3-Pyridine aldoxime → HCID 11993992, compound

HRID 1913355Notes

Reaction equation

HRID 1913355 reaction equation
[CH:1](=[N:8][OH:9])[C:2]1[CH:7]=[CH:6][CH:5]=[N:4][CH:3]=1.ClN1C(=O)CCC1=O.[CH2:18]([NH:21][C:22](=[O:28])[O:23][C:24]([CH3:27])([CH3:26])[CH3:25])[C:19]#[CH:20].C(N(CC)CC)C>CN(C=O)C.C(Cl)Cl>[N:4]1[CH:5]=[CH:6][CH:7]=[C:2]([C:1]2[CH:20]=[C:19]([CH2:18][NH:21][C:22](=[O:28])[O:23][C:24]([CH3:26])([CH3:25])[CH3:27])[O:9][N:8]=2)[CH:3]=1

Participants

7

Reactant 4

HCID 6943-Pyridine aldoximeHCID 8471TriethylamineHCID 31398ChlorosuccinimideHCID 11073648tert-butyl N-(prop-2-yn-1-yl)carbamate

Product 1

HCID 11993992HCID 11993992, compoundYield 59.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 33 (161 mg, 1.3 mmol) in anhydrous DMF (5 mL) at 0° C. was added N-chlorosuccinimide (202 mg, 1.3 mmol) portionwise over 20 min. The resultant solution was heated to 50° C. and stirred for 50 min. The solution was cooled to room temperature and transferred to a flask containing CH2Cl2 (3 mL). To the solution was added a solution of tert-butyl prop-2-ynylcarbamate (204 mg, 1.3 mmol) in CH2Cl2 (3 mL), the solution was cooled to 0° C. and triethylamine (0.18 mL, 1.3 mmol) was added dropwise, the ice bath was removed and the solution was stirred at ambient temperature for 3 h. To the solution was added saturated aqueous sodium bicarbonate (30 mL), the organic fraction was collected and the aqueous fraction was extracted with CH2Cl2 (2×15 mL), back washed with water (30 mL), and brine (30 mL), dried (Na2SO4), filtered and the solvent was removed in vacuo. The crude material was chromatographed on silica gel (EtOAc/Hex, 50/50, Rf=0.16) to afford the title compound 34 (212 mg, 59% yield) as a an off white solid: mp=67-69° C.; 1H NMR (CDCl3) δ 8.93 (br s, 1H), 8.62 (m, 1H), 8.05 (m, 1H), 7.34 (m, 1H), 6.50 (s, 1H); 5.63 (br s, 1H); 4.43 (d, J=6 Hz, 1H), 1.40 (s, 9H); LRMS (ESI) calcd for C14H18N3O3 [M+H]+ 276. found 276.

Workup

  1. customtransferred to a flask
  2. temperaturethe solution was cooled to 0° C.
  3. customthe ice bath was removed
  4. stirringthe solution was stirred at ambient temperature for 3 h
  5. additionTo the solution was added saturated aqueous sodium bicarbonate (30 mL)
  6. customthe organic fraction was collected
  7. extractionthe aqueous fraction was extracted with CH2Cl2 (2×15 mL)
  8. washback washed with water (30 mL), and brine (30 mL)
  9. dry with materialdried (Na2SO4)
  10. filtrationfiltered
  11. customthe solvent was removed in vacuo
  12. customThe crude material was chromatographed on silica gel (EtOAc/Hex, 50/50, Rf=0.16)

Sources & evidence

ORD record
ord-6e9959847eea4ff19e7eb712afee0bdf
Source dataset
uspto-grants-2013_12
Patent number
US08609708B2

Reaction notes

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