Water → tert-Butyl 4-methylideneazepane-1-carboxylate

HRID 2360493Notes

Reaction equation

HRID 2360493 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].O=[C:7]1CCC[N:10]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:9][CH2:8]1.O>O1CCCC1.CCCCCC>[CH2:4]=[C:3]1[CH2:7][CH2:8][CH2:9][N:10]([C:14]([O:16][C:17]([CH3:18])([CH3:20])[CH3:19])=[O:15])[CH2:1][CH2:2]1

Participants

6

Reactant 3

HCID 962WaterHCID 1512679N-Boc-hexahydro-1H-azepin-4-oneHCID 178418339Butyllithium

Product 1

HCID 46941824tert-Butyl 4-methylideneazepane-1-carboxylate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent2×

Procedure

Under argon 12.56 g methyltriphenylphosphonium bromide are dissolved in 100 ml of tetrahydrofuran, cooled to −14° C. and within 45 minutes a 2 M solution of 17.58 ml n-butyllithium in hexane is added dropwise. The mixture is stirred for another 1 hour and then a solution of 5 g tert-butyl 4-oxo-azepan-1-carboxylate in 20 ml of tetrahydrofuran is added dropwise. Then the mixture is heated to ambient temperature and stirred for 12 hours. It is then divided between water and hexane and the aqueous phase is extracted twice with hexane. The combined organic phases are washed with saturated aqueous sodium chloride solution and dried on magnesium sulphate. The solvents are eliminated in vacuo and the residue is stirred with petroleum ether/tert.-butyl-methyl-ether. The solid is suction filtered and the mother liquor is evaporated down in vacuo. The residue is chromatographed on silica gel (petroleum ether/ethyl acetate 100:0, then 95:5).

Workup

  1. additionis added dropwise
  2. stirringstirred for 12 hours
  3. extractionthe aqueous phase is extracted twice with hexane
  4. washThe combined organic phases are washed with saturated aqueous sodium chloride solution
  5. customdried on magnesium sulphate
  6. stirringthe residue is stirred with petroleum ether/tert.-butyl-methyl-ether
  7. filtrationfiltered
  8. customthe mother liquor is evaporated down in vacuo
  9. customThe residue is chromatographed on silica gel (petroleum ether/ethyl acetate 100:0

Sources & evidence

ORD record
ord-81d3418ce5cc46a1b194955816f664f9
Source dataset
uspto-grants-2014_04
Patent number
US08686022B2

Reaction notes

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