Benzyl Alcohol → Benzyloxycarbonyl-3-methylenecyclobutanamine

HRID 5948

Reaction equation

HRID 5948 reaction equation
[CH2:1]=[C:2]1[CH2:5][CH:4]([C:6]([OH:8])=[O:7])[CH2:3]1.C([N:11](CC)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.[CH2:33](O)[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1>C1(C)C=CC=CC=1.CCOCC>[CH2:33]([O:7][C:6]([C:4]1([NH2:11])[CH2:5][C:2](=[CH2:1])[CH2:3]1)=[O:8])[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1

Participants

7

Reactant 4

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 274753-Methylenecyclobutanecarboxylic acidHCID 199401P,P-Diphenylphosphinic azide

Product 1

HCID 86747233Benzyloxycarbonyl-3-methylenecyclobutanamineYield 68.5%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

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.

Workup

  1. waitAfter 15 h at 85° C.
  2. customthe cooled reaction mixture
  3. washwashed with saturated aqueous NaHCO3
  4. dry with materialsaturated aqueous NaCl, dried over MgSO4
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-c0218d5b5bfa40d88a5132d0538e4b9e
Source dataset
uspto-grants-1993_09
Patent number
US05246931

Linked notes

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