Diisopropyl Ether → 3,3-Dimethyl-2-oxobutyl (6-methylpyrid-2-yl)dithiocarbamate

HRID 261199Notes

Reaction equation

HRID 261199 reaction equation
Br[CH2:2][C:3](=[O:8])[C:4]([CH3:7])([CH3:6])[CH3:5].[CH3:9][C:10]1[N:15]=[C:14]([NH:16][C:17](=[S:19])[S-:18])[CH:13]=[CH:12][CH:11]=1.C([NH+](CC)CC)C.C(OC(C)C)(C)C>C(#N)C>[CH3:9][C:10]1[N:15]=[C:14]([NH:16][C:17](=[S:18])[S:19][CH2:2][C:3](=[O:8])[C:4]([CH3:7])([CH3:6])[CH3:5])[CH:13]=[CH:12][CH:11]=1

Participants

5

Reactant 3

HCID 7914Diisopropyl EtherHCID 21642BromopinacoloneHCID 20393055Triethylammonium 6-methylpyrid-2-yldithiocarbamate

Product 1

HCID 543956723,3-Dimethyl-2-oxobutyl (6-methylpyrid-2-yl)dithiocarbamateYield 69.9%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
2 °C

Procedure

1-Bromo-3,3-dimethylbutan-2-one (40.0 g) is added to a suspension of triethylammonium (6-methylpyrid-2-yl)dithiocarbamate (64.0 g) in anhydrous acetonitrile (600 cc) at a maximum temperature of 20° C. The reaction is continued for 2 hours at 20° C. The insoluble hydrobromide of triethylamine is removed by filtration and washed with acetonitrile (50 cc). The organic phases are combined and evaporated under reduced pressure (20 mm.Hg) at 45° C. The residual oil is treated with diethyl ether (1200 cc). After 1 hour at 20° C., the ethereal solution is filtered, washed twice with distilled water (total 400 cc), dried over sodium sulphate and evaporated. The product obtained (60.0 g) is dissolved in boiling diisopropyl ether (870 cc) and the boiling solution is filtered. After 1 hour's cooling at 2° C., the resulting crystals are filtered off, washed twice with ice-cold diisopropyl ether (total 100 cc) and dried under reduced pressure (0.1 mm.Hg) at 40° C. to give 3,3-dimethyl-2-oxobutyl (6-methylpyrid-2-yl)dithiocarbamate (44.1 g) melting at 80° C.

Workup

  1. customThe insoluble hydrobromide of triethylamine is removed by filtration
  2. washwashed with acetonitrile (50 cc)
  3. customevaporated under reduced pressure (20 mm.Hg) at 45° C
  4. additionThe residual oil is treated with diethyl ether (1200 cc)
  5. waitAfter 1 hour at 20° C.
  6. filtrationthe ethereal solution is filtered
  7. washwashed twice with distilled water (total 400 cc)
  8. dry with materialdried over sodium sulphate
  9. customevaporated
  10. customThe product obtained (60.0 g)
  11. dissolutionis dissolved
  12. filtrationthe boiling solution is filtered
  13. filtrationthe resulting crystals are filtered off
  14. washwashed twice with ice-cold diisopropyl ether (total 100 cc)
  15. customdried under reduced pressure (0.1 mm.Hg) at 40° C.

Sources & evidence

ORD record
ord-a73195e4051343dea9cd3fb068b107ba
Source dataset
uspto-grants-1979_08
Patent number
US04164579

Reaction notes

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