Nitromethane → Ethyl 3-(nitromethyl)hexanoate

HRID 1851729Notes

Reaction equation

HRID 1851729 reaction equation
[CH2:1]([O:3][C:4](=[O:10])[CH:5]=[CH:6][CH2:7][CH2:8][CH3:9])[CH3:2].[N+:11]([CH3:14])([O-:13])=[O:12].N12CCCN=C1CCCCC2>>[CH2:1]([O:3][C:4](=[O:10])[CH2:5][CH:6]([CH2:14][N+:11]([O-:13])=[O:12])[CH2:7][CH2:8][CH3:9])[CH3:2]

Participants

4

Reactant 3

HCID 6375NitromethaneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 519129Ethyl hex-2-enoate

Product 1

HCID 14463324Ethyl 3-(nitromethyl)hexanoateYield 99.4%

Procedure

To a stirred solution of hex-2-enoic acid ethyl ester (A) (450 g, 3.164 mol, 1 eq) in nitromethane (858 ml, 15.822 mol, 5 eq) cooled at 0° C., is added dropwise, under nitrogen, 481.8 g (3.164 mol, 1 eq.) of 1.8-diazabicyclo[5.4.0]undec-7-ene (DBU). The reaction mixture is allowed to react at room temperature for 3 h and is quenched with a 6M aqueous hydrogen chloride solution to obtain pH=4. The solution is extracted with diethyl ether (500 ml+2×300 ml). The organic layers are dried with MgSO4, filtered and concentrated to obtain an oil residue (672.13 g, HPLC purity=78.9%) which is purified by liquid chromatography eluting with dichloromethane. 639.41 g of 3-nitromethyl-hexanoic acid ethyl ester (B) are obtained (yield=99.4%).

Workup

  1. additionis added dropwise, under nitrogen
  2. customto react at room temperature for 3 h
  3. customis quenched with a 6M aqueous hydrogen chloride solution
  4. customto obtain pH=4
  5. extractionThe solution is extracted with diethyl ether (500 ml+2×300 ml)
  6. dry with materialThe organic layers are dried with MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto obtain an oil residue (672.13 g, HPLC purity=78.9%) which
  10. customis purified by liquid chromatography
  11. washeluting with dichloromethane

Sources & evidence

ORD record
ord-f70e0dbf76644f37aba8be6000906ac4
Source dataset
uspto-grants-2015_02
Patent number
US08957226B2

Reaction notes

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