Benzyl chloroformate → Benzyl[2-(4-nitrophenyl)hexahydro-2,5-methanopentalen-3a(1h)-yl]carbamate

HRID 1015518Notes

Reaction equation

HRID 1015518 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([C:10]23[CH2:18][CH:14]4[CH2:15][CH:16]([CH2:17]2)[C:12]([NH2:19])([CH2:13]4)[CH2:11]3)=[CH:6][CH:5]=1)([O-:3])=[O:2].C([O-])([O-])=O.[K+].[K+].[CH2:26]([O:33][C:34](Cl)=[O:35])[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1>C1COCC1.O>[CH2:26]([O:33][C:34](=[O:35])[NH:19][C:12]12[CH2:13][CH:14]3[CH2:18][C:10]([C:7]4[CH:6]=[CH:5][C:4]([N+:1]([O-:3])=[O:2])=[CH:9][CH:8]=4)([CH2:17][CH:16]1[CH2:15]3)[CH2:11]2)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

6

Reactant 3

HCID 10387Benzyl chloroformateHCID 11430Potassium CarbonateHCID 593749781-(4-Nitrophenyl)tricyclo[3.3.1.03,7]nonan-3-amine

Product 1

HCID 131729071Benzyl[2-(4-nitrophenyl)hexahydro-2,5-methanopentalen-3a(1h)-yl]carbamateYield 70%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred mixture of 1-(4-nitrophenyl)tricyclo[3.3.1.03,7]nonan-3-amine (2.0 g, 8.0 mmol) obtained in step III, K2CO3 (3.5 g, 24 mmol) in THF (80 mL), cooled to ice-bath temperature was added benzylchloroformate (50% w/v in Toluene, 2.2 mL, 12 mmol). After stirring the reaction mixture at r.t for 2 h, it was diluted with water and extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, and the solvent was removed under reduced pressure to obtain benzyl[2-(4-nitrophenyl)hexahydro-2,5-methanopentalen-3a(1H)-yl]carbamate as an off-white solid (2.1 g) in 70% yield. M.R: 104.1-105.9° C.; m/z (M+1) 393; IR cm−1 3440, 2952, 1714, 1518, 1349, 1216, 757; 1H NMR (CDCl3) 300 MHz δ 8.12 (d, J=8.8 Hz, 2H), 7.50-7.27 (m, 7H), 5.20-5.0 (s (br), 2H), 2.65-2.55 (m, 1H), 2.50-1.55 (m, 11H). 13C NMR (CDCl3) 75 MHz δ 155.1, 154.2, 146.1, 136.4, 131.1, 128.5 (2C), 128.1 (2C), 126.6 (2C), 123.4 (2C), 66.3, 64.4, 49.248.0, 47.5, 43.8, 42.1, 40.8, 37.0.

Workup

  1. temperaturecooled to ice-bath temperature
  2. extractionextracted with EtOAc
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over Na2SO4
  5. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-5ab5f44f251b42bb8ccc6c5993cd6806
Source dataset
uspto-grants-2011_07
Patent number
US07985759B2

Reaction notes

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