N,N,N',N'-Tetramethylethylenediamine → HCID 13825792, compound

HRID 2372800Notes

Reaction equation

HRID 2372800 reaction equation
C([Li])CCC.CCCCCC.[CH3:12][C:13]1[CH:14]=[C:15]([CH:22]=[CH:23][CH:24]=1)[CH2:16][N:17]1[CH:21]=[CH:20][N:19]=[CH:18]1.CN(CCN(C)C)C.[CH:33](=[O:38])[C:34]([CH3:37])([CH3:36])[CH3:35]>C1COCC1.O>[N:17]1([CH:16]([C:15]2[CH:14]=[C:13]([CH3:12])[CH:24]=[CH:23][CH:22]=2)[CH:33]([OH:38])[C:34]([CH3:37])([CH3:36])[CH3:35])[CH:21]=[CH:20][N:19]=[CH:18]1

Participants

7

Reactant 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 12417PivalaldehydeHCID 18679298HCID 18679298, compoundHCID 178418244HCID 178418244, compound

Product 1

HCID 13825792HCID 13825792, compoundYield 8.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-70 °C

Procedure

39 ml (60 mmol) of a 1.55 molar n-butyllithium/hexane solution were added dropwise to a solution of 5.17 g (30 mmol) of N-(3-methylbenzyl)-imidazole and 3.49 g (30 mmol) of TMEDA in 60 ml of absolute THF at -70° C. The mixture was stirred for 30 minutes at about -70° C., after which a solution of 3.80 g (33 mmol) of 75% strength pivalaldehyde in 30 ml of absolute THF was added dropwise at about -70° C. in the course of 20 minutes, stirring was continued for 20 minutes at about -70° C. and the mixture was allowed to warm up to room temperature in the course of 2 hours. Thereafter, water was added, while cooling, and the resulting mixture was extracted with ether. The residue (9.3 g) from the ether extract was crystallized from a diisopropyl ether/hexane mixture. This gave 2.2 g of crystals, which consisted of about 90% of a by-product, 1-(3-methylbenzyl)-2-(1-hydroxy-2,2-dimethylprop-1-yl)-imidazole. The residue from the mother liquor was recrystallized from a diisopropyl ether/acetonitrile solution, and the crystalline product isolated in this procedure was then recrystallized twice from acetonitrile. 0.64 g (=8.3% of theory) of pure 1-(1-imidazolyl)-1-(3-tolyl)-3,3-dimethylbutan-2-ol of melting point 126° C. was obtained in this manner.

Workup

  1. stirringstirring
  2. waitwas continued for 20 minutes at about -70° C.
  3. temperatureto warm up to room temperature in the course of 2 hours
  4. temperaturewhile cooling
  5. extractionthe resulting mixture was extracted with ether
  6. extractionThe residue (9.3 g) from the ether extract
  7. customwas crystallized from a diisopropyl ether/hexane mixture
  8. customThe residue from the mother liquor was recrystallized from a diisopropyl ether/acetonitrile solution
  9. customthe crystalline product isolated in this procedure
  10. customwas then recrystallized twice from acetonitrile

Sources & evidence

ORD record
ord-7bb36338e7654812b8cb37ea24187a58
Source dataset
uspto-grants-1992_03
Patent number
US05100890

Reaction notes

Loading…