Hydrochloric Acid → 2-Chloro-N-ethyl-6-(1,1-dimethylethyl)benzamide

HRID 368690Notes

Reaction equation

HRID 368690 reaction equation
[C:1]([C:5]1[CH:15]=[CH:14][CH:13]=[CH:12][C:6]=1[C:7]([NH:9][CH2:10][CH3:11])=[O:8])([CH3:4])([CH3:3])[CH3:2].CN(CCN(C)C)C.[Li]C(CC)C.[Cl:29]C(Cl)(Cl)C(Cl)(Cl)Cl.Cl>C1COCC1.C1CCCCC1.C(Cl)Cl.O>[Cl:29][C:12]1[CH:13]=[CH:14][CH:15]=[C:5]([C:1]([CH3:2])([CH3:3])[CH3:4])[C:6]=1[C:7]([NH:9][CH2:10][CH3:11])=[O:8]

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 6214HexachloroethaneHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 186300432-tert-butyl-N-ethylbenzamideHCID 178418400CID 53628100

Product 1

HCID 186302102-Chloro-N-ethyl-6-(1,1-dimethylethyl)benzamide

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×HCID 8078CyclohexaneSolvent

Conditions

Temperature
-30 °C

Procedure

To a solution of 2-tert-butyl-N-ethylbenzamide (44 g, 215 mmol) and TMEDA (70 mL, 446 mmol) in 500 mL THF at -70° C. under a positive nitrogen atmosphere was added at a rapid stream 520 mL 1.3M s-BuLi in cyclohexane, maintaining the temperature at below -60° C. After the addition was complete, the resulting reaction solution was warmed to -30° C. and stirred at between -30° C. and -26° C. for 50 min. The solution was then cooled to below -70° C. and a solution of hexachloroethane (80 g) in 250 mL THF was added at between -70 and -65° C. Stirring at below -70° C. was continued for 0.5 h. The resulting reaction solution was then poured into water. CH2Cl2 and 3N HCl were added. The aq layer was separated and extracted with CH2Cl2. The combined organic layers were washed with water, dried and concentrated in vacuo. The solid was triturated with hexane and then purified by flash chromatography with 15% ethyl acetate/hexane as eluent to give the desired product as a white solid. m.p. 121-123° C.

Workup

  1. temperaturemaintaining the temperature at below -60° C
  2. additionAfter the addition
  3. customthe resulting reaction solution
  4. temperatureThe solution was then cooled to below -70° C.
  5. stirringStirring at below -70° C.
  6. waitwas continued for 0.5 h
  7. customThe resulting reaction solution
  8. customThe aq layer was separated
  9. extractionextracted with CH2Cl2
  10. washThe combined organic layers were washed with water
  11. customdried
  12. concentrationconcentrated in vacuo
  13. customThe solid was triturated with hexane
  14. custompurified by flash chromatography with 15% ethyl acetate/hexane as eluent

Sources & evidence

ORD record
ord-b7c1152e897747faafbb455667ae8c49
Source dataset
uspto-grants-2000_10
Patent number
US06133252

Reaction notes

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