33509-43-2

Usage

Chemical Properties

White powder

InChI:InChI=1/C7H12N4OS/c1-7(2,3)4-5(12)11(8)6(13)10-9-4/h8H2,1-3H3,(H,10,13)

Synthetic route

trimethylpyruvic acid N-acetyl-amide (79848-80-9) + Thiocarbohydrazide (2231-57-4) → 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2)

Conditions	Yield
In hydrogenchloride; ethanol	95%
In hydrogenchloride; ethanol	95%

Thiocarbohydrazide (2231-57-4) + trimethylpyruvic acid (815-17-8) → 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2)

Conditions	Yield
With hydrogenchloride In water at 50 - 80℃; for 5h; pH=2 - 3;	85.3%
In ethanol for 12h; Reflux;
With hydrogenchloride In water at 50 - 80℃; for 5h; pH=2 - 3;	50 g
With hydrogenchloride at 20℃; for 6h; Large scale;
In ethanol for 12h; Reflux;

sulfuric acid (7664-93-9) + Thiocarbohydrazide (2231-57-4) + pivaloyl cyanide (42867-40-3) → 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2)

Conditions	Yield
With hydrogenchloride In water
With acetic anhydride In hydrogenchloride; water
With acetic anhydride In water

Thiocarbohydrazide (2231-57-4) + pivaloyl cyanide (42867-40-3) → 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2)

Conditions	Yield
With hydrogenchloride; hydrogen bromide In water; acetic acid
With hydrogenchloride In water; acetic acid

2,2-dibromo-3,3-dimethyl butyric acid (59742-86-8) + 2-bromo-2-tert-butyl acetic acid (50364-40-4) + tert-Butylacetic acid (1070-83-3) + Thiocarbohydrazide (2231-57-4) + phosphorus trichloride (7719-12-2, 52843-90-0) → 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2)

Conditions	Yield
With bromine In methanol; water

pyridinium 2,2-dibromo-3,3-dimethyl butyrate (59742-88-0) + Thiocarbohydrazide (2231-57-4) → 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2)

Conditions	Yield
In methanol; water

morpholine (110-91-8) + 3,3-dimethyl-butan-2-one (75-97-8) → 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2)

Conditions	Yield
With sulphur dichloride In water

1,1-dichloro-3,3-dimethylbutan-2-one (22591-21-5) → 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2)

Conditions	Yield
Multi-step reaction with 3 steps 1: sodium carbonate; dimethyl sulfoxide / 2 h / 80 °C 2: dihydrogen peroxide / water / 1 h / 25 °C 3: hydrogenchloride / water / 5 h / 50 - 80 °C / pH 2 - 3 View Scheme
Multi-step reaction with 3 steps 1: water / 20 °C / Alkaline conditions; Large scale 2: dihydrogen peroxide; 1-butyl-3-methylimidazolium Tetrafluoroborate / 8 h / 20 °C / Large scale 3: hydrogenchloride / 6 h / 20 °C / Large scale View Scheme

1-chloro-3,3-dimethyl-butan-2-one (13547-70-1) → 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2)

Conditions	Yield
Multi-step reaction with 3 steps 1: sodium hydroxide / water / 2 h / 110 °C 2: sodium carbonate; oxygen; palladium 10% on activated carbon / water / 5 h / 25 °C / pH 8 - 9 3: hydrogenchloride / water / 5 h / 50 - 80 °C / pH 2 - 3 View Scheme

3,3-dimethyl-butan-2-one (75-97-8) → 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2)

Conditions	Yield
Multi-step reaction with 4 steps 1: chlorine / 40 - 50 °C / Large scale 2: water / 20 °C / Alkaline conditions; Large scale 3: dihydrogen peroxide; 1-butyl-3-methylimidazolium Tetrafluoroborate / 8 h / 20 °C / Large scale 4: hydrogenchloride / 6 h / 20 °C / Large scale View Scheme

