Triethylamine → (5,7-Dibromo-adamantan-2-yl)-carbamic acid tert-butyl ester

HRID 70494Notes

Reaction equation

HRID 70494 reaction equation
[Br:1][C:2]12[CH2:12][CH:6]3[CH2:7][C:8]([Br:11])([CH2:10][CH:4]([CH:5]3C(O)=O)[CH2:3]1)[CH2:9]2.CCN(CC)CC.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.[CH3:40][C:41]([O-:44])([CH3:43])[CH3:42].[K+].[N-:46]=[C:47]=[O:48]>C1(C)C=CC=CC=1.C1COCC1>[C:41]([O:44][C:47](=[O:48])[NH:46][CH:5]1[CH:4]2[CH2:10][C:8]3([Br:11])[CH2:9][C:2]([Br:1])([CH2:12][CH:6]1[CH2:7]3)[CH2:3]2)([CH3:43])([CH3:42])[CH3:40]

Participants

8

Reactant 5

HCID 8471TriethylamineHCID 105034IsocyanateHCID 199401P,P-Diphenylphosphinic azideHCID 149770365,7-Dibromoadamantane-2-carboxylic acidHCID 23665647Potassium tert-butoxide

Product 1

HCID 16100375(5,7-Dibromo-adamantan-2-yl)-carbamic acid tert-butyl ester

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
85 °C

Procedure

A suspension of the acid 24 (2.00 g, 5.92 mmol) in dry toluene (30 mL) was treated successively with Et3N (1.0 mL, 7.10 mmol) and diphenylphosphoryl azide (DPPA, 1.6 mL, 7.10 mmol). The resulting mixture was stirred at 85° C. for 15 h. To a separated flask containing a solution of t-BuOK (1.35 g, 11.8 mmol) in dry THF (80 mL) at 0° C. was added the isocyanate solution dropwise via a dropping funnel. The resulting reaction mixture was allowed to warm to rt over 30 min, and then it was quenched with water. The THF was removed in vacuo, and the resulting material was diluted with EtOAc. The organic layer was washed with 1N HCl, sat. NaHCO3 and brine, dried (Na2SO4), filtered and concentrated in vacuo. Flash chromatography (SiO2, 95:5 to 8:2, hexanes/EtOAc) afforded 1.20 g (50%, 2 steps) of the title compound as a white powder. 1H NMR (300 MHz, CDCl3) δ 4.68 (bs, 1H), 3.76 (bs, 1H), 2.87 (s, 2 H), 2.47-2.13 (m, 10H), 1.46 (s, 9H).

Workup

  1. customThe resulting reaction mixture
  2. temperatureto warm to rt over 30 min
  3. customit was quenched with water
  4. customThe THF was removed in vacuo
  5. additionthe resulting material was diluted with EtOAc
  6. washThe organic layer was washed with 1N HCl, sat. NaHCO3 and brine
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-dd24cb2b5112410fb83d58a9b207c8c1
Source dataset
uspto-grants-2014_09
Patent number
US08822541B2

Reaction notes

Loading…