Urea → 4-(2,2-Dichlorocyclopropyl)phenol

HRID 1085990Notes

Reaction equation

HRID 1085990 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+].NC(N)=O.N(O)=O.[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

10

Reactant 6

HCID 1176UreaHCID 14798Sodium HydroxideHCID 24529Nitrous AcidHCID 3327661HCID 3327661, compoundHCID 23667548Sodium AscorbateHCID 23668193Sodium Nitrite

Product 1

HCID 142247024-(2,2-Dichlorocyclopropyl)phenolYield 101.8%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent3×HCID 1118Sulfuric AcidSolventHCID 3283Diethyl EtherSolvent

Procedure

(+)-4-(2,2-Dichlorocyclopropyl)aniline (3 g, 0.015 mol) from the previous resolution was dissolved in concentrated sulphuric acid (15 ml) to which was added iced water (30 ml). With the reaction temperature maintained below 5° C. a solution of sodium nitrite (1.3 g, 0.019 mol) in distilled water (15 ml) was added. After a further 5 minutes, urea (0.27 g, 0.0045 mol) was added to eliminate excess nitrous acid. The pH of the mixture was then adjusted to 3 by addition of an aqueous solution of sodium hydroxide (10M) whilst the temperature of less than 5° C. was maintained. This mixture was then added slowly to a vigorously stirred mixture of cupric nitrate hemipentahydrate (60 g, 0.26 mol) and sodium ascorbate (2.8 g, 0.014 mol) in distilled water (530 ml) and diethyl ether (200 ml). After 5 minutes 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 crude (+)-4-(2,2-dichlorocyclopropyl)phenol (3.1 g) which was used directly in the following reaction.

Workup

  1. additionwas added
  2. temperaturewas maintained
  3. customAfter 5 minutes the organic phase was removed
  4. extractionthe aqueous phase extracted with diethyl ether (3× 100 ml)
  5. washThe combined organic phases were washed with distilled water
  6. dry with materialdried over anhydrous magnesium sulphate
  7. customthe solvent removed by evaporation under reduced pressure

Sources & evidence

ORD record
ord-efbb6077f93e4ac0b25adb3b27895d5a
Source dataset
uspto-grants-1991_04
Patent number
US05011986

Reaction notes

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