Hydrofluoric Acid → HCID 462654, compound

HRID 1080897Notes

Reaction equation

HRID 1080897 reaction equation
[OH:1][C:2]1[CH:26]=[CH:25][CH:24]=[CH:23][C:3]=1[C:4]([NH:6][CH2:7][C:8]1[S:9][S:10][C:11]([CH2:14][O:15][Si](C(C)(C)C)(C)C)=[CH:12][CH:13]=1)=[O:5].F>C(#N)C>[OH:1][C:2]1[CH:26]=[CH:25][CH:24]=[CH:23][C:3]=1[C:4]([NH:6][CH2:7][C:8]1[S:9][S:10][C:11]([CH2:14][OH:15])=[CH:12][CH:13]=1)=[O:5]

Participants

4

Reactant 2

HCID 14917Hydrofluoric AcidHCID 10250978HCID 10250978, compound

Product 1

HCID 462654HCID 462654, compoundYield 65%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

To a stirred solution of the above (silyloxy)amide 22 (52 mg; 0.127 mmol) in 2.0 mL of acetonitrile was added 2.0 mL of a 1:3 solution of 30% aqueous hydrofluoric acid solution in acetonitrile. The resulting orange solution was stirred for 40 minutes in the ice bath then the excess acid was destroyed by the addition of about 10 mL of a 10% aqueous potassium carbonate solution. The reaction mixture was partitioned between 50 mL of ethyl acetate and 20 mL of saturated aqueous sodium chloride. The layers were separated and the aqueous phase was extracted with 50 mL of ethyl acetate. The combined organic phases were washed with 50 mL of saturated aqueous sodium chloride, dried (Na2SO4) and concentrated in vacuo. The residue (35 mg) was chromatographed over 20 g of silica gel (ethyl acetate-hexane, 1:1) to give 24.4 mg (65%) of the benzamide as an orange oil. 1H NMR (CD3OD; spectrum shows amide bond isomers) δ7.773 (dd, J=8.0, 1.6 Hz, 1H, ArH), 7.383 (dt, J=8.4, 1.6 Hz, 1H, ArH), 6.925-6.860 (m, 2H, ArH), 6.371 (br s, 2H, C=CH), 4.691 (s, 2H, CH2 ; minor isomer), 4.669 (s, 2H, CH2 ; minor isomer), 4.198 (s, 2H, CH2 ; major isomer), 4.173 (s, 2H, CH2 ; major isomer); 13C NMR (CD3OD; spectrum shows amide bond isomers) δ170.987, 161.079, 136.252, 134.962, 133.294, 129.055, 127.061, 125.984, 120.175, 118.424, 116.816, 64.778 (major isomer), 60.079 (minor isomer), 44.033 (major isomer), 39.112 (minor isomer); MS (LSIMS) m/z=55.0 (100%), 295.1 (M+).

Workup

  1. customthe excess acid was destroyed by the addition of about 10 mL of a 10% aqueous potassium carbonate solution
  2. customThe reaction mixture was partitioned between 50 mL of ethyl acetate and 20 mL of saturated aqueous sodium chloride
  3. customThe layers were separated
  4. extractionthe aqueous phase was extracted with 50 mL of ethyl acetate
  5. washThe combined organic phases were washed with 50 mL of saturated aqueous sodium chloride
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated in vacuo
  8. customThe residue (35 mg) was chromatographed over 20 g of silica gel (ethyl acetate-hexane, 1:1)

Sources & evidence

ORD record
ord-7521a622505d47db85123b58d74127ab
Source dataset
uspto-grants-1996_12
Patent number
US05583235

Reaction notes

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