Synthesis of novel thiadiazolotriazin-4-ones and study of their mosquito-larvicidal and antibacterial properties
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A series of novel 3-tert-butyl-7-(aryloxymethyl)-4H-[1,3,4]thiadiazolo[2,3- c][1,2,4]triazin-4-ones (5a-5n) were synthesized by refluxing 3,3-dimethyl-2-oxobutanoic acid (trimethyl pyruvic acid) (1) and thiocarbohydrazide (2) in ethanol as solvent for 12 h, to yield 3-mercapto-4-amino-6-tert-butyl-1,2,4-triazine-5(4H)-one (3) (Scheme 1), then the compound (3) was condensed with different substituted aryloxyacetic acids (4) in POCl3 at 90 °C for 8 h (Scheme 2). The structures of the newly synthesized compounds were confirmed by IR, 1H NMR, 13C NMR, elemental analyses and mass spectroscopic studies. Few of the synthesized compounds exhibited moderate mosquito-larvicidal and antibacterial activities. Among the novel derivatives, the compound (5f) showed relatively high larvicidal activity against a malaria vector. Compounds (5i) and (5m) exhibited a broad spectrum antibacterial activity against Gram positive and Gram negative species and hence they may be considered as drug candidates for bacterial pathogens.
- Castelino, Prakash Anil,Naik, Prashantha,Dasappa, Jagadeesh Prasad,Sujayraj,Sharath Chandra,Chaluvaiah, Kumara,Nair, Ramya,Sandya Kumari,Kalthur, Guruprasad,Adiga, Satish Kumar
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p. 194 - 199
(2014/08/05)
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- Structure and Synthesis of the Metribuzin Blue Dye. Synthesis and Reactions of 2,5-Dihydrazino-1,3,4-thiadiazole and its Derivatives
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A blue pigment which sometimes accompanies the manufacture of the triazine herbicide metribuzin (5) was identified as the novel thiadiazole formazan 10 which arises from the reaction of two impurities 3 and 7.The latter compound is a keto acid derivative of 2,4-dihydrazinothiadiazole which in turn is an impurity in carbonothioic dihydrazide.Compound 7 has the interesting property of undergoing a facile oxidative decarboxylation in the presence of alcohols to form hydrazonate esters and in the presence of aliphatic amines to form red amidrazone dyes 9.The N-substituted dyes can be oxidized to ditriazolothiadiazoles 12.
- Jackman, Dennis Earl
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p. 1053 - 1057
(2007/10/02)
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- A New Method for the Synthesis of Heterocyclic S-Alkyl Thiolactams
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The reaction of S-substituted heterocyclic thiolactams with thiols is described.In some cases, rearrangement or tricyclic products were produced instead of the compounds expected from simple alkylthiol displacement.
- Jackman, Dennis E.,Westphal, Dietmar B.
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p. 1134 - 1136
(2007/10/02)
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- Preparation of novel 5-acyloxy-4-(5H)-oxazolonium salts suited for use as intermediates for triazinone herbicides
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Novel 5-acyloxy-4(5H)-oxazolonium salts of the formula STR1 in which R1 represents an optionally substituted aliphatic group with up to 12 carbon atoms, an optionally substituted cycloalkyl group with 3 to 10 carbon atoms, an optionally substituted phenyl or naphthyl group or an optionally substituted heterocyclic group and R2 and R3 are identical or different and represent a hydrogen atom or an optionally substituted aliphatic group with up to 8 carbon atoms or an optionally substituted phenyl group and X? represents the anion of an inorganic or organic acid having a pKa value of less than 2, are obtained in solution when an acyl cyanide of the general formula is reacted with a carboxylic acid anhydride of the general formula wherein R1, R2 and R3 each have the abovementioned meaning, in the presence of one or more inorganic or organic acids having a pKa value of less than 2, and if appropriate in the presence of a solvent, and if appropriate at a temperature between 0° and 120° C. The novel oxazolonium salts (I) can be used as intermediate products for the preparation of known, herbicidally active 3,4,6-trisubstituted 1,2,4-triazin-5(4H)-ones.
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- Preparation of α-ketocarboxylic acid N-acylamides
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α-Ketocarboxylic acid N-acylamides of the formula in which R1 is an optionally substituted aliphatic radical with up to 12 carbon atoms, an optionally substituted cycloalkyl radical with 3 to 10 carbon atoms, an optionally substituted heterocyclic radical, and R2 is an optionally substituted aliphatic radical with up to 8 carbon atoms or an optionally substituted phenyl radical, are prepared by reacting an acyl cyanide of the formula with a carboxylic acid anhydride of the formula in the presence of a strong acid, and then adding water to the reaction mixture. The products can be used directly in the synthesis of known herbicides.