C11H5Cl3O3 + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → 7-[5-(2,4,5-trichlorophenyl)-2-furyl]-3-t-butyl-4(H)-1,3,4-thiadiazolo[2,3-c]-1,2,4-triazin-4-one

Conditions	Yield
With trichlorophosphate for 6h; Heating;	95%

5-(4-chloro-2-nitrophenyl)-2-furoic acid (95611-88-4) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → C18H14ClN5O4S

Conditions	Yield
With trichlorophosphate for 6h; Heating;	95%

methyl chlorosulfate (812-01-1) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one (21087-64-9)

Conditions	Yield
In sulfuric acid	95%

4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) + methyl trifluoromethanesulfonate (333-27-7) → 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one (21087-64-9)

Conditions	Yield
With trifluorormethanesulfonic acid In toluene at 8 - 25℃; for 3h; Temperature;	94%

dimethyl sulfate (77-78-1) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one (21087-64-9)

Conditions	Yield
With sodium carbonate; potassium iodide In acetone at 25 - 30℃; for 5h; Temperature;	93.56%
With sodium carbonate; potassium iodide In acetone at 40 - 45℃; for 4h; Temperature; Concentration;	93.56%
With sulfuric acid In para-xylene at 70 - 80℃; for 7.5h; Temperature;	92.1%
With sodium carbonate; potassium iodide In acetone at 30 - 35℃; for 3h; Temperature;	293.6 g

methyl bromide (74-83-9) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one (21087-64-9)

Conditions	Yield
With sodium hydroxide; sodium sulfite In water at 50℃; for 1h; pH=8.5; Reagent/catalyst; Temperature; Inert atmosphere;	93.5%
With sodium hydroxide In MML (metribuzin mother liquor, which is filtrate from a prior metribuzin synthesis) at 25 - 55℃; for 2.5 - 3h; Product distribution / selectivity;
With sodium hydroxide In MML (metribuzin mother liquor, which is filtrate from a prior metribuzin synthesis); water at 25 - 50℃; for 2.5h; Product distribution / selectivity;
With sodium hydroxide In water at 25 - 50℃; for 2.5 - 3.16667h; Product distribution / selectivity;
Stage #1: 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one With sodium hydroxide; sodium sulfite In MML (metribuzin mother liquor, which is filtrate from a prior metribuzin synthesis) for 0.5h; pH=10.5 - 11.0; Stage #2: methyl bromide In MML (metribuzin mother liquor, which is filtrate from a prior metribuzin synthesis) at 15 - 55℃; for 3.16667h; Product distribution / selectivity;

5-(3,4-dichlorophenyl)furan-2-carboxylic acid (54023-01-7) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → C18H14Cl2N4O2S

Conditions	Yield
With trichlorophosphate for 6h; Heating;	92%

5-(2-chloro-5-trifluoromethylphenyl)furan-2-carboxylic acid (302911-88-2) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → C19H14ClF3N4O2S

Conditions	Yield
With trichlorophosphate for 6h; Heating;	91%

5-((4-methoxy)phenyl)furan-2-carboxylic acid (52938-99-5) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → C19H18N4O3S

Conditions	Yield
With trichlorophosphate for 6h; Heating;	90%

5-(3-trifluoromethylphenyl)furan-2-carboxylic acid (54022-99-0) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → C19H15F3N4O2S

Conditions	Yield
With trichlorophosphate for 6h; Heating;	90%

5-(2-(trifluoromethyl)phenyl)furan-2-carboxylic acid (92973-24-5) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → 7-[5-(2-trifluoromethylphenyl)-2-furyl]-3-t-butyl-4H-1,3,4-thiadiazolo[2,3-c]-1,2,4-triazin-4-one

Conditions	Yield
With trichlorophosphate for 6h; Heating;	88%

5-p-tolyl-furan-2-carboxylic acid (52938-98-4) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → C19H18N4O2S

