Sodium Azide → {[1-(3-Azidopropyl)cyclohexyl]oxy}(tert-butyl)dimethylsilane

HRID 44723Notes

Reaction equation

HRID 44723 reaction equation
[N-:1]=[N+:2]=[N-:3].[Na+].CS(O[CH2:10][CH2:11][CH2:12][C:13]1([O:19][Si:20]([C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:22])[CH3:21])[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]1)(=O)=O>CN(C)C=O.C(OCC)C>[N:1]([CH2:10][CH2:11][CH2:12][C:13]1([O:19][Si:20]([C:23]([CH3:24])([CH3:26])[CH3:25])([CH3:21])[CH3:22])[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18]1)=[N+:2]=[N-:3]

Participants

5

Reactant 2

HCID 33557Sodium Azide2×HCID 574578163-(1-{[Tert-butyl(dimethyl)silyl]oxy}cyclohexyl)propyl methanesulfonate

Product 1

HCID 57457817{[1-(3-Azidopropyl)cyclohexyl]oxy}(tert-butyl)dimethylsilaneYield 95.2%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

Sodium azide (1.78 g, 27.4 mmol) was added to a solution of 3-(1-{[tert-butyl(dimethyl)silyl]oxy}cyclohexyl)propyl methanesulfonate (prepared as described in Part D, 24.9 mmol) in dimethylformamide (100 mL). The reaction mixture was stirred for 2.5 d and additional sodium azide (160 mg) was added. The mixture was stirred an additional 1d, then was diluted with diethyl ether (250 mL) and washed with water (3×75 mL). The combined aqueous layers were back-extracted with diethyl ether (50 mL). The combined organic layers were washed with brine (100 mL), dried over MgSO4, filtered, and concentrated to afford {[1-(3-azidopropyl)cyclohexyl]oxy}(tert-butyl)dimethylsilane (7.05 g, 95% over two steps) as a pale yellow oil. A mixture of the {[1-(3-azidopropyl)cyclohexyl]oxy}(tert-butyl)dimethylsilane (7.05 g, 23.7 mmol) and 5% palladium on carbon (0.71 g) in ethanol (100 mL) was hydrogenated at 30 psi (2.1×105 Pa) for 4 h on a Parr apparatus. The reaction mixture was filtered through CELITE filter agent, which was rinsed afterwards with dichloromethane, and the filtrate was concentrated to give 3-(1-{[tert-butyl(dimethyl)silyl]oxy}cyclohexyl)propan-1-amine as a pale yellow oil (6.57 g, 102%) that contained a trace amount of solvent.

Workup

  1. washwashed with water (3×75 mL)
  2. extractionThe combined aqueous layers were back-extracted with diethyl ether (50 mL)
  3. washThe combined organic layers were washed with brine (100 mL)
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-f4dfc273a5344a92ad4c8a50e1d889f7
Source dataset
uspto-grants-2013_09
Patent number
US08541438B2

Reaction notes

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