Benzyl Alcohol → benzyl N-(3-methylidenecyclobutyl)carbamate
Reaction equation
C=[C:2]1[CH2:5][CH:4]([C:6](O)=O)[CH2:3]1.C([N:11]([CH2:14]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:23])C=CC=CC=1.[CH2:33]([OH:40])[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1>C1(C)C=CC=CC=1.CCOCC>[CH2:33]([O:40][C:14]([NH:11][CH:2]1[CH2:3][C:4](=[CH2:6])[CH2:5]1)=[O:23])[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1Participants
Reactant 4
Product 1
Reagents, catalysts & solvents 2
Conditions
- Temperature
- 80 °C
Procedure
To a stirred solution of 26.7 g (238 mmol) of 3-methylenecyclobutane carboxylic acid (Cripps, H. N.; Williams, J. K.; Sharkey, W. H. J. Am. Chem. Soc. 1959, 81, 2723 2728) in 100 mL of toluene at 0° C. was added 36.4 mL (262 mmol) of triethylamine and then 72.1 g (262 mmol) of diphenylphosphoryl azide. The reaction mixture was then heated at 80° C., and after 1 h, 28.33 g (262 mmol) of benzyl alcohol was added. After 15 h at 85° C., the cooled reaction mixture was poured into 1 L of ether, washed with saturated aqueous NaHCO3, and then saturated aqueous NaCl, dried over MgSO4, and then concentrated under reduced pressure. Chromatography of the residue in three portions on 1400 g of silica gel with 80:20/hexane:EtOAc afforded 35.4 g (63%) of the desired compound. MS DCI/NH3M?Z: 218 (M+H)+, 235 (M+NH4)+ ;1H NMR (CDCl3) 2.60 (m, 2H), 3.05 (m, 2H), 4.20 (m, 1H), 4.83 (m, 2H), 5.21 (s, 2H), 7.45 (m, 5H).
Workup
- waitAfter 15 h at 85° C.
- customthe cooled reaction mixture
- washwashed with saturated aqueous NaHCO3
- dry with materialsaturated aqueous NaCl, dried over MgSO4
- concentrationconcentrated under reduced pressure
Sources & evidence
- ORD record
- ord-041bfb4883434aee92b85070da816987
- Source dataset
- uspto-grants-1992_10
- Patent number
- US05153352
Reaction notes
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