Lithium hydroxide, monohydrate → HCID 118276659, compound

HRID 1053656Notes

Reaction equation

HRID 1053656 reaction equation
[CH2:1]([O:8][C:9]([NH:11][CH:12]([CH2:17][C:18]1[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[CH:20][C:19]=1[CH3:27])[C:13]([O:15]C)=[O:14])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.[OH-].[Li+]>O1CCCC1>[CH2:1]([O:8][C:9]([NH:11][CH:12]([CH2:17][C:18]1[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[CH:20][C:19]=1[CH3:27])[C:13]([OH:15])=[O:14])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 168937Lithium hydroxide, monohydrateHCID 118276665HCID 118276665, compound

Product 1

HCID 118276659HCID 118276659, compoundYield 48.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Adapting a literature protocol (Dayal, et al., Steroids, 1990, 55(5), 233-237), a reaction mixture of methyl 2-benzyloxycarbonylamino-3-(2-methyl-4-nitro-phenyl)propanoate (4d) (1.94 g, 5.20 mmol) and commercial lithium hydroxide monohydrate (LiOH.H2O) (436 mg, 10.4 mmol) in a mixture of tetrahydrofuran (THF)/methanol (MeOH)/water (20:10:10 mL v/v/v) was stirred at room temperature. The reaction was followed by TLC and LC/MS to completion. Acidic aqueous work-up at about pH 4 and subsequent crystallization from ethyl acetate (EtOAc) furnished 900 mg (48% yield) of the target compound (4e) as a colorless solid. 1H NMR (400 MHz, CDCl3): δ 7.96-7.92 (m, 1H), 7.90-7.80 (m, 1H), 7.36-7.18 (m, 6H), 5.62 (d, 1H), 5.00 (d, 1H), 4.93 (d, 1H), 4.60-4.50 (m, 1H), 3.26 (dd, 1H), 2.98 (dd, 1H), 2.38 (s, 3H) ppm. LC/MS: Rt=1.818 min; ESI (pos.) m/z=359.1 (M+H+)+; ESI (neg.) m/z=357.0 (M−H+)−.

Workup

  1. customAcidic aqueous work-up at about pH 4 and subsequent crystallization from ethyl acetate (EtOAc)

Sources & evidence

ORD record
ord-bc7414f426c545df8d9732eababf7a48
Source dataset
uspto-grants-2016_07
Patent number
US09394237B2

Reaction notes

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