Carbon Disulfide → HCID 136118801, compound

HRID 1647415Notes

Reaction equation

HRID 1647415 reaction equation
[CH3:1][C:2]([C:5]1[C:10]([O:11]COCCOC)=[C:9]([C:18]([CH3:21])([CH3:20])[CH3:19])[N:8]=[C:7]([C:22]([NH:24][NH2:25])=[O:23])[N:6]=1)([CH3:4])[CH3:3].[OH-].[K+].[C:28](=[S:30])=S>CO>[CH3:4][C:2]([C:5]1[C:10]([OH:11])=[C:9]([C:18]([CH3:20])([CH3:19])[CH3:21])[N:8]=[C:7]([C:22]2[O:23][C:28](=[S:30])[NH:25][N:24]=2)[N:6]=1)([CH3:1])[CH3:3]

Participants

5

Reactant 3

HCID 6348Carbon DisulfideHCID 14797Potassium HydroxideHCID 67780415HCID 67780415, compound

Product 1

HCID 136118801HCID 136118801, compoundYield 20%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

4,6-Bis(1,1-dimethylethyl)-5-[(2-methoxyethoxy)methoxy]-2-pyrimidine carboxylic acid hydrazide (0.9 g, 2.5 moles), KOH (0.16 g, 2.8 moles), and carbon disulfide (0.44 g, 5.8 mmoles) are dissolved in 20 mL of MeOH. The reaction mixture is warmed to reflux under argon for 24 hours. It is cooled to room temperature, quenched with 150 mL of 10% HOAc/H2O, and extracted with ether (3×100 mL). The ether extract is washed with brine (3×100 mL) and evaporated. The oil remaining is taken up in 20 mL of TFA and stirred at room temperature for 30 minutes. The TFA is evaporated on the rotovap, and the oil is partitioned between 100 mL of ether and 100 mL of H2O. The pH of the water layer is adjusted to 5 by the addition of saturated sodium bicarbonate. The layers are separated and the organic layer is washed with 50 mL of brine. Drying over MgSO4 and evaporation of solvent gives a yellow oil. Flash chromatography in 50% Et2O/hexane followed by two recrystallizations from Et2O/hexane gives 0.16 g (20%) of 5-[ 4,6-bis (1,1-dimethylethyl) -5-hydroxy-2-pyrimidinyl ]-1,3,4-oxadiazole-2(3H )-thione, 234°-236° C. dec. Analysis for C14H20N4O2S: Calcd.: C, 54.52; H, 6.54; N, 18.17; S, 10.40. Found: C, 54.46; H, 6.40; N, 18.38; S, 10.53.

Workup

  1. temperatureThe reaction mixture is warmed
  2. temperatureto reflux under argon for 24 hours
  3. customquenched with 150 mL of 10% HOAc/H2O
  4. extractionextracted with ether (3×100 mL)
  5. extractionThe ether extract
  6. washis washed with brine (3×100 mL)
  7. customevaporated
  8. customThe TFA is evaporated on the rotovap
  9. customthe oil is partitioned between 100 mL of ether and 100 mL of H2O
  10. additionThe pH of the water layer is adjusted to 5 by the addition of saturated sodium bicarbonate
  11. customThe layers are separated
  12. washthe organic layer is washed with 50 mL of brine
  13. dry with materialDrying over MgSO4 and evaporation of solvent
  14. customgives a yellow oil
  15. customFlash chromatography in 50% Et2O/hexane followed by two recrystallizations from Et2O/hexane

Sources & evidence

ORD record
ord-3a46c5ce5fcd4d22a8e2d2fb54a0891e
Source dataset
uspto-grants-1995_07
Patent number
US05432181

Reaction notes

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