Trimethylsilyldiazomethane → HCID 86724887, compound

HRID 510429Notes

Reaction equation

HRID 510429 reaction equation
[C:1](O)(=O)C.[Cl:5][C:6]1[C:29]([Cl:30])=[CH:28][CH:27]=[CH:26][C:7]=1[CH2:8][C:9]1[C:10]([CH3:25])=[N:11][N:12]2[C:17](=[O:18])[CH:16]=[C:15]([C:19]3[CH:24]=[CH:23][N:22]=[CH:21][CH:20]=3)[NH:14][C:13]=12.[CH3:31][Si](C=[N+]=[N-])(C)C>ClCCl.CO>[Cl:5][C:6]1[C:29]([Cl:30])=[CH:28][CH:27]=[CH:26][C:7]=1[CH2:8][C:9]1[C:13]2=[N:14][C:15]([C:19]3[CH:24]=[CH:23][N:22]=[CH:21][CH:20]=3)=[CH:16][C:17](=[O:18])[N:12]2[N:11]([CH3:1])[C:10]=1[CH3:25].[Cl:5][C:6]1[C:29]([Cl:30])=[CH:28][CH:27]=[CH:26][C:7]=1[CH2:8][C:9]1[C:10]([CH3:25])=[N:11][N:12]2[C:17]([O:18][CH3:31])=[CH:16][C:15]([C:19]3[CH:24]=[CH:23][N:22]=[CH:21][CH:20]=3)=[N:14][C:13]=12

Participants

5

Reactant 2

HCID 167693TrimethylsilyldiazomethaneHCID 178475921HCID 178475921, compound

Product 2

HCID 71270798HCID 71270798, compoundYield 15%HCID 86724887HCID 86724887, compoundYield 40%

Reagents, catalysts & solvents 1

HCID 21226129Dichloromethane methanolSolvent

Procedure

To a solution of 3-(2,3-dichlorobenzyl)-2-methyl-5-(pyridin-4-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one acetate (600 mg, 1.347 mmol) in dichloromethane/methanol (30 mL/15 mL) was added trimethylsilyldiazomethane (2 mL, 4.04 mmol). The mixture was stirred at room temperature overnight. Then the mixture was concentrated under reduced pressure. The residue was purified by a silica gel chromatography to give 3-(2,3-dichlorobenzyl)-1,2-dimethyl-5-(pyridin-4-yl)pyrazolo[1,5-a]pyrimidin-7(1H)-one (214 mg, 40%) and 3-(2,3-dichlorobenzyl)-7-methoxy-2-methyl-5-(pyridin-4-yl)pyrazolo[1,5-a]pyrimidine (83 mg, 15%). The structures of the two products were assigned according to NOESY. Example 33: 3-(2,3-dichlorobenzyl)-1,2-dimethyl-5-(pyridin-4-yl)pyrazolo[1,5-a]pyrimidin-7(1H)-one: LC/MS: MS (ES+) m/e 399 (MH+); 1H NMR (300 MHz, DMSO-d6) □ ppm 2.42 (s, 3H), 4.15 (s, 2H), 4.21 (s, 3H), 6.59 (s, 1H), 7.28 (t, J=7.8 Hz, 1H), 7.36 (dd, J=1.8, 7.8 Hz, 1H), 7.51 (dd, J=1.8, 7.8 Hz, 1H), 7.95 (d, J=6.3 Hz, 2H), 8.66 (d, J=6.3 Hz, 2H). Example 34: 3-(2,3-dichlorobenzyl)-7-methoxy-2-methyl-5-(pyridin-4-yl)pyrazolo[1,5-a]pyrimidine: LC/MS: MS (ES+); 1H NMR (300 MHz, CDCl3) δ ppm 2.44 (s, 3H), 4.31 (s, 5H), 6.58 (s, 1H), 7.04-7.07 (m, 2H), 7.32 (dd, J=3.0, 6.6 Hz, 1H), 7.50 (dd, J=1.5, 4.5 Hz, 2H), 8.76 (dd, J=1.5, 4.5 Hz, 2H).

Workup

  1. concentrationThen the mixture was concentrated under reduced pressure
  2. customThe residue was purified by a silica gel chromatography

Sources & evidence

ORD record
ord-e0c98e8277fe454fb9476fc7852bee74
Source dataset
uspto-grants-2015_08
Patent number
US09096605B2

Reaction notes

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