Triethylamine → 1,1-Dimethyl-2-(3-(1-adamantyl)ethoxyphenyl)ethylamine

HRID 1925526Notes

Reaction equation

HRID 1925526 reaction equation
[CH3:1][C:2](C)([CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([O:13][CH2:14][CH2:15][C:16]23[CH2:25][CH:20]4[CH2:21][CH:22]([CH2:24][CH:18]([CH2:19]4)[CH2:17]2)[CH2:23]3)[CH:8]=1)[C:3](O)=O.C([N:29](CC)CC)C.[N-]=[N+]=[N-].[Na+]>CC(C)=O.O>[CH3:1][C:2]([NH2:29])([CH3:3])[CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([O:13][CH2:14][CH2:15][C:16]23[CH2:25][CH:20]4[CH2:21][CH:22]([CH2:24][CH:18]([CH2:19]4)[CH2:17]2)[CH2:23]3)[CH:8]=1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 33557Sodium AzideHCID 675211592,2-Dimethyl-3-(3-(1-adamantyl)ethoxyphenyl) propionic acid

Product 1

HCID 675204661,1-Dimethyl-2-(3-(1-adamantyl)ethoxyphenyl)ethylamine

Reagents, catalysts & solvents 2

HCID 180AcetoneSolvent2×HCID 962WaterSolvent2×

Conditions

Temperature
0 °C

Procedure

2.17 g (6.09 mmol) of the Intermediate 86 are dissolved in 200 ml of acetone. 1.95 ml (13.99 mmol) of triethylamine are added and the solution is cooled to 0° C. A solution of 0.89 ml (6.84 mmol) of isobutyl chloroformiate in 15 ml of acetone is dropped into the system. After 30′ at 0° C. a solution of 0.99 g (15.23 mmol) of sodium azide in 10 ml of water is slowly added, and the stirring at 0° C. is prosecuted for an additional period of 30 min. Excess water is added, the system is extracted with ethyl ether which is washed with water, dried and concentrated at room temperature. The residue is dissolved in 15 ml of toluene and this solution added slowly to 150 ml of refluxing toluene. The reflux is prosecuted for an additional hour and the solution is concentrated. The residue is dissolved in 15 ml of dioxane, 35 ml of 5N HCl are added and the system is stirred at 100° C. for 30′. The solution is neutralised with 2N NaOH and is extracted with ethyl ether. The ethereal layer is washed with water, dried and concentrated. The residue is chromatographied on silicagel eluting with ethyl acetate/methanol 10:1 then 6:1 giving 1.46 g (72%) of yellowish oil.

Workup

  1. extractionthe system is extracted with ethyl ether which
  2. washis washed with water
  3. customdried
  4. concentrationconcentrated at room temperature
  5. dissolutionThe residue is dissolved in 15 ml of toluene
  6. additionthis solution added slowly to 150 ml of refluxing toluene
  7. waitThe reflux is prosecuted for an additional hour
  8. concentrationthe solution is concentrated
  9. dissolutionThe residue is dissolved in 15 ml of dioxane
  10. addition35 ml of 5N HCl are added
  11. extractionis extracted with ethyl ether
  12. washThe ethereal layer is washed with water
  13. customdried
  14. concentrationconcentrated
  15. washeluting with ethyl acetate/methanol 10:1

Sources & evidence

ORD record
ord-a3cfcfe933934446a99f36edf71c212a
Source dataset
uspto-grants-2012_05
Patent number
US08178679B2

Reaction notes

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