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

HRID 1646377Notes

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,3 H, OMe); 3.86 (s,3 H, OMe); 5.38 (s,2 H, NCH2): 5.65 (s,2 H, OCH2); 6.95 (d,1 H); 7.36 (m,3 H); 7.46 (m,5 H): 7.86 (m,2 H); 8.66 (s,1 H).

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-0c8a56ffa73f4324b98966f1d21296ed
Source dataset: uspto-grants-1993_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05179112

Reaction notes

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