Dimethylformamide → HCID 19003281, compound

HRID 1654566Notes

Reaction equation

HRID 1654566 reaction equation
[CH3:1][C:2]1([CH3:24])[CH2:7][CH:6]([N:8]2[C:12](=[O:13])[C:11]3=[CH:14][C:15]([C:18]([OH:20])=[O:19])=[CH:16][CH:17]=[C:10]3[C:9]2=[O:21])[CH2:5][C:4]([CH3:23])([CH3:22])[NH:3]1.[CH2:25](Br)[CH2:26][CH2:27][CH3:28].C(=O)([O-])[O-].[Na+].[Na+].CN(C)C=O>CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-].C(Cl)(Cl)Cl.CCCCC.O.C(OC)(C)(C)C>[CH3:22][C:4]1([CH3:23])[CH2:5][CH:6]([N:8]2[C:12](=[O:13])[C:11]3=[CH:14][C:15]([C:18]([O:20][CH2:25][CH2:26][CH2:27][CH3:28])=[O:19])=[CH:16][CH:17]=[C:10]3[C:9]2=[O:21])[CH2:7][C:2]([CH3:24])([CH3:1])[NH:3]1

Participants

10

Reactant 4

HCID 6228DimethylformamideHCID 8002Butyl bromideHCID 10340Sodium CarbonateHCID 15217370HCID 15217370, compound

Product 1

HCID 19003281HCID 19003281, compound

Reagents, catalysts & solvents 5

HCID 21218Trioctylmethylammonium chlorideCatalystHCID 962WaterSolventHCID 6212ChloroformSolventHCID 8003PentaneSolventHCID 15413tert-Butyl methyl etherSolvent

Procedure

Into a 125 ml reaction flask equipped with a magnetic stirrer, thermometer, condenser and nitrogen atmosphere were placed the HALS-acid of Example 1 (3.3 g (0.01 mol), n-butylbromide (3.13 g, 0.022 mol), ADOGEN 464® (Ashland Chemical Co.) (0.19 g), sodium carbonate (6.64 g, 0.044 mol) and 50 ml of dimethylformamide. The reaction was heated to 80°-90° C. for 2 hours, allowed to stand at ambient temperature for 15 hours then heated again at 80°-90° C. for 6.5 additional hours. The mixture was transferred to a separatory funnel with 100 ml methyl t-butyl ether and 500 ml water. The phases were agitated then allowed to separate. The ether solution was retained and the aqueous solution was extracted with 100 ml fresh ether. The combined ether extracts were dried with anhydrous magnesium sulfate and stripped using aspirator and high vacuum systems. A white solid residue was isolated using a small amount of pentane (the product is quite soluble in this solvent). The product was 3.0 g of white crystals melting at 90°-92° C. The infrared spectrum (chloroform) showed a broad carbonyl absorption at 1700 cm-1 (imide and ester). The NMR spectrum showed the anticipated aromatic ring (7.7-8.5 ppm, multiplet, 3H), the --N--C--H and --O--CH2 merged (4.2-4.8, triplet and multiplet, 3H) and the rest of the HALS group and butyl group [0.9-2.3 ppm, several multiplets including two singlets (1.2 and 1.3 ppm)].

Workup

  1. customInto a 125 ml reaction flask
  2. customequipped with a magnetic stirrer
  3. customthermometer, condenser and nitrogen atmosphere were placed
  4. temperatureThe reaction was heated to 80°-90° C. for 2 hours
  5. temperaturethen heated again at 80°-90° C. for 6.5 additional hours
  6. customto separate
  7. extractionthe aqueous solution was extracted with 100 ml fresh ether
  8. dry with materialThe combined ether extracts were dried with anhydrous magnesium sulfate
  9. customA white solid residue was isolated
  10. customa broad carbonyl absorption at 1700 cm-1 (imide and ester)

Sources & evidence

ORD record
ord-b8ce9a2656ea42fd8339554120802a08
Source dataset
uspto-grants-1995_04
Patent number
US05408008

Reaction notes

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