Acetic Acid → 4-Chloro-2,6-bis(hydroxymethyl)phenol

HRID 722302Notes

Reaction equation

HRID 722302 reaction equation
[OH-:1].[K+].[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[CH:6][CH:5]=1.[CH2:11]=O.[C:13]([OH:16])(=O)C>O.CC(C)=O>[Cl:3][C:4]1[CH:9]=[C:8]([CH2:11][OH:1])[C:7]([OH:10])=[C:6]([CH2:13][OH:16])[CH:5]=1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 712FormaldehydeHCID 46844-ChlorophenolHCID 14797Potassium Hydroxide

Product 1

HCID 869144-Chloro-2,6-bis(hydroxymethyl)phenol

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Conditions

Temperature
35 °C

Procedure

Potassium hydroxide (84.82 g, 1.30 mole) was dissolved in H2O (200 mL) in a two liter 3-neck round bottom flask fitted with thermocouple, mechanical stirrer, and stopper. With stirring, 4-chlorophenol (128.56 g, 1.0 mole) was added with cooling (ice bath) resulting in the temperature rising to 26° C. Formalin (230 mL of 37% aqueous solution, 2.83 mole) was added portion-wise maintaining the temperature below 25° C. The reaction was warmed to 35° C. for 48 hours. To this solution was added aqueous acetic acid (80.0 mL, 84.1 g, 1.40 mole in 800 mL H2O) causing the solution to become turbid. Vacuum filtration of the suspension yielded a tan solid. The solid was stirred with acetone (100 mL) and the insoluble product collected by vacuum filtration. The solution was diluted with hexanes yielding several crops of the diol as fine tan needles (35.0 g, 19%). mp 160.6–163.3° C. 1H NMR (acetone-d6, NaOD, D2O/300 MHz) 6.69 (s, 2H), 4.48 (s, 4H), 7.88 (d, 1H, J=2.6 Hz), 7.75 (d, 1H, J=2.6 Hz), 6.08 (q, 1H, J=6.9 Hz). ESLRMS m/z 206 (M+NH4+). ESHRMS m/z 187.0131 (M−H, Calc'd 187.0162).

Workup

  1. customfitted with thermocouple, mechanical stirrer, and stopper
  2. temperaturewith cooling (ice bath)
  3. customresulting in the temperature
  4. customrising to 26° C
  5. temperaturemaintaining the temperature below 25° C
  6. filtrationVacuum filtration of the suspension
  7. customyielded a tan solid
  8. filtrationthe insoluble product collected by vacuum filtration
  9. additionThe solution was diluted with hexanes yielding several crops of the diol as fine tan needles (35.0 g, 19%)

Sources & evidence

ORD record
ord-188814b60df14e638c266fefe9a258fa
Source dataset
uspto-grants-2006_11
Patent number
US07138411B2

Reaction notes

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