Pyridine → 1,1-dimethylethyl 3-(1,2,4-thiadiazol-5-yl)-5,6-dihydro[1,2,4]triazolo[4,3-a]pyrazine-7(8H)-carboxylate

HRID 1889043Notes

Reaction equation

HRID 1889043 reaction equation
C[N:2](/[CH:4]=[N:5]/[C:6]([C:8]1[N:12]2[CH2:13][CH2:14][N:15]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:16][C:11]2=[N:10][N:9]=1)=[S:7])C.N1C=CC=CC=1>C(O)C.CO>[S:7]1[C:6]([C:8]2[N:12]3[CH2:13][CH2:14][N:15]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:16][C:11]3=[N:10][N:9]=2)=[N:5][CH:4]=[N:2]1

Participants

5

Reactant 2

HCID 1049PyridineHCID 178484361HCID 178484361, compound

Product 1

HCID 665993371,1-dimethylethyl 3-(1,2,4-thiadiazol-5-yl)-5,6-dihydro[1,2,4]triazolo[4,3-a]pyrazine-7(8H)-carboxylateYield 53.9%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 887MethanolSolvent

Conditions

Temperature
25 °C

Procedure

A mixture of 1,1-dimethylethyl 3-({[(1E)-(dimethylamino)methylidene]amino}carbonothioyl)-5,6-dihydro[1,2,4]triazolo[4,3-a]pyrazine-7(8H)-carboxylate (I113)(0.118 g, 0.349 mmol) and pyridine (0.056 ml, 0.698 mmol) in ethanol (2 ml) was stirred at 25° C. and hydroxylamine O-sulfonic acid (0.043 g, 0.384 mmol) in methanol (1.2 ml) was added in one batch. The mixture was stirred at RT and after a few minutes the solution became clear. After 1 h, the mixture had changed from orange to pale yellow in colour. The solvents were evaporated and the concentrated mixture was diluted with DCM (50 ml) and washed with water (5 ml), 0.2M NaOH (5 ml) and water (5 ml) and the organic layer was dried and concentrated. Chromatography (SP4, 0-100% ethyl acetate in isohexane) gave a white foam (58 mg). NMR showed some high field impurities therefore the foam was triturated with isohexane to give a white solid in 51.2 mg of desired product.

Workup

  1. stirringThe mixture was stirred at RT and after a few minutes the solution
  2. customThe solvents were evaporated
  3. additionthe concentrated mixture was diluted with DCM (50 ml)
  4. washwashed with water (5 ml), 0.2M NaOH (5 ml) and water (5 ml)
  5. customthe organic layer was dried
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-8ad768e271454baca1a9ba1fcb931d7e
Source dataset
uspto-grants-2013_08
Patent number
US08501946B2

Reaction notes

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