Acetic Acid → 4-({[Tert-butyl(dimethyl)silyl]oxy}methyl)-6-ethylpyridin-2-amine

HRID 1814010Notes

Reaction equation

HRID 1814010 reaction equation
[Si:1]([O:8][CH2:9][C:10]1[CH:15]=[C:14]([CH2:16][CH3:17])[N:13]=[C:12]([NH:18]C(=O)OC(C)(C)C)[CH:11]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C(N(C(C)C)C(C)C)C.C([O-])(O)=O.[Na+].C(O)(=O)C>C(Cl)Cl.CO>[Si:1]([O:8][CH2:9][C:10]1[CH:15]=[C:14]([CH2:16][CH3:17])[N:13]=[C:12]([NH2:18])[CH:11]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 81531DiisopropylethylamineHCID 516892Sodium BicarbonateHCID 69550702Tert-butyl 4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-6-ethylpyridin-2-ylcarbamate

Product 1

HCID 695514044-({[Tert-butyl(dimethyl)silyl]oxy}methyl)-6-ethylpyridin-2-amine

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

tert-Butyl 4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-6-ethylpyridin-2-ylcarbamate (0.352 g, 0.96 mmol) was dissolved in 2 mL CH2Cl2. tert-Butyl (dimethyl)silyl trifluoromethanesulfonate was added and the solution was stirred for 5.5 hours. N-Ethyl-N,N-diisopropylamine (0.669 mL, 3.84 mmol) was added and the solution was stirred for 0.5 hour. Saturated NaHCO3 (aq) was added and the precipitate was extracted with CH2Cl2 (3×). The combined organic layers were dried (Na2SO4), filtered, and concentrated to afford a yellow oil. The oil was dissolved in 10 mL MeOH. Acetic acid (0.20 mL) was added and the solution was stirred for 0.5 hour. The reaction was concentrated in vacuo to afford an off white solid. The solid was purified by flash column chromatography (1:1 EtOAc/hexanes). The fractions containing the desired compound were concentrated to dryness to afford 12-1 as a colorless oil. 1H NMR (CDCl3) δ 6.54 (s, 1H), 6.46 (s, 1H), 5.87 (bs, 2H), 4.65 (s, 2H), 2.73 (q, 2H, J=7.63 Hz), 1.29 (t, 3H, J=7.63 Hz), 0.95 (s, 9H), 0.12 (s, 6H).

Workup

  1. stirringthe solution was stirred for 0.5 hour
  2. extractionthe precipitate was extracted with CH2Cl2 (3×)
  3. dry with materialThe combined organic layers were dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto afford a yellow oil
  7. stirringthe solution was stirred for 0.5 hour
  8. concentrationThe reaction was concentrated in vacuo
  9. customto afford an off white solid
  10. customThe solid was purified by flash column chromatography (1:1 EtOAc/hexanes)
  11. additionThe fractions containing the desired compound
  12. concentrationwere concentrated to dryness

Sources & evidence

ORD record
ord-3bbc044c762c49c0b179e606fb8338aa
Source dataset
uspto-grants-2005_04
Patent number
US06875767B2

Reaction notes

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