Dimethylformamide → HCID 11688411, compound

HRID 229739Notes

Reaction equation

HRID 229739 reaction equation
[CH:1]1([O:6][C:7]2[CH:14]=[CH:13][C:10]([CH:11]=[O:12])=[CH:9][C:8]=2[O:15][C:16]2[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[CH:18][C:17]=2Br)[CH2:5][CH2:4][CH2:3][CH2:2]1.CN(C)C=O.C(=O)([O-])[O-].[Na+].[Na+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1COCC1>[CH:1]1([O:6][C:7]2[C:8]3[O:15][C:16]4[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[CH:18][C:17]=4[C:9]=3[C:10]([CH:11]=[O:12])=[CH:13][CH:14]=2)[CH2:5][CH2:4][CH2:3][CH2:2]1

Participants

6

Reactant 3

HCID 6228DimethylformamideHCID 10340Sodium CarbonateHCID 11675824HCID 11675824, compound

Product 1

HCID 11688411HCID 11688411, compoundYield 60%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalyst3×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
135 °C

Procedure

In a 20 L 4 necked RB Flask, fitted with a mechanical stirrer, reflux condenser, add 4-cyclopentyloxy-3(4′-nitro-2′-bromophenoxy)benzaldehyde (1.3 kg, 3.20 M), dimethyl formamide (7.8 L), sodium carbonate (0.51 kg, 4.8M) at temperature in the range of 25-35° C. under stirring. Heat the reaction mixture to temperature of 130-140° C. and add palladium acetate. Trimer (75 g, 0.11M) and maintain at temperature of 130-140° C. for 1 h under stirring. After 1 hr maintenance, the second lot of palladium acetate trimer (75 g, 0.11M) was added at temperature of 130-140° C. under stirring and maintained for 1 hr. After 2 hr maintenance the third lot of palladium acetate trimer (75 g, 0.11M) was added at temperature of 130-140° C. under stirring and maintained for 1 hr. The progress of the reaction mixture was monitored by HPLC. The reaction mixture was cooled to 70° C. and 4.7 L of THF was added to the reaction mixture and stirred for 30 min. The inorganic insolubles were filtered and washed with THF (1 L×2). Collect the THF MLS and add to DM water (15 L) under stirring. The precipitated product was filtered, washed with water (5 L) and dried in the vacuum oven at temp. below 60° C. The dried product was subjected to reflux in a mixture of THF (1.3 L) and Ethyl acetate (2.6 L) for 2 h and brought to room temperature. The precipitated product was filtered, dried in oven at temp. below 60° C. under vaccum till MC reaches <1%. The dried product appears as pale yello solid, weighs about 650-700 g , yield 60-65%, purity 97-98% by HPLC, m.p. 230-232° C. The IR (KBr) spectrum shows 3120 (CH str), 2960 (CH str), 1682 (CHO str), 1340 (NO2 str)

Workup

  1. temperaturereflux condenser
  2. temperatureTrimer (75 g, 0.11M) and maintain at temperature of 130-140° C. for 1 h
  3. stirringunder stirring
  4. stirringunder stirring
  5. temperaturemaintained for 1 hr
  6. stirringunder stirring
  7. temperaturemaintained for 1 hr
  8. temperatureThe reaction mixture was cooled to 70° C.
  9. stirringstirred for 30 min
  10. filtrationThe inorganic insolubles were filtered
  11. washwashed with THF (1 L×2)
  12. customCollect the THF MLS
  13. additionadd to DM water (15 L)
  14. stirringunder stirring
  15. filtrationThe precipitated product was filtered
  16. washwashed with water (5 L)
  17. customdried in the vacuum oven at temp
  18. custombelow 60° C
  19. temperatureto reflux in a mixture of THF (1.3 L) and Ethyl acetate (2.6 L) for 2 h
  20. custombrought to room temperature
  21. filtrationThe precipitated product was filtered
  22. customdried in oven at temp
  23. custombelow 60° C.

Sources & evidence

ORD record
ord-c8816d1785d5458ead3a1bdf345b8cfe
Source dataset
uspto-grants-2009_07
Patent number
US07563900B2

Reaction notes

Loading…