Chloroacetonitrile → 3-Amino-4,6-dimethylthieno[2,3-b]pyridine-2-carbonitrile

HRID 2173663Notes

Reaction equation

HRID 2173663 reaction equation
[C:1]([C:3]1[C:4]([SH:11])=[N:5][C:6]([CH3:10])=[CH:7][C:8]=1[CH3:9])#[N:2].[OH-].[K+].Cl[CH2:15][C:16]#[N:17]>CN(C=O)C>[NH2:2][C:1]1[C:3]2[C:4](=[N:5][C:6]([CH3:10])=[CH:7][C:8]=2[CH3:9])[S:11][C:15]=1[C:16]#[N:17]

Participants

5

Reactant 3

HCID 7856ChloroacetonitrileHCID 14797Potassium Hydroxide2×HCID 178425247HCID 178425247, compound

Product 1

HCID 6088783-Amino-4,6-dimethylthieno[2,3-b]pyridine-2-carbonitrileYield 94%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

The 3-cyano-4,6-dimethyl-2-mercaptopyridine (500 mg, 3.04 mmol) was stirred in DMF (6.0 mL). An aqueous 10% KOH solution (1.71 mL, 3.04 mmol) was added, followed by chloroacetonitrile (0.19 mL, 3.04 mmol). The reaction was stirred at RT for 15 minutes, LC/MS indicates initial thio-alkylation is complete. A second equivalent of 10% KOH (1.71 mL, 3.04 mmol) was added and the resulting slurry was warmed to 50° C. and stirred about 30 min. LC/MS indicates reaction is done. The slurry was cooled to RT, then poured into 80 g of crushed ice and allowed to warm until the ice melted. The cold slurry was poured through filter paper, washing the solid with cold water. The solid was collected and dried in a vacuum oven to give 580 mg (94%) of the pure product as a light yellow solid. 1H NMR (400 MHz, DMSO-d6): δ ppm 7.09 (s, 1H), 6.50 (s, 2H), 2.70 (s, 3H), 2.49 (s, 3H). LC/MS: RT=0.56 min., m/z=204.0 [M+H]+.

Workup

  1. temperaturethe resulting slurry was warmed to 50° C.
  2. stirringstirred about 30 min
  3. customreaction
  4. temperatureThe slurry was cooled to RT
  5. additionThe cold slurry was poured
  6. filtrationthrough filter paper
  7. washwashing the solid with cold water
  8. customThe solid was collected
  9. customdried in a vacuum oven

Sources & evidence

ORD record
ord-b306cec520794e53bbdb8bcf61844c5c
Source dataset
uspto-grants-2015_06
Patent number
US09056876B2

Reaction notes

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