Vanillin → HCID 86653389, compound

HRID 1192777Notes

Reaction equation

HRID 1192777 reaction equation
[C:1]([CH2:4][C:5](=[O:7])[CH3:6])(=[O:3])[CH3:2].B(OCCCC)(OCCCC)OCCCC.[CH3:24][O:25][C:26]1[CH:27]=[C:28]([CH:31]=[CH:32][C:33]=1[O:34][C:35](=[O:57])[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=[CH:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH2:55][CH3:56])[CH:29]=O.O=[CH:59][C:60]1[CH:68]=[CH:67][C:65]([OH:66])=[C:62]([O:63][CH3:64])[CH:61]=1.C(N)CCC>CN(C=O)C.C(O)(=O)C>[C:35]([O:34][C:33]1[CH:32]=[CH:31][C:28]([CH:29]=[CH:6][C:5](=[O:7])[CH2:4][C:1](=[O:3])[CH:2]=[CH:59][C:60]2[CH:68]=[CH:67][C:65]([OH:66])=[C:62]([O:63][CH3:64])[CH:61]=2)=[CH:27][C:26]=1[O:25][CH3:24])(=[O:57])[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=[CH:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH2:55][CH3:56]

Participants

8

Reactant 5

HCID 1183VanillinHCID 8007ButylamineHCID 12712Tributyl borateHCID 31261AcetylacetoneHCID 86653390HCID 86653390, compound

Product 1

HCID 86653389HCID 86653389, compoundYield 25.6%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
65 °C

Procedure

To a solution of boric oxide (183 mg, 2.65 mmol) in DMF (1 mL), was added acetyl acetone (0.236 mL, 2.30 mmol) followed by tributyl borate (1.25 mL, 4.62 mmol) at rt and stirred at 65° C. for 15 min. To the above borate complex, a mixture of 3-methoxy-4-docosahexaenoyloxybenzaldehyde (1 g, 2.30 mmol) and vanillin (350 mg, 2.30 mmol) was added and stirred for 5 min at the same temperature. A mixture of n-butyl amine (0.045 mL) and acetic acid (0.13 mL) in DMF (1 mL) was added to the reaction mixture and stirred at 90-95° C. for 4 h. After cooling to 15° C., acetic acid (20%, 20 mL) was added with stirring and again the reaction mixture was stirred at 70° C. for another 1 h. Then it was cooled to rt, extracted with chloroform (3×100 mL) and the combined chloroform layer was washed with water, brine and dried over sodium sulfate. The solution was filtered and the residue was chromatographed over silica gel column using hexane-ethyl acetate (85:15) as eluents to give 1-(4-docosahexaenoyloxy-3-methoxyphenyl)-7-(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione (400 mg, 25%). LCMS (ESI, negative ion mode): m/z (M-H)−.

Workup

  1. additionwas added
  2. stirringstirred for 5 min at the same temperature
  3. additionwas added to the reaction mixture
  4. stirringstirred at 90-95° C. for 4 h
  5. temperatureAfter cooling to 15° C.
  6. stirringwith stirring
  7. stirringagain the reaction mixture was stirred at 70° C. for another 1 h
  8. temperatureThen it was cooled to rt
  9. extractionextracted with chloroform (3×100 mL)
  10. washthe combined chloroform layer was washed with water, brine
  11. dry with materialdried over sodium sulfate
  12. filtrationThe solution was filtered
  13. customthe residue was chromatographed over silica gel column

Sources & evidence

ORD record
ord-8bd51b70eba745c591ee6208c4c74faa
Source dataset
uspto-grants-2014_03
Patent number
US08680143B2

Reaction notes

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