Pyridine → N-(4-Chloro-phenyl)-2-(2,2-dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-N-(4-methyl-benzyl)-acetamide

HRID 392834Notes

Reaction equation

HRID 392834 reaction equation
[CH3:1][C:2]1([CH3:12])[O:6][C:5](=[O:7])/[C:4](=[CH:8]/[C:9](Cl)=[O:10])/[O:3]1.[Cl:13][C:14]1[CH:19]=[CH:18][C:17]([NH:20][CH2:21][C:22]2[CH:27]=[CH:26][C:25]([CH3:28])=[CH:24][CH:23]=2)=[CH:16][CH:15]=1.N1C=CC=CC=1>ClCCl>[Cl:13][C:14]1[CH:15]=[CH:16][C:17]([N:20]([CH2:21][C:22]2[CH:23]=[CH:24][C:25]([CH3:28])=[CH:26][CH:27]=2)[C:9](=[O:10])[CH:8]=[C:4]2[C:5](=[O:7])[O:6][C:2]([CH3:12])([CH3:1])[O:3]2)=[CH:18][CH:19]=1

Participants

5

Reactant 3

HCID 1049PyridineHCID 292568N-(4-Chlorophenyl)-4-methylbenzylamineHCID 12147055(Z)-2-(2,2-dimethyl-5-oxo-1,3-dioxolan-4-ylidene)acetyl chloride

Product 1

HCID 69773433N-(4-Chloro-phenyl)-2-(2,2-dimethyl-5-oxo-[1,3]dioxolan-4-ylidene)-N-(4-methyl-benzyl)-acetamideYield 87.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
22 °C

Procedure

A solution of (Z)-2,2-dimethyl-5-(chlorocarbonylmethylene)-1,3-dioxolan-4-one (0.553 g, 2.90 mmol) in dry dichloromethane (5 ml) was added dropwise to a cold (0-5° C.) solution of (4-chlorophenyl)-(4-methylbenzyl)-amine (0.545 g, 2.35 mmol) (Ballistreri et al., J. Org. Chem., 41, 1976, 3364), pyridine (0.35 ml) and a small crystal of 4-N,N-dimethylaminopyridine in dry dichloromethane (10 ml). After 30 min, the cooling bath was removed and the resulting clear solution was stirred at 22° C. for another 30 min. The reaction mixture was then diluted wih ethyl acetate, washed with saturated sodium bicarbonate, brine and dried (magnesium sulfate). Evaporation of the solvent in vacuo, filtration of the residue on a short silica gel pad (elution-toluene ethyl acetate; 85:15) followed by crystallization from ethyl acetate-hexane gave 0.794 g (87%) of the title amide as white needles: mp 149° C. 1HNMR 400 MHz (CDCl3) δ (ppm): 1.72 (6H, s, CH3), 2.31 (3H, s, CH3), 4.88 (2H, s, NCH2), 5.64 (1H, s, CH), 6.93 (2H, d, J=8.5 Hz, aromatics), 7.08 (4H, m, aromatics), 7.3 (2H, d, J=8.5 Hz, aromatics). Anal. Calcd for C21H20ClNO4: C, 65.37; H, 5.22; N, 3.63. Found: C, 65.22; H, 5.25; N, 3.52.

Workup

  1. customthe cooling bath was removed
  2. additionThe reaction mixture was then diluted wih ethyl acetate
  3. washwashed with saturated sodium bicarbonate, brine
  4. dry with materialdried (magnesium sulfate)
  5. customEvaporation of the solvent
  6. filtrationin vacuo, filtration of the residue
  7. washon a short silica gel pad (elution-toluene ethyl acetate; 85:15)
  8. customfollowed by crystallization from ethyl acetate-hexane

Sources & evidence

ORD record
ord-79efdd8651ad42679af5774a1d8cd496
Source dataset
uspto-grants-2004_10
Patent number
US06803378B2

Reaction notes

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