Conditions	Yield
With trichlorophosphate for 6h; Heating;	87%

5-(3-nitro-phenyl)-furan-2-carboxylic acid (13130-13-7) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → C18H15N5O4S

Conditions	Yield
With trichlorophosphate for 6h; Heating;	86%

4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) + 5-(2,4-dichlorophenyl)furan-2-carboxylic acid (134448-46-7) → 3-tert-butyl-7-[5-(2,4-dichloro-phenyl)-furan-2-yl]-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one

Conditions	Yield
With trichlorophosphate for 5h; Heating;	85%

4-Fluorobenzoic acid (456-22-4) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → 3-tert-butyl-7-(4-fluoro-phenyl)-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one

Conditions	Yield
With trichlorophosphate In toluene; acetonitrile for 6h; Heating;	85%

4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) + 4-fluoro-3-phenoxy benzoic acid (77279-89-1) → 3-tert-butyl-7-(4-fluoro-3-phenoxy-phenyl)-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one

Conditions	Yield
With trichlorophosphate In toluene; acetonitrile for 6h; Heating;	85%

5-(2,5-dichlorophenyl)furan-2-carboxylic acid (186830-98-8) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → C18H14Cl2N4O2S

Conditions	Yield
With trichlorophosphate for 6h; Heating;	85%

5-(4-methyl-2-nitrophenyl)furan-2-carboxylic acid (55377-91-8) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → C19H17N5O4S

Conditions	Yield
With trichlorophosphate for 6h; Heating;	85%

oxalic acid (144-62-7) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → 3,3'-di-tert-butyl-[7,7']bi[[1,3,4]thiadiazolo[2,3-c][1,2,4]triazinyl]-4,4'-dione

Conditions	Yield
With trichlorophosphate for 5h; Heating;	84%

5-(4-methoxy-2-nitrophenyl)-2-furancarboxylic acid (95611-90-8) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → C19H17N5O5S

Conditions	Yield
With trichlorophosphate for 6h; Heating;	84%

5-(4-nitrophenyl)-furan-2-carboxylic acid (28123-73-1) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → 3-tert-butyl-7-[5-(4-nitro-phenyl)-furan-2-yl]-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one

Conditions	Yield
With trichlorophosphate for 5h; Heating;	83%

5-(4-bromophenyl)furan-2-carboxylic acid (52938-96-2) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → 7-[5-(4-bromo-phenyl)-furan-2-yl]-3-tert-butyl-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one

Conditions	Yield
With trichlorophosphate for 5h; Heating;	82%

4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) + 5-(3-chloro-4-fluorophenyl)-2-furoic acid (496044-15-6) → 3-tert-butyl-7-[5-(3-chloro-4-fluoro-phenyl)-furan-2-yl]-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one

Conditions	Yield
With trichlorophosphate for 5h; Heating;	81%

5-(4-chlorophenyl)-2-furoic acid (41019-45-8) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → 3-tert-butyl-7-[5-(4-chloro-phenyl)-furan-2-yl]-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one

Conditions	Yield
With trichlorophosphate for 5h; Heating;	80%

4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) + 2,4-dichloro-5-fluoro-benzoic acid (86522-89-6) → 3-tert-butyl-7-(2,4-dichloro-5-fluoro-phenyl)-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one

Conditions	Yield
With trichlorophosphate In toluene; acetonitrile for 6h; Heating;	80%

dimethyl sulfate (77-78-1) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → 4-amino-6-t-butyl-2,3-dihydro-2-methyl-3-thioxo-1,2,4-triazin-5(4H)-one + 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one (21087-64-9)

Conditions	Yield
With sodium methylate In methanol for 1h; Heating;	A 78% B 26%
With sodium methylate In methanol for 1h; Heating;	A 68% B 26%

malonic acid (141-82-2) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → C17H20N8O2S2

Conditions	Yield
With trichlorophosphate for 5h; Heating;	78%

2,4,5-Trichlorophenoxyacetic acid (93-76-5) + 4-amino-3-mercapto-6-tert-butyl-1,2,4-triazin-5-one (33509-43-2) → 3-tert-butyl-7-[(2,4,5-trichlorophenoxy)methyl]-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one (1621091-21-1)

Conditions	Yield
With trichlorophosphate at 90℃; for 8h;	78%

Upstream product

• 2231-57-4 Thiocarbohydrazide 
• 42867-40-3 pivaloyl cyanide 
• 79848-80-9 trimethylpyruvic acid N-acetyl-amide 
• 59742-86-8 2,2-dibromo-3,3-dimethyl butyric acid 
• 50364-40-4 2-bromo-2-tert-butyl acetic acid 
• 1070-83-3 tert-Butylacetic acid 
• 7719-12-2 phosphorus trichloride 
• 38941-46-7 methyl trimethylpyruvate 
• 130231-67-3 2,5-dihydrazino-1,3,4-thiadiazole dihydrochloride 
• 21087-64-9 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one 
• 43165-46-4 sodium 3,3-dimethyl-2-oxobutyrate 
• 60166-88-3 2-(1-Carboxy-2,2-dimethylpropylidene)carbonothioic dihydrazide 
• 815-17-8 trimethylpyruvic acid 
• 75-97-8 3,3-dimethyl-butan-2-one 

Downstream Products

• 21087-64-9 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one 
• 1621091-11-9 3-tert-butyl-7-[(4-chlorophenoxy)methyl]-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 
• 1621091-12-0 3-tert-butyl-7-[(2,4-dichlorophenoxy)methyl]-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 
• 1621091-13-1 3-tert-butyl-7-[(2,3,5-trimethylphenoxy)methyl]-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 
• 1621091-14-2 3-tert-butyl-7-[(2,6-dimethylphenoxy)methyl]-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 
• 1621091-15-3 3-tert-butyl-7-[(2-nitrophenoxy)methyl]-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 
• 1621091-16-4 3-tert-butyl-7-[(4-hydroxyphenoxy)methyl]-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 
• 1621091-17-5 3-tert-butyl-7-[(2-methoxyphenoxy)methyl]-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 
• 1621091-18-6 3-tert-butyl-7-(phenoxymethyl)-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 
• 1621091-19-7 3-tert-butyl-7-[2-(4-chlorophenoxy)propan-2yl]-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 
• 1621091-20-0 3-tert-butyl-7-[(2-chlorophenoxy)methyl]-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 
• 1621091-21-1 3-tert-butyl-7-[(2,4,5-trichlorophenoxy)methyl]-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 
• 1621091-22-2 3-tert-butyl-7-[(4-iodophenoxy)methyl]-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 
• 1621091-23-3 7-[(4-acetylphenoxy)methyl]3-tert-butyl-4H-[1,3,4]thiadiazolo[2,3-c][1,2,4]triazin-4-one 

Relevant academic research and scientific papers

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

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

Novel synthesis method of metribuzin intermediate

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.

Triazinone preparation method

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.

Method for preparing a triazones (by machine translation)

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)

Synthesis of novel thiadiazolotriazin-4-ones and study of their mosquito-larvicidal and antibacterial properties

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.

Structure and Synthesis of the Metribuzin Blue Dye. Synthesis and Reactions of 2,5-Dihydrazino-1,3,4-thiadiazole and its Derivatives

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.

A New Method for the Synthesis of Heterocyclic S-Alkyl Thiolactams

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.

Preparation of novel 5-acyloxy-4-(5H)-oxazolonium salts suited for use as intermediates for triazinone herbicides

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.

Preparation of α-ketocarboxylic acid N-acylamides

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.

Preparation of 4-amino-6-tert.-butyl-3-alkylthio-1,2,4-triazin-5(4H)-ones

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.