Dimethylformamide → 2-Methyl-6-nitrobenzaldoxime

HRID 1645475Notes

Reaction equation

HRID 1645475 reaction equation
CN(C=O)C.C[O-].[K+].[N+:9]([C:12]1[CH:17]=[CH:16][CH:15]=[C:14]([CH3:18])[C:13]=1[CH3:19])([O-:11])=[O:10].[N:20](OCCCC)=[O:21]>C(O)(=O)C.O>[CH3:18][C:14]1[CH:15]=[CH:16][CH:17]=[C:12]([N+:9]([O-:11])=[O:10])[C:13]=1[CH:19]=[N:20][OH:21]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 67391,2-Dimethyl-3-nitrobenzeneHCID 10996Butyl nitriteHCID 23664618Potassium methoxide

Product 1

HCID 853610482-Methyl-6-nitrobenzaldoxime

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Conditions

Temperature
-40 °C

Procedure

1200 ml of anhydrous DMF are initially charged in a 4 l reaction flask and cooled to −40° C. At this temperature, 336.5 g (4.56 mol) of potassium methoxide (95%) are added and suspended with stirring. A mixture of 300 g (1.92 mol) of 3-nitro-o-xylene (97%) and 274 g (2.52 mol) of n-butyl nitrite (95%) is then added dropwise at −40° C. over a period of 7 hours (if the mixture is cooled accordingly, the duration of this addition can be reduced as desired). The complete conversion of the starting material is checked by HPLC. The reaction discharge is then added with stirring, at from −5 to 0° C., to a mixture of 300 ml of water and 300 ml of glacial acetic acid. The reaction mixture is then poured onto 6 kg of ice-water and the solid is separated off by filtration and washed twice with in each case 500 ml of water. The crude product (HPLC: 96 area %) is purified by suspending the moist solid in 800 ml of toluene for 1.5 h. The solid is filtered off and dried at 50° C. in a vacuum drying cabinet.

Workup

  1. additionis then added dropwise at −40° C. over a period of 7 hours (if the mixture
  2. temperatureis cooled accordingly
  3. additionthe duration of this addition
  4. additionThe reaction discharge is then added
  5. customthe solid is separated off by filtration
  6. washwashed twice with in each case 500 ml of water
  7. customThe crude product (HPLC: 96 area %) is purified
  8. customfor 1.5 h
  9. filtrationThe solid is filtered off
  10. customdried at 50° C. in a vacuum
  11. customdrying cabinet

Sources & evidence

ORD record
ord-1292c71545554ce48ed83fd96700b4e7
Source dataset
uspto-grants-2012_02
Patent number
US08124810B2

Reaction notes

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