Sodium → Methyl 4-(3-benzyloxy-6-nitroindazol-1-ylmethyl)-3-methoxybenzoate

HRID 1742345Notes

Reaction equation

[OH:1][C:2]1[C:10]2[C:5](=[CH:6][C:7]([N+:11]([O-:13])=[O:12])=[CH:8][CH:9]=2)[N:4]([CH2:14][C:15]2[CH:24]=[CH:23][C:18]([C:19]([O:21][CH3:22])=[O:20])=[CH:17][C:16]=2[O:25][CH3:26])[N:3]=1.[Na]>CO>[CH2:2]([O:1][C:2]1[C:10]2[C:5](=[CH:6][C:7]([N+:11]([O-:13])=[O:12])=[CH:8][CH:9]=2)[N:4]([CH2:14][C:15]2[CH:24]=[CH:23][C:18]([C:19]([O:21][CH3:22])=[O:20])=[CH:17][C:16]=2[O:25][CH3:26])[N:3]=1)[C:10]1[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=1

Participants

Conditions

Temperature: 0 °C

Procedure

Methyl 4-(3-hydroxy-6-nitroindazol-1-ylmethyl)-3-methoxybenzoate (T) (35.7 g.) was added to a mixture of sodium (2.3 g.) and methanol (200 ml.). The mixture was stirred for 18 hours, and evaporated. The residue was dissolved in N,N-dimethylformamide (100 ml.), cooled to 0° C. , and benzyl bromide (15.5 ml.) added. After 18 hours at ambient temperature, ethyl acetate and 1N sodium hydroxide solution were added. The precipitate was isolated by filtration, washed with ether, and chromatographed by HPLC on silica gel, eluting with dichloromethane, to give methyl 4-(3-benzyloxy-6-nitroindazol-1-ylmethyl)-3-methoxybenzoate (CC) (27 g., 60%) as a solid; NMR (250 MHz, DMSO--d6): 3.84(s,3H, OMe); 3.86(s,3H, OMe); 5.38(s,2H, NCH2); 5.65(s,2H, OCH2); 6.95(d,1H); 7.36 (m,3H); 7.46(m,5H); 7.86(m,2H); 8.66(s,1H).

Workup

customevaporated
dissolutionThe residue was dissolved in N,N-dimethylformamide (100 ml.)
additionbenzyl bromide (15.5 ml.) added
waitAfter 18 hours at ambient temperature
additionethyl acetate and 1N sodium hydroxide solution were added
customThe precipitate was isolated by filtration
washwashed with ether
customchromatographed by HPLC on silica gel
washeluting with dichloromethane

Sources & evidence

ORD record: ord-9d1bb094adbc40989a69fa463d07c864
Source dataset: uspto-grants-1994_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05338734

Reaction notes

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