Triethylamine → Methyl 4-[3-(1-adamantyl)-4-methoxyphenylureido]benzoate

HRID 274030Notes

Reaction equation

HRID 274030 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:13]=[CH:12][C:8](C(O)=O)=[CH:7][CH:6]=1)=[O:4].C([N:16]([CH2:19]C)CC)C.ClC(OCC)=[O:23].[N-]=[N+]=[N-].[Na+].[C:31]12([C:41]3[CH:42]=[C:43]([CH:45]=[CH:46][C:47]=3[O:48][CH3:49])[NH2:44])[CH2:40][CH:35]3[CH2:36][CH:37]([CH2:39][CH:33]([CH2:34]3)[CH2:32]1)[CH2:38]2>O1CCCC1.O>[C:31]12([C:41]3[CH:42]=[C:43]([NH:44][C:19](=[O:23])[NH:16][C:8]4[CH:7]=[CH:6][C:5]([C:3]([O:2][CH3:1])=[O:4])=[CH:13][CH:12]=4)[CH:45]=[CH:46][C:47]=3[O:48][CH3:49])[CH2:38][CH:37]3[CH2:39][CH:33]([CH2:34][CH:35]([CH2:36]3)[CH2:40]1)[CH2:32]2

Participants

8

Reactant 5

HCID 8471TriethylamineHCID 10928Ethyl chloroformateHCID 15513Monomethyl terephthalateHCID 33557Sodium AzideHCID 80271163-(1-Adamantyl)-4-methoxyaniline

Product 1

HCID 67714159Methyl 4-[3-(1-adamantyl)-4-methoxyphenylureido]benzoateYield 91%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 2.81 g (15.6 mmol) of 4-(methoxycarbonyl)benzoic acid in 30 ml of tetrahydrofuran is placed at 0° C., then treated with 2.61 ml (18.7 mmol) of triethylamine and 1.94 ml (20.3 mmol) of ethyl chloroformate and left stirring for 1 hour at 0° C. A solution of 1.52 g (23.4 mmol) of sodium azide in 10 ml of water is added to this medium, the mixture is left stirring at 0° C. for 3 hours and the reaction medium is then poured into ice-cold water and extracted with ethyl ether. The organic phase is washed with water, dried over magnesium sulphate and evaporated. The residue is dissolved in 30 ml of toluene, heated to 100° C. for 1.5 hours and then cooled to room temperature. 4.82 g (18.7 mmol) of 3-(1-adamantyl)-4-methoxyaniline are then added dropwise to the foregoing solution and the mixture is stirred at 50° C. for 1.5 hours. It is evaporated to dryness, the solid is taken up with ethyl ether and the organic phase is dried over magnesium sulphate and evaporated. The residue is recrystallized in ethyl acetate to yield 6.16 g (91%) of methyl 4-[3-(1-adamantyl)-4-methoxyphenylureido]benzoate, melting point 223°-224° C.

Workup

  1. customis placed at 0° C.
  2. waitleft
  3. waitthe mixture is left
  4. stirringstirring at 0° C. for 3 hours
  5. additionthe reaction medium is then poured into ice-cold water
  6. extractionextracted with ethyl ether
  7. washThe organic phase is washed with water
  8. dry with materialdried over magnesium sulphate
  9. customevaporated
  10. dissolutionThe residue is dissolved in 30 ml of toluene
  11. temperatureheated to 100° C. for 1.5 hours
  12. temperaturecooled to room temperature
  13. stirringthe mixture is stirred at 50° C. for 1.5 hours
  14. customIt is evaporated to dryness
  15. dry with materialthe organic phase is dried over magnesium sulphate
  16. customevaporated
  17. customThe residue is recrystallized in ethyl acetate

Sources & evidence

ORD record
ord-5a87be63396a4345838fd92970a9f558
Source dataset
uspto-grants-1995_02
Patent number
US05387594

Reaction notes

Loading…