Ethanethiol → CHEBI:40460

HRID 2179127Notes

Reaction equation

HRID 2179127 reaction equation
[P:1]([O:5][CH2:6][C@H:7]1[O:11][C@@H:10]([N:12]2[C:26]3[N:25]=[CH:24][N:23]=[C:16]([NH:17]C(=O)CCC)[C:15]=3[N:14]=[CH:13]2)[C@H:9]([O:27][CH3:28])[C@@H:8]1[O:29]C(=O)C1C=CC=CC=1)([OH:4])([OH:3])=[O:2].C(N(CC)CC)C.C[Si](Cl)(C)C.II.O.C(S)C>N1C=CC=CC=1>[P:1]([O:5][CH2:6][C@H:7]1[O:11][C@@H:10]([N:12]2[C:26]3[N:25]=[CH:24][N:23]=[C:16]([NH2:17])[C:15]=3[N:14]=[CH:13]2)[C@H:9]([O:27][CH3:28])[C@@H:8]1[OH:29])([OH:3])([OH:4])=[O:2]

Participants

7

Reactant 5

HCID 6343EthanethiolHCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 86660149HCID 86660149, compoundHCID 129818843HCID 129818843, compound

Product 1

HCID 161605CHEBI:40460Yield 37%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent3×

Procedure

3′-O-Benzoyl-N6-butyryl-2′-O-methyl adenosine 5′-H-phosphonate 10 (55 mg, 0.088 mmol) was dried by evaporation of added dry pyridine (5 mL) and 30 min drying on a vacuum pump. To the compound was added pyridine (0.8 mL), triethylamine (5 eq, 0.44 mmol, 61 μL) and trimethyl silyl chloride (5 eq, 0.44 mmol, 55.7 μL). The reaction was stirred for 15 min at room temperature, whereupon a solution of I2/H2O in pyridine (1.1 eq 12, 24 mg, 50 μL H2O, 500 μL pyridine) was added. After an additional 5 min a sample was taken and analysed by 31P NMR which showed complete oxidation. A drop of ethanethiol was added to achieve a colorless solution, the solvent was removed under reduced pressure and the crude compound was dissolved in MeOH/NH3 (sat.). The mixture was left overnight at room temperature, whereupon the solvent was removed under reduced pressure and the solid was dissolved in water. The aqueous solution was washed with diethyl ether (2×). The water layer was then collected, concentrated under reduced pressure and purified by RP-HPLC using a triethyl ammonium acetate buffer pH 6.5. RT=14 min (0-20 min 12% B, B=50% CH3CN). Yield 37% of compound 11 as triethyl ammonium salt (18.4 mg). 31P NMR (D2O) δ-1.02, 13C NMR δ 7.3, 22.4, 45.7, 57.2, 63.0, 68.3, 70.7, 82.3, 84.1, 84.4, 118.2, 126.5, 140.2, 148.2, 151.8, 154.6, 180.4, 199.5, MS (ES-TOF) m/z calculated: 361.08. found: 361.10.

Workup

  1. customdrying on a vacuum pump
  2. additionwas added
  3. customthe solvent was removed under reduced pressure
  4. dissolutionthe crude compound was dissolved in MeOH/NH3 (sat.)
  5. waitThe mixture was left overnight at room temperature, whereupon the solvent
  6. customwas removed under reduced pressure
  7. dissolutionthe solid was dissolved in water
  8. washThe aqueous solution was washed with diethyl ether (2×)
  9. customThe water layer was then collected
  10. concentrationconcentrated under reduced pressure
  11. custompurified by RP-HPLC
  12. customRT=14 min (0-20 min 12% B, B=50% CH3CN)

Sources & evidence

ORD record
ord-f723c026e2a943279cf093fd7e3dae35
Source dataset
uspto-grants-2015_06
Patent number
US09067964B2

Reaction notes

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