Dimethyl Sulfate → 3-Amino-2-carbomethoxy-5-Cyanothieno[3,2-b]pyridine

HRID 235077Notes

Reaction equation

HRID 235077 reaction equation
[NH2:1][C:2]1[C:6]2=[N+:7]([O-])[CH:8]=[CH:9][CH:10]=[C:5]2[S:4][C:3]=1[C:12]([O:14][CH3:15])=[O:13].S(OC)(OC)(=O)=O.[C-:23]#[N:24].[K+]>O>[NH2:1][C:2]1[C:6]2=[N:7][C:8]([C:23]#[N:24])=[CH:9][CH:10]=[C:5]2[S:4][C:3]=1[C:12]([O:14][CH3:15])=[O:13]

Participants

5

Reactant 3

HCID 6497Dimethyl SulfateHCID 9032Potassium CyanideHCID 104893153-Amino-2-carbomethoxythieno[3,2-b]pyridine-4-oxide

Product 1

HCID 233532833-Amino-2-carbomethoxy-5-Cyanothieno[3,2-b]pyridineYield 47%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

3-Amino-2-carbomethoxythieno[3,2-b]pyridine-4-oxide (3.1 g, 13.8 mmol) is stirred mechanically under N2 at 25° C. as dimethyl sulfate (1.3 mL, 14 mmol) is added dropwise. After stirring at 80° C. for 2 h, the reaction is cooled to 250C and the resulting solid is washed with acetone (50 mL) is added. The solid is dissolved in 10 mL H2O and is added dropwise to a 0° C. solution of KCN (2.7 g, 41 mmol) in H2O (10 mL). After stirring at 25° C. 18 h. The reaction was extracted with CH2Cl2. The organic layer was dried (MgSO4), filtered, concentrated, and chromatographed (CH2Cl2). 1.5 g (47%) of the title compound was obtained: 1H NMR (300 MHz, CDCl3) δ3.94 (s, 3H), 6.25 (bs, 2H), 7.70 (d, 1H), 8.20 (d, 1H); MS (DCI/NH3) m/e 234 (M+H)+.

Workup

  1. additionis added dropwise
  2. washthe resulting solid is washed with acetone (50 mL)
  3. additionis added
  4. dissolutionThe solid is dissolved in 10 mL H2O
  5. stirringAfter stirring at 25° C
  6. custom18 h
  7. extractionThe reaction was extracted with CH2Cl2
  8. dry with materialThe organic layer was dried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customchromatographed (CH2Cl2)

Sources & evidence

ORD record
ord-1c7faa1443ad4efcbee532d1a6808413
Source dataset
uspto-grants-1997_01
Patent number
US05597823

Reaction notes

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