O-(tert-Butyldimethylsilyl)hydroxylamine → HCID 178433359, compound

HRID 656597Notes

Reaction equation

HRID 656597 reaction equation
[NH2:1][C:2]1[N:3]=[C:4]([CH3:21])[C:5]2[C:11](=S)[NH:10][C@@H:9]([C:13]3[CH:18]=[CH:17][C:16]([F:19])=[CH:15][C:14]=3[Br:20])[CH2:8][C:6]=2[N:7]=1.[Si:22]([O:29][NH2:30])([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23]>[Hg](OC(C)=O)OC(C)=O.C1(C)C=CC=CC=1>[Si:22]([O:29]/[N:30]=[C:11]1\[NH:10][C@@H:9]([C:13]2[CH:18]=[CH:17][C:16]([F:19])=[CH:15][C:14]=2[Br:20])[CH2:8][C:6]2[N:7]=[C:2]([NH2:1])[N:3]=[C:4]([CH3:21])[C:5]\1=2)([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23]

Participants

5

Reactant 2

HCID 4691350O-(tert-Butyldimethylsilyl)hydroxylamineHCID 45257321HCID 45257321, compound

Product 1

HCID 178433359HCID 178433359, compoundYield 80%

Reagents, catalysts & solvents 2

HCID 16683746DiacetyloxymercuryCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of (R)-2-amino-7-(2-bromo-4-fluorophenyl)-4-methyl-7,8-dihydropyrido[4,3-d]pyrimidine-5(6H)-thione (366 mg, 1.0 mmol), O-(tert-butyldimethylsilyl)hydroxylamine (588 mg, 4.0 mmol), Hg(OAc)2 (640 mg, 2.0 mmol) and toluene (5 mL) was heated at 100° C. for 2 h. The mixture was cooled to r.t. and filtered through celite. Filtrate concentrated and the resulting oily residue was triturated with dry methanol to afford a pale yellow solid. Filtered and dried to afford ((R,Z)-2-amino-7-(2-bromo-4-fluorophenyl)-4-methyl-7,8-dihydropyrido[4,3-d]pyrimidin-5(6H)-one O-tert-butyldimethylsilyloxime (384 mg, 80%) as a pale yellow solid. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.22 (s, 3H), 0.23 (s, 3H) 0.97 (s, 9H) 2.70 (s, 3H) 2.91 (dd, J=16.42, 8.08 Hz, 1H) 3.19 (ddd, J=16.36, 4.86, 1.26 Hz, 1H) 4.99 (ddd, J=7.77, 5.12, 2.02 Hz, 1H) 7.05 (td, J=8.27, 2.65 Hz, 1H) 7.33 (dd, J=8.08, 2.78 Hz, 1H) 7.39 (dd, J=8.72, 5.94 Hz, 1H). MS (ES) [M+H] calculated for C20H28BrFN5OSi, 480.12. found 480.30.

Workup

  1. temperatureThe mixture was cooled to r.t.
  2. filtrationfiltered through celite
  3. concentrationFiltrate concentrated
  4. customthe resulting oily residue was triturated with dry methanol
  5. customto afford a pale yellow solid
  6. filtrationFiltered
  7. customdried

Sources & evidence

ORD record
ord-42c5ebba7bc94043ad3a9537368069c8
Source dataset
uspto-grants-2011_12
Patent number
US08071766B2

Reaction notes

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