Triethylamine → 5-Bromo-1-methyl-1-indanamine

HRID 2046557Notes

Reaction equation

HRID 2046557 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[C:7]([CH3:14])(C(O)=O)[CH2:6][CH2:5]2.C([N:17](CC)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.C[Si](C)(C)[O-].[Na+].[OH-].[Na+]>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[C:7]([NH2:17])([CH3:14])[CH2:6][CH2:5]2

Participants

7

Reactant 5

HCID 8471TriethylamineHCID 14798Sodium HydroxideHCID 199401P,P-Diphenylphosphinic azideHCID 23672319Sodium trimethylsilanolateHCID 574194875-Bromo-1-methyl-2,3-dihydro-1H-indene-1-carboxylic acid

Product 1

HCID 682967755-Bromo-1-methyl-1-indanamineYield 91%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (rac)-5-bromo-1-methyl-indan-1-carboxylic acid (1.197 g, 4.69 mmol) in dry toluene (65 ml) was added triethylamine (570 mg, 475 μl, 5.63 mmol) and diphenylphosphoryl azide (1.33 g, 1.04 ml, 4.69 mmol) and the colorless solution was heated to reflux for 3 h. After cooling to 0° C., sodium trimethylsilanolate (9.38 ml, 9.38 mmol, 1M solution in THF) was added and the mixture was stirred for 30 minutes at room temperature. After quenching the reaction with 5% citric acid (100 ml), the pH was adjusted to 12-13 by addition of 3N NaOH and the mixture was extracted three times with CH2Cl2. The combined organic layers were washed with brine, dried with Na2SO4 and evaporated. The remaining crude material was partitioned between 0.1N HCl and diethylether and the aqueous layer was extracted with diethylether. The pH of the aqueous layer was adjusted to 12 by addition of 0.1N NaOH and the aqueous layer was extracted three times with CH2Cl2. The combined CH2Cl2-layers were washed with brine, dried with Na2SO4 and evaporated to obtain the title compound as light yellow oil (963 mg, 91%). MS: 209.1 [M+H−NH3]+.

Workup

  1. temperaturethe colorless solution was heated
  2. temperatureto reflux for 3 h
  3. customAfter quenching
  4. customthe reaction with 5% citric acid (100 ml)
  5. extractionthe mixture was extracted three times with CH2Cl2
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried with Na2SO4
  8. customevaporated
  9. customThe remaining crude material was partitioned between 0.1N HCl and diethylether
  10. extractionthe aqueous layer was extracted with diethylether
  11. additionThe pH of the aqueous layer was adjusted to 12 by addition of 0.1N NaOH
  12. extractionthe aqueous layer was extracted three times with CH2Cl2
  13. washThe combined CH2Cl2-layers were washed with brine
  14. dry with materialdried with Na2SO4
  15. customevaporated

Sources & evidence

ORD record
ord-fe2beea08bb6470681f4c43f9fa37cde
Source dataset
uspto-grants-2013_11
Patent number
US08592426B2

Reaction notes

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