3,5-Diaminobenzoic acid → 6-{4-[(1E)-3-(4-pentyloxyphenoxy)-3-oxoprop-1-enyl]phenoxy}hexyl 3,5 diamino-benzoate

HRID 2246018Notes

Reaction equation

HRID 2246018 reaction equation
Cl[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][O:8][C:9]1[CH:14]=[CH:13][C:12](/[CH:15]=[CH:16]/[C:17]([O:19][C:20]2[CH:25]=[CH:24][C:23]([O:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])=[CH:22][CH:21]=2)=[O:18])=[CH:11][CH:10]=1.[NH2:32][C:33]1[CH:34]=[C:35]([CH:39]=[C:40]([NH2:42])[CH:41]=1)[C:36]([OH:38])=[O:37]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C)C=O>[NH2:32][C:33]1[CH:34]=[C:35]([CH:39]=[C:40]([NH2:42])[CH:41]=1)[C:36]([O:38][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][O:8][C:9]1[CH:14]=[CH:13][C:12](/[CH:15]=[CH:16]/[C:17]([O:19][C:20]2[CH:25]=[CH:24][C:23]([O:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])=[CH:22][CH:21]=2)=[O:18])=[CH:11][CH:10]=1)=[O:37]

Participants

5

Reactant 2

HCID 120623,5-Diaminobenzoic acidHCID 592174574-pentoxyphenyl (2E)-3-{4-(6-chlorohexyloxy)phenyl}acrylate

Product 1

HCID 592174606-{4-[(1E)-3-(4-pentyloxyphenoxy)-3-oxoprop-1-enyl]phenoxy}hexyl 3,5 diamino-benzoateYield 69.9%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

7.50 g (16.85 mmol) 4-pentoxyphenyl (2E)-3-{4-(6-chlorohexyloxy)phenyl}acrylate, 2.82 g (18.54 mmol) 3,5-diaminobenzoic acid and 0.62 g (1.69 mmol) tetrabutylammonium iodide were dissolved in 80 ml dimethylformamide. 3.00 ml (20.22 mmol) 1,8-diazabicyclo[5.4.0]undec-7-ene(1,5-5) (DBU) were added dropwise in the course of 10 minutes. The reaction temperature rose to 30° C. The mixture was then heated at 80° C. for 22 h. The reaction mixture was cooled and then partitioned between ethyl acetate and a saturated sodium bicarbonate solution; the organic phase was washed repeatedly with water, dried over sodium sulphate, filtered and concentrated by rotary evaporation. Chromatography of the residue on 1 kg silica gel using cyclohexane:ethyl acetate 1:1 as eluent yielded 6.6 g of 6-{4-[(1E)-3-(4-pentyloxyphenoxy)-3-oxoprop-1-enyl]phenoxy}hexyl 3,5 diamino-benzoate.

Workup

  1. customrose to 30° C
  2. temperatureThe reaction mixture was cooled
  3. custompartitioned between ethyl acetate
  4. washthe organic phase was washed repeatedly with water
  5. dry with materialdried over sodium sulphate
  6. filtrationfiltered
  7. concentrationconcentrated by rotary evaporation

Sources & evidence

ORD record
ord-a9ab002286ee488ab4e8b6c5e90c9475
Source dataset
uspto-grants-2010_03
Patent number
US07687118B2

Reaction notes

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