Some common heterocyclic compound, 116632-39-4, name is 5-Bromo-2-iodotoluene, molecular formula is C7H6BrI, 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. category: iodides-buliding-blocks
General procedure: (R)-(4-bromo-2-methylphenyl)((2R,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6- ((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)methanol (101R) and (S)-(4-bromo-2- methylphenyl)((2R,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6- ((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)methanol (101S). Synthesis B: Into a flask containing 4-bromo-1-iodo-2-methylbenzene (22.6 g, 76.1 mmol) in anhydrous Et2O (200 mL) under N2, was added n-BuLi/Hexanes (2.5 M, 26 mL, 65.23 mmol) dropwise at -78 C. After 1 h, the freshly prepared crude 2,3,4,6-Tetra-O-benzyl-alpha-D-mannopyranosyl carbaldehyde (12.0 g, 21.74 mmol) dissolved in Et2O (90 mL) was added via cannula over a period of 5 minutes. The mixture was stirred at -78 C for 30 min, and then slowly warmed to 0 C over a period of 1.5 h. The reaction mixture was quenched with saturated aq. NH4Cl and extracted with EtOAc (250 mL x 3). The combined organic phase was washed with brine (100 mL), dried over Na2SO4 and filtered .The filtrate was concentrated under reduced pressure and the residue was purified by silica gel chromatography (phase A: PE, phase B: CH2Cl2 / EtOAc / PE (20/1/2)) to give the 101R (4.0 g, 26% yield for two steps) as light yellow oil and 101S (8.0 g, 51% yield for two steps) as light yellow oil. Formula: C42H43BrO6 Exact Mass: 722.22 Molecular Weight: 723.69 Analytical data for Intermediate 101R: 1H NMR (300 MHz, CDCl3) delta 7.41-7.28 (m, 21H), 7.18-7.13 (m, 2H), 5.08 (d, J = 5.1 Hz, 1H), 4.71(2d, J = 11.7 Hz, 1H), 4.64-4.56 (m, 3H), 4.49 (s, 2H), 4.40 (s, 2H), 4.28 – 4.21(2m, 1H), 4.18 – 4.13 (m, 1H), 4.10 (t, J = 5.1 Hz, 1H), 3.99-3.94 (m, 1H), 3.89 (t, J = 5.9 Hz, 1H), 3.83-3.70 (m, 2H), 3.49 (br. s., 1H), 2.29 (s, 3H). ESI-MS [M+Na+] calcd for (C42H43BrO6Na) found: 745.5 (100%), 747.5 (97.3%). Formula: C42H43BrO6 Exact Mass: 722.22 Molecular Weight: 723.69 Analytical data for Intermediate 101S: 1H NMR (300 MHz, CDCl3) delta 7.37 – 7.16 (m, 23H), 5.06 (d, J=5.5 Hz, 1H), 4.73 – 4.67 (m, 1H), 4.62 – 4.44 (m, 7H), 4.11 – 4.03 (m, 2H), 3.85 – 3.76 (m, 3H), 3.73 – 3.67 (m, 2H), 3.19 (br. s., 1H), 2.18 (s, 3H). ESI-MS [M+Na]+ calcd for C42H43BrO6Na+ 745.21, found 745.5 (100%), 747.5 (97.3%).
These compound has a wide range of applications. It is believed that with the continuous development of the source of the synthetic route 116632-39-4, its application will become more common.
Reference:
Patent; FIMBRION THERAPEUTICS, INC.; JANETKA, James, W.; MYDOCK-MCGRANE, Laurel; (136 pag.)WO2017/156508; (2017); A1;,
Iodide – Wikipedia,
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