3-Substituted thiophenes. VI. Substitution reactions of 3-thenoic acid was written by Campaigne, E. E.;Bourgeois, R. C.. And the article was included in Journal of the American Chemical Society in 1954.Product Details of 36157-41-2 This article mentions the following:
3-Thenoic acid (I) was brominated, chlorinated, and nitrated in the 5-position. A 2nd substituent was found to enter in the 2-position to form the 2,5-disubstituted-3-thenoic acids, but 5-nitro-3-thenoic acid (II) could not be further nitrated, even at high temperatures in mixed acid. LiAlH4 caused the reductive dehalogenation of 5-bromo-(III) and 2,5-dichloro-3-thenoic acid (IV) to 3-thenyl alc. (V). Br (46 g.) in 225 cc. glacial AcOH added slowly with stirring to 38 g. I in 350 cc. glacial AcOH at room temperature, the mixture stirred 15 min., poured into 2 l. H2O, and the white precipitate washed with H2O and recrystallized from hot H2O yielded 42 g. (69%) III, white needles, m. 117-18°. III refluxed in excess SOCl2, the mixture poured into cold NH4OH, and the precipitate recrystallized from H2O gave the amide, white plates, m. 100-1°. The crude acid chloride from III warmed with PhNH2 in C6H6 yielded the anilide, m. 142-3° (from aqueous EtOH). III (2 g.) in 25 cc. glacial AcOH warmed with 5.6 g. Br, the mixture poured into H2O, decolorized with NaHSO3, and the white precipitate recrystallized from H2O gave 1.0 g. 2,5-dibromo-3-thenoic acid (VI), m. 175-6°, also obtained from I or 2-bromo-3-thenoic acid by the same method. I (3 g.) in 200 cc. glacial AcOH treated at room temperature with gaseous Cl to a weight increase of 1.6 g., the mixture allowed to stand a few min., poured into 1 l. ice water, stirred, refrigerated overnight, a small amount of white crystals filtered off, the filtrate extracted with Et2O, the extract dried, evaporated, and the combined solids recrystallized from hot H2O yielded 1.5 g. (40%) 5-chloro-3-thenoic acid (VII), m. 156-7°; amide, white needles, m. 135-6° (from H2O); anilide, white microcrystalline powder, m. 170-1° (from 50% EtOH). Cl gas passed into 3 g. I in 100 cc. glacial AcOH at room temperature to a weight increase of 3.2 g., and the mixture allowed to stand 0.5 hr. and worked up as for VII yielded 2 g. IV, m. 147-8°, also obtained from VII or 2-chloro-3-thenoic acid in AcOH by the same method. I (5 g.) added in small portions with stirring below -5° to 20 cc. concentrated HNO3 (d. 1.42) and 11.5 cc. 96% H2SO4, the mixture poured on ice, steam distilled, the distillate washed with Et2O, cooled, and the resulting yellow needles (4.1 g.) recrystallized 3 times from C6H6 gave II, m. 145-6°; amide, light tan needles, m. 162-3° (from H2O); anilide, light tan plates, m. 179-80° (from 50% EtOH). II (5-g. samples) stirred into 2 parts concentrated HNO3 and 1 part concentrated H2SO4 at temperatures between -10° and 140° gave at 20-120 min. reaction times 95-50% recovered II. N’-(2-Pyridyl)-N,N-dimethylethylenediamine (16.4 g.) in 200 cc. pyridine treated with the crude acid chloride from 15 g. III, the mixture warmed 8 hrs., the pyridine distilled off in vacuo, the residue poured into ice water, extracted with Et2O, the Et2O solution extracted with dilute HCl, the acid extract treated with Norit, neutralized with cold dilute aqueous NaOH, the precipitated oil extracted into Et2O, the extract dried, evaporated, the residual dark oil (13 g.) distilled, the pale oily orange distillate (8 g., 32%), b1 193-7°, reduced with LiAlH4 in Et2O, the resulting pale yellow oil (2 g.), b1 165-70°, dissolved in 10 cc. iso-PrOH, the solution treated with 0.7 cc. concentrated HCl, refrigerated overnight, cooled in ice-MeOH, and the crystalline deposit dried gave N’-(2-pyridyl)-N’-(3-thenyl)-N,N-dimethylethylenediamine HCl salt, m. 168-9°. III (42 g.) in Et2O reduced with an equimol. amount of LiAlH4 yielded 30% V, b10 88-90°. V (2 cc.) and 1 cc. 1-C10H7NCO heated 5 min. on the steam bath, and the resulting brown solid recrystallized from CCl4 gave V 1-naphthylurethan, m. 133-4° (authentic sample, m. 132-3°). The reduction of IV under the same conditions yielded 35% V, b10 86-8°. In the experiment, the researchers used many compounds, for example, 2,5-Dichlorothiophene-3-carboxylic acid (cas: 36157-41-2Product Details of 36157-41-2).
2,5-Dichlorothiophene-3-carboxylic acid (cas: 36157-41-2) belongs to organic chlorides. Organochlorines stimulate the central nervous system and cause convulsions, tremor, nausea, and mental confusion. Examples are dichlorodiphenyltrichloroethane (DDT), chlordane, lindane, endosulfan, and dieldrin. Alkyl chlorides readily react with amines to give substituted amines. Alkyl chlorides are substituted by softer halides such as the iodide in the Finkelstein reaction.Product Details of 36157-41-2
Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics