Triethylamine → HCID 18964308, compound

HRID 2254544Notes

Reaction equation

HRID 2254544 reaction equation
Cl[C:2]([O:4][CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)=[O:3].[CH3:12][C:13]([CH3:41])([CH3:40])[C:14](=[O:39])[C:15](=[N:27][C:28]1[CH:33]=[CH:32][C:31]([N:34]([CH2:37][CH3:38])[CH2:35][CH3:36])=[CH:30][CH:29]=1)[C:16]([NH:18][C:19]1[CH:24]=[CH:23][C:22]([Cl:25])=[CH:21][C:20]=1[Cl:26])=[O:17].C(N(CC)CC)C>CN(C1C=CN=CC=1)C.ClCCl>[CH2:5]([O:4][C:2]([N:18]([C:16](=[O:17])[C:15](=[N:27][C:28]1[CH:29]=[CH:30][C:31]([N:34]([CH2:35][CH3:36])[CH2:37][CH3:38])=[CH:32][CH:33]=1)[C:14](=[O:39])[C:13]([CH3:40])([CH3:41])[CH3:12])[C:19]1[CH:24]=[CH:23][C:22]([Cl:25])=[CH:21][C:20]=1[Cl:26])=[O:3])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

6

Reactant 3

HCID 8471Triethylamine2×HCID 10387Benzyl chloroformate3×HCID 18964312HCID 18964312, compound

Product 1

HCID 18964308HCID 18964308, compoundYield 39%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

Benzyl chloroformate (0.16 mL, 1.12 mmol) was added to a solution of N-[4,4-dimethyl-2-[4-diethylaminophenyl]imino-3-oxopentanoyl]-2,4-dichloroaniline, prepared as in Example 5 above (478 mg, 1.07 mmol), triethylamine (0.15 mL, 1.08 mmol) and DMAP (135 mg, 1.1 mmol) in dry dichloromethane (5 mL) and the resultant solution was stirred for 3 hours under nitrogen. Additional benzyl chloroformate (0.2 mL, 1.4 mmol) was then added, followed one hour later by more benzyl chloroformate (0.2 mL, 1.4 mmol) and additional triethylamine (0.15 mL, 1.08 mmol). The resultant solution was stirred under nitrogen for 7 days, after which the solvent was removed. The crude product was purified by flash chromatography on silica gel with 3% ethyl acetate/hexanes as eluant to give slightly impure Dye C. Further purification was effected by a second chromatographic separation on silica gel in the same manner as above. Dye C (240 mg, 39% yield) was obtained as an orange foam which had a principal absorption in the visible region of the electromagnetic spectrum at 438 nm, ε=15,900. The structure of this compound was confirmed by mass spectroscopy and by 1H and 13C NMR spectroscopy.

Workup

  1. customafter which the solvent was removed
  2. customThe crude product was purified by flash chromatography on silica gel with 3% ethyl acetate/hexanes as eluant
  3. customto give slightly impure Dye C
  4. customFurther purification
  5. customwas effected by a second chromatographic separation on silica gel in the same manner as above
  6. customDye C (240 mg, 39% yield) was obtained as an orange foam which
  7. customa principal absorption in the visible region of the electromagnetic spectrum at 438 nm, ε=15,900

Sources & evidence

ORD record
ord-90bdbafa4d5f4babad1e94478880a84d
Source dataset
uspto-grants-1993_08
Patent number
US05236884

Reaction notes

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