4-Methoxybenzyl alcohol → HCID 89463489, compound

HRID 1473276Notes

Reaction equation

HRID 1473276 reaction equation
[NH:1]1[CH:5]=[C:4]([C:6]([O:8][CH3:9])=[O:7])[C:3]([C:10]([O:12][CH3:13])=[O:11])=[N:2]1.[CH3:14][O:15][C:16]1[CH:23]=[CH:22][C:19]([CH2:20]O)=[CH:18][CH:17]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.CCOC(C)=O>[CH3:14][O:15][C:16]1[CH:23]=[CH:22][C:19]([CH2:20][N:2]2[C:3]([C:10]([O:12][CH3:13])=[O:11])=[C:4]([C:6]([O:8][CH3:9])=[O:7])[CH:5]=[N:1]2)=[CH:18][CH:17]=1.[CH3:14][O:15][C:16]1[CH:23]=[CH:22][C:19]([CH2:20][N:1]2[CH:5]=[C:4]([C:6]([O:8][CH3:9])=[O:7])[C:3]([C:10]([O:12][CH3:13])=[O:11])=[N:2]2)=[CH:18][CH:17]=1

Participants

8

Reactant 4

HCID 77384-Methoxybenzyl alcoholHCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 178498889HCID 178498889, compound

Product 2

HCID 89463489HCID 89463489, compoundYield 32%HCID 89473329HCID 89473329, compoundYield 29%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of dimethyl 1H-pyrazole-3,4-dicarboxylate (2.5 g, 13.6 mmol) in THF (100 mL) was added 4-methoxybenzyl alcohol (1.78 mL, 14.2 mmol) and triphenylphosphine 3.74 g, 14.2 mmol) followed by dropwise addition of DIAD (2.8 mL, 14.2 mmol) and the mixture was stirred at ambient temperature under nitrogen atmosphere for 3 h. The mixture was diluted with EtOAc and washed with saturated sodium bicarbonate/water. The organic phase was dried over sodium sulfate, concentrated and purified on silica using EtOAc/hexanes 0-50% to provide the title compound (1.4 g, 32%) and isomer dimethyl 1{{4-(methyloxy)phenyl]methyl}-1H-pyrazole-3,4-dicarboxylate (1.3 g, 29%). 1H NMR (400 MHz, DMSO-d6) δ ppm 7.98 (s, 1H), 7.18 (d, 2H), 6.9 (d, 2H), 5.4 (s, 2H), 3.92 (s, 3H), 3.89 (s, 3H), 3.87 (s, 3H); ES-LCMS: 305.28 (M+1).

Workup

  1. washwashed with saturated sodium bicarbonate/water
  2. dry with materialThe organic phase was dried over sodium sulfate
  3. concentrationconcentrated
  4. custompurified on silica

Sources & evidence

ORD record
ord-7816454bd8ae4eb6bf4c3efd1ae2fbf1
Source dataset
uspto-grants-2015_04
Patent number
US09012642B2

Reaction notes

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