Formaldehyde → HCID 15531554, compound

HRID 1062525Notes

Reaction equation

HRID 1062525 reaction equation
C([Mg]Br)C.[C:5]([C:9]1[CH:14]=[C:13]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH:12]=[CH:11][C:10]=1[OH:21])([CH3:8])([CH3:7])[CH3:6].[CH2:22]=[O:23].C(N(CC)CC)C>C1COCC1.C1(C)C=CC=CC=1>[C:5]([C:9]1[CH:14]=[C:13]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH:12]=[C:11]([CH:22]=[O:23])[C:10]=1[OH:21])([CH3:8])([CH3:6])[CH3:7]

Participants

7

Reactant 4

HCID 712FormaldehydeHCID 8471TriethylamineHCID 162519[1,1'-Biphenyl]-4-ol, 3-(1,1-dimethylethyl)-HCID 178418443HCID 178418443, compound

Product 1

HCID 15531554HCID 15531554, compoundYield 78%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

Into a 1 liter reactor thoroughly purged with nitrogen, 66.80 ml of an ether solution containing 200.4 mmol of ethylmagnesium bromide and 100 ml of THF were introduced. To the reactor, a solution containing 43.16 g (190.7 mmol) of 2-t-butyl-4-phenylphenol diluted with 90 ml of a THF was dropwise added at 0° C. over a period of 40 minutes, then the temperature of the system was slowly raised to room temperature, and the reaction solution was stirred at room temperature for 30 minutes. Then, 700 ml of toluene was added, and the system was heated to 100° C. to distill off 52 ml of a mixed solution of ether and THF, whereby an opaque white slurry was obtained. After the slurry was cooled to −20° C., 13.84 g (460.9 mmol) of paraformaldehyde and 38.1 ml (273.4 mmol) of triethylamine were added, followed by stirring at 90° C. for 30 minutes. After ice cooling, the reaction solution was quenched with 133 ml of 18% hydrochloric acid. The organic layer was washed with 300 ml of water, 300 ml of a sodium hydrogencarbonate aqueous solution and 300 ml of a sodium chloride aqueous solution, and then concentrated. The resulting liquid was purified by silica gel column chromatography to obtain 37.73 g (yield: 78%) of 3-t-butyl-5-phenylsalicylaldehyde.

Workup

  1. customInto a 1 liter reactor thoroughly purged with nitrogen, 66.80 ml of an ether solution
  2. additionwere introduced
  3. additionwas dropwise added at 0° C. over a period of 40 minutes
  4. temperaturethe system was heated to 100° C.
  5. distillationto distill off 52 ml of a mixed solution of ether and THF, whereby an opaque white slurry
  6. customwas obtained
  7. temperatureAfter the slurry was cooled to −20° C.
  8. stirringby stirring at 90° C. for 30 minutes
  9. customAfter ice cooling, the reaction solution was quenched with 133 ml of 18% hydrochloric acid
  10. washThe organic layer was washed with 300 ml of water, 300 ml of a sodium hydrogencarbonate aqueous solution and 300 ml of a sodium chloride aqueous solution
  11. concentrationconcentrated
  12. customThe resulting liquid was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-f158801f322a450f8ac387fb3d2fdb21
Source dataset
uspto-grants-2005_11
Patent number
US06962890B2

Reaction notes

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