3-Hydroxybenzaldehyde → HCID 11416458, compound

HRID 222552Notes

Reaction equation

HRID 222552 reaction equation
[C:1]([C:5]1[CH:11]=[CH:10][C:8]([NH2:9])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].FC(F)(F)C(O)=O.[O:19]1[CH:24]=[CH:23][CH2:22][CH2:21][CH2:20]1.[OH:25][C:26]1[CH:27]=[C:28]([CH:31]=[CH:32][CH:33]=1)[CH:29]=O.NC1C=CC=CC=1>C(#N)C>[C:1]([C:5]1[CH:6]=[CH:7][C:8]2[NH:9][CH:29]([C:28]3[CH:27]=[C:26]([OH:25])[CH:33]=[CH:32][CH:31]=3)[CH:21]3[CH2:22][CH2:23][CH2:24][O:19][CH:20]3[C:10]=2[CH:11]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 5

HCID 1013-HydroxybenzaldehydeHCID 6115AnilineHCID 6422Trifluoroacetic acid2×HCID 80803,4-dihydro-2H-pyranHCID 698614-Tert-Butylaniline

Product 1

HCID 11416458HCID 11416458, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Conditions

Temperature
50 °C

Procedure

99.0 g (663 mmol) of 4-tert-butylaniline was dissolved in 500 ml of acetonitrile, and 51.6 ml (670 mmol) of trifluoroacetic acid was added with ice-cooling. 46.4 g (670 mmol) of 3,4-dihydro-2H-pyran and 81.8 g (670 mmol) of 3-hydroxybenzaldehyde in 500 ml of acetonitrile were initially introduced in a second flask with ice-cooling. The aniline*|trifluoroacetic acid salt pre-cooled to 50° C. was added rapidly to this reaction solution, and stirring was continued at this temperature for about 2 h. The reaction mixture was evaporated, and the residue was suspended in 2 l of water and adjusted to pH 12 using sodium hydroxide solution. The emulsion formed was extracted 2× with 1 l of tert-butyl methyl ether. The org. phase was dried over Na2SO4 and crystallised overnight in at 4° C. Precipitated colourless product 1 was filtered off and dried, giving 6.00 of colourless crystals. 3-(9-tert-Butyl-3,4,4a,5,6,10b-hexahydro-2H-pyrano[3,2-c]quinolin-5-yl)phenol was isolated from the filtrate as described under DE10360154.6 and could also be converted into comp. 1 as described under c.

Workup

  1. temperaturecooling
  2. temperaturecooling
  3. additionwas added rapidly to this reaction solution
  4. customThe reaction mixture was evaporated
  5. customThe emulsion formed
  6. extractionwas extracted 2× with 1 l of tert-butyl methyl ether
  7. dry with materialphase was dried over Na2SO4
  8. customcrystallised overnight in at 4° C
  9. customPrecipitated colourless product 1
  10. filtrationwas filtered off
  11. customdried
  12. customgiving 6.00 of colourless crystals

Sources & evidence

ORD record
ord-0a09c58f6c354f12ab12cfe143596350
Source dataset
uspto-grants-2012_06
Patent number
US08207345B2

Reaction notes

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