Hydrochloric Acid → HCID 14011774, compound

HRID 986220Notes

Reaction equation

HRID 986220 reaction equation
C([Li])CCC.C(NC(C)C)(C)C.[CH3:13][N:14]([CH3:24])[C:15]1[N:20]=[C:19]([CH3:21])[C:18]([O:22][CH3:23])=[CH:17][N:16]=1.Cl[C:26]([O:28][CH2:29][CH3:30])=[O:27].Cl>C1COCC1.CCCCCC.C(OCC)(=O)C.O>[CH3:24][N:14]([CH3:13])[C:15]1[N:20]=[C:19]([CH2:21][C:26]([O:28][CH2:29][CH3:30])=[O:27])[C:18]([O:22][CH3:23])=[CH:17][N:16]=1

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 7912DiisopropylamineHCID 10928Ethyl chloroformateHCID 14011773HCID 14011773, compoundHCID 178418339Butyllithium

Product 1

HCID 14011774HCID 14011774, compoundYield 47.2%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×HCID 21226206Ethyl acetate hexaneSolvent

Conditions

Temperature
5 °C

Procedure

A three-necked 150 ml flask fitted with a septum, a low temperature thermometer and an addition funnel was charged under nitrogen with 11.6 ml (18.6 mmol) of 1.6 M n-butyllithium. After cooling the flask to 5° C., a solution of 2.6 ml (18.6 mmol) of diisopropylamine in 20 ml dry THF was added dropwise over 5 minutes. After addition was completed, the mixture was stirred at 5° C. for 15 minutes and then cooled to -70° C. To the reaction mixture was added a solution of 1.56 g (9.3 mmol) of 2-dimethylamino-4-methyl-5-methoxypyrimidine in 20 ml dry THF over ten minutes. The reaction mixture was then stirred at -70° C. for 1.5 hour, and a solution added of 2.0 g (18.6 mmol) of ethyl chloroformate in 20 ml dry THF over five minutes. The reaction mixture was stirred at -70° C. for a half hour and then allowed to warm to -15° C. over 15 minutes. The reaction mixture was poured into 100 ml of water, the aqueous mixture brought to pH 8.5 with 1N HCl and extracted with three 25 ml portions of chloroform. The combined extracts were dried over Na2SO4, filtered and evaporated leaving an oil. Chromatography over 100 g of silica gel with hexane/ethyl acetate (9:1) yielded 47% (1.05 g) of the title compound as a colorless liquid. NMR(CDCl3) 8.0 (s, 1H), 4.19 (q, J=7 Hz, 2H), 3.75 (s, 3H), 3.65 (s, 2H), 3.05 (s, 6H), 1.1 (t, J=7 Hz, 3H).

Workup

  1. customA three-necked 150 ml flask fitted with a septum
  2. additionAfter addition
  3. temperaturecooled to -70° C
  4. stirringThe reaction mixture was then stirred at -70° C. for 1.5 hour
  5. stirringThe reaction mixture was stirred at -70° C. for a half hour
  6. temperatureto warm to -15° C. over 15 minutes
  7. extractionextracted with three 25 ml portions of chloroform
  8. dry with materialThe combined extracts were dried over Na2SO4
  9. filtrationfiltered
  10. customevaporated
  11. customleaving an oil

Sources & evidence

ORD record
ord-4a57ac28e24f4763a766ae300ea31356
Source dataset
uspto-grants-1987_12
Patent number
US04711888

Reaction notes

Loading…