Sodium Hydroxide → 4-(2,2-Dichlorocyclopropyl)phenol

HRID 1085991Notes

Reaction equation

HRID 1085991 reaction equation
[Cl:1][C:2]1([Cl:12])[CH2:4][CH:3]1[C:5]1[CH:11]=[CH:10][C:8](N)=[CH:7][CH:6]=1.N([O-])=[O:14].[Na+].[OH-].[Na+].O=C1O[C@H]([C@H](CO)O)C([O-])=C1O.[Na+]>S(=O)(=O)(O)O.O.C(OCC)C>[Cl:1][C:2]1([Cl:12])[CH2:4][CH:3]1[C:5]1[CH:11]=[CH:10][C:8]([OH:14])=[CH:7][CH:6]=1

Participants

8

Reactant 4

HCID 14798Sodium HydroxideHCID 3327661HCID 3327661, compoundHCID 23667548Sodium AscorbateHCID 23668193Sodium Nitrite

Product 1

HCID 142247024-(2,2-Dichlorocyclopropyl)phenolYield 94.4%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolvent3×HCID 3283Diethyl EtherSolvent

Procedure

(-)-4-(2,2-Dichlorocyclopropyl)aniline (5 g, 0.024 mol) from the above resolution was dissolved in concentrated sulphuric acid (25 ml) and added in aliquots (1 ml) to iced water (100 ml). The mixture was allowed to stand overnight and the resulting precipitate then removed by filtration. The solid was suspended with stirring in sulphuric acid (0.05M, 70 ml) whilst being cooled to below 5° C. and a solution of sodium nitrite (2.2 g, 0.032 mol) in sulphuric acid (0.05M, 30 ml) added. After stirring for 1.5 hours the remaining precipitate was dissolved by addition of concentrated sulphuric acid (2.4 ml) and stirring maintained for a further 1.5 hours. The pH of the solution was then adjusted to 2 by addition of an aqueous solution of sodium hydroxide (10M) before being added to a stirred mixture of cupric nitrate hemipentahydrate (50 g, 0.21 mol) and sodium ascorbate (2.3 g, 0.012 mol) in distilled water (440 ml) and diethyl ether (150 ml). The mixture was stirred for 10 minutes before the organic phase was removed and the aqueous phase extracted with diethyl ether (3×100 ml). The combined organic phases were washed with distilled water, dried over anhydrous magnesium sulphate and the solvent removed by evaporation under reduced pressure to afford the crude (-)-4-(2,2-dichlorocyclopropyl)phenol (4.6 g) which was used directly in the following reaction.

Workup

  1. customthe resulting precipitate then removed by filtration
  2. temperaturewhilst being cooled to below 5° C.
  3. stirringAfter stirring for 1.5 hours the remaining precipitate
  4. stirringstirring
  5. temperaturemaintained for a further 1.5 hours
  6. stirringThe mixture was stirred for 10 minutes before the organic phase
  7. customwas removed
  8. extractionthe aqueous phase extracted with diethyl ether (3×100 ml)
  9. washThe combined organic phases were washed with distilled water
  10. dry with materialdried over anhydrous magnesium sulphate
  11. customthe solvent removed by evaporation under reduced pressure

Sources & evidence

ORD record
ord-d42ca30b27604b9d97f9276bcb086ba2
Source dataset
uspto-grants-1991_04
Patent number
US05011985

Reaction notes

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