Synthetic Route of 4117-09-3, These common heterocyclic compound, 4117-09-3, name is 7-Bromo-1-heptene, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.
Grignard reagent hept-6-en-1-ylmagnesium bromide was prepared by suspending magnesium granules (0.22g, 9.05mmol) in anhydrous tetrahydrofuran (20mL) and subsequently adding 7-bromo-1-heptene (1.63g, 9.19mmol) dropwise. The mixture was refluxed for 30min. In a separate flask, copper(I) iodide (1.72g, 9.03mmol) was suspended in anhydrous tetrahydrofuran (10mL) and cooled to-78C in an isopropyl alcohol-dry ice bath. Methyllithium solution (1.6M in diethyl ether, 5.65mL, 9.04mmol) was added very slowly via syringe. The resultant mixture was stirred at-78C for 1h and then slowly allowed to warm to 0C, whereupon a brownish suspension formed, which was immediately cooled to-78C. After that, the aforementioned solution of Grignard reagent in tetrahydrofuran was added via syringe. The mixture thus obtained was stirred at-78C for 1h and then allowed to warm to 0C, whereupon a purple colouration appeared. The mixture was then cooled again to-78C and a solution of 1 (1.47g, 4.51mmol) in tetrahydrofuran (20mL) was added via syringe. That mixture was allowed to stir at-78C for 1h and at room temperature for 2h, and the reaction was quenched by adding saturated aqueous ammonium chloride (15mL). After addition of diethyl ether (50mL), two layers and a brown insoluble formed which was filtered off. The organic phase was separated and the royal blue aqueous phase was extracted with diethyl ether. The combined organic fractions were washed with brine, dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure. Flash column chromatography of the residual brown oil with n-hexane-diethyl ether (95:5) yielded the crude ester mixture (0.56g, 42%). A 0.23g portion was separated from the by-product 3 by passing over a 10g SPE cartridge. Step gradient elution from acetonitrile-water (9:1) to pure acetonitrile yielded pure ester 2 as a white solid (0.20g, 96%) after concentration under reduced pressure. TLC (n-hexane-diethyl ether 9:1): Rf 0.43. RP-TLC (acetonitrile): Rf 0.22. 1H NMR (400MHz, CDCl3): delta 5.80 (1H, ddt, J=16.9, 10.1, 6.6Hz), 5.00-4.89 (2H, m), 3.65 (3H, s), 2.28 (2H, t, J=7.4Hz), 2.05-1.99 (2H, m), 1.60 (2H, qui, J=7.3Hz), 1.38-1.20 (24H, m). 13C NMR (100MHz, CDCl3): delta 174.4, 139.3, 114.1, 51.5, 34.2, 33.9, 29.7 (3), 29.6, 29.5, 29.3, 29.2, 29.0, 25.0. GC: tR 16.6min. EIMS (70eV): m/z (%) 296 (1), 264 (51), 222 (28), 180 (19), 111 (19), 97 (45), 87 (59), 74 (83), 55 (100), 41 (58).
The synthetic route of 4117-09-3 has been constantly updated, and we look forward to future research findings.
Reference:
Article; Huber, Thimo; Firlbeck, Doris; Riepl, Herbert M.; Journal of Organometallic Chemistry; vol. 744; (2013); p. 144 – 148;,
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