Sodium hydride → N-tert-Butoxycarbonyl-(3-cyclohex-3-enyl-propyl)-carbamic acid tert-butyl ester

HRID 1690867Notes

Reaction equation

HRID 1690867 reaction equation
[H-].[Na+].[C:3]([O:7][C:8]([NH:10][C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[O:9])([CH3:6])([CH3:5])[CH3:4].[CH:18]1([CH2:24][CH2:25][CH2:26]OS(C2C=CC(C)=CC=2)(=O)=O)[CH2:23][CH2:22][CH:21]=[CH:20][CH2:19]1.C1(C)C=CC=CC=1.C1CCCCC1>CN(C)C=O.O1CCCC1.O>[C:14]([O:13][C:11](=[O:12])[N:10]([CH2:26][CH2:25][CH2:24][CH:18]1[CH2:23][CH2:22][CH:21]=[CH:20][CH2:19]1)[C:8]([O:7][C:3]([CH3:6])([CH3:5])[CH3:4])=[O:9])([CH3:17])([CH3:16])[CH3:15]

Participants

8

Reactant 4

HCID 24758Sodium hydrideHCID 279800Di-tert-butyl IminodicarboxylateHCID 21910790Toluene cyclohexaneHCID 87119180Toluene-4-sulfonic acid 3-cyclohex-3-enyl-propyl ester

Product 1

HCID 66707503N-tert-Butoxycarbonyl-(3-cyclohex-3-enyl-propyl)-carbamic acid tert-butyl esterYield 86.6%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×HCID 8028TetrahydrofuranSolvent2×

Procedure

Sodium hydride (60% in mineral oil, 2.5 g, 62.5 mmol, corrected) was added in several portions over a period of 15 min to an ice-cold mixture of di-tert-butyl-iminodicarboxylate (22.0 g, 100 mmol) in 60 ml of dimethyl formamide and 180 ml of tetrahydrofuran under stirring. A solution of toluene-4-sulfonic acid 3-cyclohex-3-enyl-propyl ester (Marvell, E.; Sturmer, D.; Kunston, R. Journal of Organic Chemistry 1968, 33, 2991-2993) (14.8 g, 50.0 mmol) in a mixture of 15 ml of dimethyl formamide and 45 ml of tetrahydrofuran was charged to it dropwise over 30 minutes. The mixture was stirred for 7 hours at 70° C. and 16 hours at room temperature, diluted with water and extracted with tert-butyl methyl ether. The organic extract was washed with water, brine and stripped of the solvent to give a mixture. After chromatography of the mixture (silica, toluene/cyclohexane=75/25) the title compound (ethyl acetate/toluene=15/85, Rf=0.19, 14.7 g, 86% yield, uncorrected) was obtained as clear yellow oil.

Workup

  1. additionwas charged to it dropwise over 30 minutes
  2. stirringThe mixture was stirred for 7 hours at 70° C. and 16 hours at room temperature
  3. extractionextracted with tert-butyl methyl ether
  4. extractionThe organic extract
  5. washwas washed with water, brine
  6. customto give a mixture

Sources & evidence

ORD record
ord-a4b6e96004ae4743a8ab52f4cd2d25e5
Source dataset
uspto-grants-2012_04
Patent number
US08153689B2

Reaction notes

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