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- Preparation of 4-amino-6-tert.-butyl-3-alkylthio-1,2,4-triazin-5(4H)-one
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In the preparation of 4-amino-6-tert.-butyl-3-alkylthio-1,2,4-triazin-5-(4H)-one of the formula STR1 wherein (1) pivaloyl cyanide of the formula is reacted to form a derivative of pyruvic acid, (2) the pyruvic acid derivative is condensed with thiocarbohydrazide of the formula to form 4-amino-6-tert.-butyl-3-mercapto-1,2,4-triazin-5(4H)-one of the formula STR2 and (3) this is alkylated, the improvement which comprises effecting step (1) by reaction with a carboxylic acid anhydride of the formula in which R is an optionally substituted aliphatic radical with up to 8 carbon atoms or an optionally substituted phenyl radical, in the presence of a strong acid at a temperature between about -50° and +150° C., and then adding water to the reaction mixture, thereby to form trimethylpyruvic acid N-acylamide of the formula
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- Preparation of 4-amino-6-tert.-butyl-3-alkylthio-1,2,4-triazin-5(4H)-ones
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In the preparation of 4-amino-6-tert.-butyl-3-alkylthio-1,2,4-triazin-5(4H)-ones of the formula STR1 wherein (a) pivaloyl cyanide of the formula is converted to a derivative of trimethylpyruvic acid, (b) the derivative is condensed with thiocarbohydrazide of the formula to form 4-amino-6-tert.-butyl-3-mercapto-1,2,4-triazin-5(4H)-one, and (c) that is alkylated to form the indicated end products, the improvement which comprises effecting (a) by reacting the pivaloyl cyanide with a strong anhydrous inorganic acid at about -50° to +50° C. thereby to form trimethylpyruvic acid amide. The derivative in (a) can be trimethylpyruvic acid amide or it may first be saponified to the free acid. The inorganic acid in (a) can be hydrochloric or hydrobromic acid in glacial acetic acid, or it can be concentrated sulphuric acid plus some chloride ion and followed by water. Trimethyl pyruvic acid amide is a new compound.
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- Preparation of 4-amino-6-tert.-butyl-3-alkylthio-1,2,4-triazin-5-(4H)-ones
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In the preparation of 4-amino-6-tert.-butyl-3-methylthio-1,2,4-triazin-5-(4H)-one of the formula STR1 wherein pivaloyl cyanide of the formula is reacted to form an intermediate, the intermediate is condensed with thiocarbohydrazide of the formula to form 4-amino-6-tert.-butyl-3-mercapto-1,2,4-triazin-5-(4H)-one of the formula STR2 and the 4-amino-6-tert.-butyl-3-mercapto-1,2,4-triazin-5-(4H)-one is alkylated to replace the H atom on the sulphur by --C1-4 --alkyl, the improvement which comprises reacting the pivaloyl cyanide with a carboxylic acid anhydride of the formula in which R is an optionally substituted aliphatic radical with up to 8 carbon atoms or an optionally substituted phenyl radical, in the presence of a strong acid at a temperature between about -50° and +150° C., and then directly reacting the reaction mixture thus obtained with the thiocarbahydrazide. Advantageously R is CH3, the strong acid is concentrated sulphuric acid, the pivaloyl cyanide is effected at a temperature between about 0° and 100° C., the condensation with thiocarbohydrazide is effected, in the presence of a mineral acid, in an aqueous or aqueous-alcoholic medium, and the alkylation is effected using methyl iodide or methyl bromide in the presence of sodium hydroxide at about 0° to 50° C.
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- Process for the production of 1,2,4-triazin-5-one derivatives
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1,2,4-triazin-5-one compounds of the general formula (I) STR1 where R is STR2 are prepared by reacting a compound of general formula (II) STR3 in which R is defined above with either (a) a tertiary alcohol of general formula (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) STR4 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 α-ketocarboxylic acid amide of general formula (V) STR5 and this, in a given case after previous saponification to the free acid, condensed with thiocarbohydrazide STR6 to form a 1,2,4-triazin-5-one compound of general formula (VI) STR7 and then the mercapto group is methylated.
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- Process for the preparation of alkali metal salts of 3,3-dimethyl-2-oxo-butyric acid
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6-Tert.-butyl-3-mercapto-4-amino-1,2,4-triazin-5(4H)-one is prepared by reacting pinacolone with a sulfur chloride at 0° to 80° C, optionally reacting the mixture with an aqueous amine solution, hydrolyzing the resulting product with an alkali metal hydroxide, heating the resulting mixture from 2 to 10 hours at 80° to 150° C, liberating a 3,3-dimethyl-2-oxo-butyric acid by acidifying with a mineral acid and reacting an aqueous solution of said 3,3-dimethyl-2-oxo-butyric acid with thiocarbohydrazide to yield the desired product.
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- Method of making 4-amino-6-t-butyl-3-mercapto-1,2,4-triazin-5-one
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Method of making 4-amino-6-t-butyl-3-mercapto-1,2,4-triazin-5-one comprising halogenating a 3,3-dimethylbutyric acid with Br2 or Cl2 to produce a 2,2-dihalo-3,3-dimethylbutyric acid then reacting the latter with thiocarbohydrazide. Alternatively, a 3,3-dimethylbutyryl chloride can be used as starting material, in which case the halogenation product is contacted with water, an aqueous base, an alcohol, a mercaptan, or an amine to convert it to an acid or salt thereof, anhydride, ester, thioester or amide, and the latter is reacted with thiocarbohydrazide.
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