Electric Literature of 53087-13-1,Some common heterocyclic compound, 53087-13-1, name is 1-(Benzyloxy)-3-bromobenzene, molecular formula is C13H11BrO, 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.
General procedure: To a 30 mL flamed-dried flask equipped with stir bar and a nitrogen-filled balloon were added 2,2,6,6-tetramethylpiperidine (1.2 equiv) and THF (12 mL). After cooled to 0 C with an ice waterbath, n-BuLi (2.5 M in hexane, 1.2 equiv) was added dropwise and the reaction was stirred at 0 C for 0.5 h. To a 100 mL flame-dried flask equipped with a stir bar and a nitrogen-filled balloon were added THF (30 mL), benzyne precursor (1 equiv), and corresponding ketene silyl acetals9 (1.5 equiv) and was cooled to 78 C with an acetone-dry ice bath before in situ generated lithium tetramethylpiperidine was added dropwise. The reaction was monitored and aqueous NH4Cl was added upon disappearance of the benzyne precursor. After warming to rt, the reaction mixture was extracted with ethyl acetate (30 mLx3), washed with brine, and concentrated under reduced pressure. Acetonitrile (30 mL) was added to the concentrated reaction system and cooled to 0 C with an ice-water bath followed by slow addition of hydrofluoric acid (27.6 M, 10 equiv). Upon completion, the reaction was heated to 40 C overnight before water (100 mL) was added. The mixture was extracted with ethyl acetate (30 mLx3), washed with brine, and dried with Na2SO4. The combined organic extract was concentrated under reduced pressure and purified by column chromatography on silica gel to afford the following compounds. 4.6.1. 5-(Benzyloxy)-8-methylbicyclo[4.2.0]octa-1,3,5-trien-7-one (9). Compound 9 was obtained as light yellow oil (271 mg) from 6d and tert-butyl((1-methoxyprop-1-en-1-yl)oxy)dimethylsilane in 23% yield, Rf=0.6 (Hexane/EtOAc=5:1); 1H NMR (400 MHz, CDCl3) delta 7.48-7.30 (m, 6H), 7.02 (d, J7.0 Hz, 1H), 6.89 (d, J8.4 Hz, 1H), 5.45 (s, 2H), 4.21 (q, J7.2 Hz, 1H), 1.47 (d, J7.2 Hz, 3H). 13C NMR (101 MHz, CDCl3) delta 189.3 (s), 157.0 (s), 152.6 (s), 137.8 (s), 136.4 (s), 130.7 (s), 128.5 (s), 128.2 (s), 127.9 (s), 116.7 (s), 114.2 (s), 74.0 (s), 58.3 (s), 15.0 (s). IR: gamma 2964, 2927, 2360, 2342, 1756, 1602, 1571, 1473, 1452, 1386, 1273, 1161, 1125, 991, 886, 795, 767, 748, 699 cm-1. HRMS calcd for C16H14NaO2 [M+Na]+: 261.0886, found: 261.0879.
The synthetic route of 53087-13-1 has been constantly updated, and we look forward to future research findings.
Reference:
Article; Chen; Savage, Nikolas A.; Dong, Guangbin; Tetrahedron; vol. 70; 27-28; (2014); p. 4135 – 4146;,
Ether – Wikipedia,
Ether | (C2H5)2O – PubChem