Heterocyclics. XIII. Synthesis of substituted bromothiophenes was written by Fournari, Pierre;Guilard, Roger;Person, Maurice. And the article was included in Bulletin de la Societe Chimique de France in 1967.Category: bromides-buliding-blocks This article mentions the following:
Bromothiophenecarboxaldehydes of the general formula I are prepared and treated with aryl ketones to give compounds of the general formula II. Thus, 66 g. 2,3-dibromothiophene is treated with 0.273 mole BuLi and the organic Li compound obtained is treated with 30 g. HCONMe2 to give 13.5 g. 3-bromo-2-formylthiophene (III), b12 109-12鎺? thiosemicarbazone m. 246鎺? oxime m. 159鎺? Similarly prepared are (b.p./mm., m.p., m.p. thiosemicarbazone, and m.p. oxime given): I (R = R3 = H, R1 = CHO, R2 = Br), 118-20鎺?13, -, 221鎺? 104鎺? I (R = R1 = CHO, R2 = Br, R3 = H), 158-60鎺?13, 117-18鎺? -, -. I [R = R2 = R3 = H, R1 = CH(OEt)2] is treated with 0.13 mole BuLi and a solution of 12 g. Br is added to give 5 g. I (R = Br, R1 = CHO, R2 = R3 = H), m. 34鎺?(hexane); thiosemicarbazone m. 235鎺? oxime m. 86鎺? Similarly prepared are the following I (R2 = H) (R, R1, R3, b.p./mm., m.p., m.p. thiosemicarbazone, and m.p. oxime given): H, CHO, Br, 114-16鎺?17-18, -, 180鎺? 91鎺? Br, CHO, Br, 122-35鎺?12-14, 45-6鎺?(ligroine), 266鎺? 136鎺? The following I (R1 = H) are prepared according to known methods (R, R2, R3, b.p./mm., m.p., m.p. thiosemicarbazone, and m.p. oxime given): CHO, Br, H, -, 45-6鎺? 216鎺? 174鎺? CHO, H, Br, 112-14鎺?14, -, 173-4鎺? 152-4鎺? A mixture of 0.01 mole 0-HOC6H4Ac, 0.01 mole III, 1 ml. 5N NaOH, and 10 ml. EtOH is heated 2 hrs. at 60鎺?to give 10% 0-hydroxyphenyl 2-(3-bromo-2-thienyl)vinyl ketone, m. 124鎺? Similarly prepared are the following II (R = R2 = H, R1 = Br) (Ar, m.p., and % yield given): 0-HOC6H4, 108鎺? 11; 2,5-HO(O2N)C6H3, 195鎺? 65. A mixture of 0.01 mole 5-bromo-2-acetylthiophene, 0.01 mole 2-formylthiophene, 3.2 ml. N NaOH, and 20 ml. EtOH is refrigerated 2 hrs. to give 20% II (R = R1 = R2 = H, Ar + 5-bromo-2-thienyl), m. 113鎺? Similarly prepared are the following II (R2 = H) (Ar, R, R1, m.p., and % yield given): 5-bromo-2-thienyl, H, Br, 135鎺? 33; 5-bromo-2-thienyl, Br, H, 144鎺? 40; 2-thienyl, Br, H, 100鎺? 60; 2-pyridyl, Br, H, 145鎺? 80; 2-pyridyl, H, Br, 136鎺? 70. 3-Bromo-2-cyanothiophene (m. 50鎺? and the following I are prepared according to the P. Reynaud-R. Delaby method for the preparation of 2-cyanothiophene (R, R1, R2, R3, b.p./mm., and m.p. given): CN, H, Br, H, -, 45鎺?(ether-ligroine); CN, H, H, Br, 124鎺?34, -; Br, CN, H, H, 130鎺?22, -; H, CN, Br, H, -, 56 (ether-ligroine); H, CN, H, Br, -, 33鎺?(aqueous alc.); Br, CN, H, Br, -, 76鎺?(aqueous alc.). The bromocyanothiophenes (0.01 mole) are treated with 10 ml. H2O2 at 50鎺?in the presence of 4 ml. 25% KOH to give 4-bromo-2-thiophenecarboxamide, m. 153-4鎺? and the following I (R, R1, R2, R3, and m.p. given): CONH2, H, H, Br, 164鎺? Br, CONH2, H, H, 142鎺? H, CONH2, Br, H, 146鎺? H, CONH2, H, Br, 146鎺? Br, CONH2, H, Br, 140-1鎺? CONH2, Br, H, H, 103鎺? 5-Bromo-3-formylthiophene (0.005 mole) is treated with 800 mg. KMnO4 to give 0.6 g. 5-bromo-3-thiophenecarboxylic acid, m. 139鎺?(aqueous alc.). Similarly prepared are the following I (R, R1, R2, R3, and m.p. given): CO2H, Br, H, H, 197-8鎺? CO2H, H, Br, H, 123鎺? CO2H, H, H, Br, 142鎺? Br, CO2H, H, H, 180鎺? H, CO2H, Br, H, 159鎺? H, CO2H, H, Br, 139鎺? Br, CO2H, H, Br, 178鎺? N.M.R. data are given. In the experiment, the researchers used many compounds, for example, 5-Bromothiophene-3-carbaldehyde (cas: 18791-79-2Category: bromides-buliding-blocks).
5-Bromothiophene-3-carbaldehyde (cas: 18791-79-2) belongs to organobromine compounds. Bromo compounds are employed in a variety of metal-catalyzed coupling reactions. They are also ideal candidates for the synthesis of Grignard reagents that have wide-applicability in organic synthesis. alpha-Bromoesters are employed in the Reformatsky reaction for the synthesis of beta-hydroxyesters. One prominent application of synthetic organobromine compounds is the use of polybrominated diphenyl ethers as fire-retardants, and in fact fire-retardant manufacture is currently the major industrial use of the element bromine.Category: bromides-buliding-blocks
Referemce:
Bromide – Wikipedia,
bromide – Wiktionary