14559-13-8

Basic information

• Product Name: methyl 4,5-dimethylthiophene-3-carboxylate
• Synonyms: 3-thiophenecarboxylic acid, 4,5-dimethyl-, methyl ester; Methyl 4,5-dimethylthiophene-3-carboxylate
• CAS NO: 14559-13-8
• Molecular Formula: C₈H₁₀O₂S
• Molecular Weight: 170.2288
• EINECS: 604-481-3
• Mol File: 14559-13-8.mol
• Article Data: 5

Chemical Properties

• Boiling Point: 234°C at 760 mmHg
• Flash Point: 95.3°C
• Density: 1.139g/cm³
• Vapor Pressure: 0.0541mmHg at 25°C
• Refractive Index: 1.528
• CAS DataBase Reference: methyl 4,5-dimethylthiophene-3-carboxylate(CAS DataBase Reference)
• NIST Chemistry Reference: methyl 4,5-dimethylthiophene-3-carboxylate(14559-13-8)
• EPA Substance Registry System: methyl 4,5-dimethylthiophene-3-carboxylate(14559-13-8)

Safety Data

• Hazardous Substances Data: 14559-13-8(Hazardous Substances Data)

Upstream product

• 40789-98-8 3-mercapto-2-butanone 
• 42201-71-8 methyl (trimethylsilyl)propiolate 
• 623-43-8 methyl crotonate 
• 34846-90-7 methyl 3-methoxyprop-2-enoate 

Downstream Products

• 175217-20-6 silthiofam 
• 175217-23-9 4,5-dimethyl-2-trimethylsilylthiophene-3-carboxylic acid 
• 1448631-52-4 C₂₀H₁₆ClN₃O₂S 
• 1380088-21-0 2-((6R)-4-(4-chlorophenyl)-2,3,9-trimethyl-6H-isoxazolo[5,4-c]thieno[2,3-e]azepin-6-yl)acetic acid 
• 1380088-18-5 2-((6S)-4-(4-chlorophenyl)-2,3,9-trimethyl-6H-isoxazolo[5,4-c]thieno[2,3-e]azepin-6-yl)acetic acid 
• 1380087-72-8 C₂₁H₂₁N₃O₂S 
• 1380088-64-1 (2R)-2-((6S)-4-(4-cyanophenyl)-2,3,9-trimethyl-6H-isoxazolo[5,4-c]thieno[2,3-e]azepin-6-yl)propanamide 
• 1380088-45-8 (6S)-4-(4-chlorophenyl)-2,3,9-trimethyl-6-(thiazol-2-ylmethyl)-6H-isoxazolo[5,4-c]thieno[2,3-e]azepine 
• 1380088-44-7 (6S)-6-((1H-imidazol-2-yl)methyl)-4-(4-chlorophenyl)-2,3,9-trimethyl-6H-isoxazolo[5,4-c]thieno[2,3-e]azepine 
• 1380088-23-2 2-((6R)-4-(4-chlorophenyl)-2,3,9-trimethyl-6H-isoxazolo[5,4-c]thieno[2,3-e]azepin-6-yl)-N-ethylacetamide 
• 1380088-19-6 2-((6S)-4-(4-chlorophenyl)-2,3,9-trimethyl-6H-isoxazolo[5,4-c]thieno[2,3-e]azepin-6-yl)-N-ethylacetamide 
• 1380087-45-5 2-((6S)-4-(4-chlorophenyl)-2,3,9-trimethyl-6H-isoxazolo[5,4-c]thieno[2,3-e]azepin-6-yl)acetamide 
• 1448631-44-4 C₂₄H₂₅ClN₂O₃S 
• 1019115-42-4 methyl 2-bromo-4,5-dimethylthiophene-3-carboxylate 

Relevant articles and documents

Synthesis of 2-(substituted-silyl)thiophene-3-carboxylates via a facile [3+2] cycloaddition reaction catalyzed by potassium tert-butoxide

Background: Substituted-silyl thiophene carboxylates are important intermediates for the synthesis of substituted-silyl thiophene carboxamides which have been found to show high biological activities. Methods: Using α-mercapto ketones and 3-(substituted-silyl)propiolates as raw materials, 2-(substituted-silyl)thiophene-3-carboxylates could be synthesized smoothly via cycloaddition reaction catalyzed by potassium tert-butoxide. Results: A small library of target compounds was prepared under optimized reaction conditions in moderate to good yields. The reaction mechanism has been proposed. Conclusion: Potassium tert-butoxide is an environmentally friendly and efficient catalyst for the cycloaddition reaction of α -mercapto ketones and 3-(substituted-silyl)propiolates. This methodology provides ready access to 2-(substituted-silyl)thiophene-3-carboxylic acids which can be serve as the raw materials of 2-(substituted-silyl)thiophene-3-carboxamide and other pharmaceutically intriguing compounds.

Process research on the synthesis of silthiofam: A novel fungicide for wheat

The development of an efficient, low-cost synthesis of the novel wheat fungicide silthiofam (1) is described. Improvements to the original Discovery route allowed 300 kg of material to be prepared in two, overlapping pilot-plant campaigns. Thereafter, efforts were focused on further optimizing the pilot-plant route, and on devising alternate, lower cost routes to silthiofam. One potential new route involved a cydoaddition reaction between 3-mereapto-2-butanone and N-(2-propenyl)-3-trimethylsilyl-propynamide. The cyclic product could be directly dehydrated to silthiofam, however the overall yield was modest, raw material costs were high, and there were purification problems. The route ultimately selected for development proceeds in 6 chemical steps and about 60% yield from the inexpensive precursors 3-chloro-2-butanone and methyl 3-methoxyacrylate. Key features of the route are a novel thiophene-3-carboxylate synthesis involving cycloaddition of 3-mercapto-2-butanone with the acrylate followed by acid catalyzed aromatization, the room temperature formation and silylation of a thiophene-3-carboxylate dianion, and conversion of the resulting carboxylic acid into silthiofam with negligible loss of the silyl group. The process involves isolation of just two intermediates, only one of which is purified, and uses only three organic solvents, all of which are recycled. It can be run safely on large scale to give highpurity silthiofam.

Synthesis of 3-carbomethoxy-4,5-dimethylthiophene

Fungicides having thiophene rings may be made from the intermediate compound 3-carbomethoxy-4,5-dimethylthiophene. That compound, and related compounds, may be produced by reacting an alpha mercaptoketone, e.g., 3-mercapto-2-butanone, with an acrylate, e.g., methyl-3-methoxy acrylate, in the presence of an alkoxide base, e.g., NaOMe, to form the substituted tetrahydrothiophene, followed by conversion to the aromatic thiophene with an acid treatment. The substituted tetrahydrothiophene is a novel compound.