Acetic Acid → HCID 71599540, compound

HRID 1507705Notes

Reaction equation

HRID 1507705 reaction equation
[CH3:1][N:2]([CH3:23])[C:3](=[O:22])[CH2:4][N:5]([C:14]1[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=1)[CH2:6][C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8].[C:24](OC(C)(C)C)(=[O:32])[C:25](OC(C)(C)C)=[O:26].CC(C)([O-])C.[K+].C(O)(=O)C>C(O)(C)(C)C.C1COCC1>[CH3:23][N:2]([CH3:1])[C:3]([C:4]1[N:5]([C:14]2[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=2)[C:6]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])=[C:25]([OH:26])[C:24]=1[OH:32])=[O:22]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 69651Di-tert-butyl oxalate2×HCID 23665647Potassium tert-butoxide2×HCID 89610496HCID 89610496, compound

Product 1

HCID 71599540HCID 71599540, compoundYield 38.5%

Reagents, catalysts & solvents 2

HCID 6386tert-ButanolSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of tert-butyl 2-((2-(dimethylamino)-2-oxoethyl)(4-methoxyphenyl)amino)acetate (16) (1.98 g, 6.14 mmol) and di-tert-butyl oxalate (1.37 g, 6.76 mmol) in anhydrous tert-butanol (6 mL) was added potassium tert-butoxide (20 wt. % in THF) (10.77 ml, 15.35 mmol) and the reaction was stirred at 100° C. for 1.5 h, di-tert-butyl oxalate (300 mg, 1.5 mmol), potassium tert-butoxide (20 wt. % in THF) (4 mL, 5.71 mmol), THF (10 mL), and tert-butanol (4 mL) were added and the mixture stirred for a further 1 h. The mixture was allowed to cool to RT and acetic acid (4 ml, 69.9 mmol) added, the mixture was poured on to ice-cold water (50 mL) and the resulting precipitate was collected by vacuum filtration and recrystallised from hot ethanol to afford tert-butyl 5-(dimethylcarbamoyl)-3,4-dihydroxy-1-(4-methoxyphenyl)-1H-pyrrole-2-carboxylate (UL1-036) (890 mg, 37%) as a white powder: m/z 377 (M+H)+ (ES+); 375 (M−H)− (ES−). 1H NMR (400 MHz, DMSO-d6) δ: 8.62 (s, 1H), 8.45 (s, 1H), 7.12-6.99 (m, 2H), 6.94-6.81 (m, 2H), 3.76 (s, 3H), 2.83 (br s, 6H), 1.17 (s, 9H).

Workup

  1. stirringthe mixture stirred for a further 1 h
  2. temperatureto cool to RT
  3. filtrationthe resulting precipitate was collected by vacuum filtration
  4. customrecrystallised from hot ethanol

Sources & evidence

ORD record
ord-5f8926403d76494b8483865481c08189
Source dataset
uspto-grants-2015_12
Patent number
US09221756B2

Reaction notes

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