Dimethylformamide → 2-Methyl-6-nitrobenzaldoxime

HRID 434208Notes

Reaction equation

HRID 434208 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 with stirring and suspended. 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 subsequently added dropwise at −40° C. over a period of 7 hours (if the mixture is cooled appropriately, the duration of this addition can be reduced at will; an extension has hitherto not been examined; temperature variations between −35 and −45° C. can be tolerated). By HPLC, it is checked that the starting material has been converted completely. The reaction discharge is subsequently added with stirring to a mixture of 300 ml of water and 300 ml of glacial acetic acid, at from −5 to 0° C. The reaction mixture is then poured into 6 kg of ice-water and the solid is separated off by filtration (without any problems, the flow resistance has not yet been determined) and washed twice with 500 ml of water each time (caution: the crude product smells strongly). 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 (without any problems, the flow resistance has not yet been determined) and dried in a vacuum drying cabinet at 50° C.

Workup

  1. additionis subsequently added dropwise at −40° C. over a period of 7 hours (if the mixture
  2. temperatureis cooled appropriately
  3. additionthe duration of this addition
  4. customtemperature variations between −35 and −45° C.
  5. additionThe reaction discharge is subsequently added
  6. customthe solid is separated off by filtration (without any problems
  7. washwashed twice with 500 ml of water each time (caution
  8. customThe crude product (HPLC: 96 area %) is purified
  9. customfor 1.5 h
  10. filtrationThe solid is filtered off (without any problems
  11. customdried in a vacuum
  12. customdrying cabinet at 50° C.

Sources & evidence

ORD record
ord-ad80c458a10445ba84bd41107ec32fbb
Source dataset
uspto-grants-2003_12
Patent number
US06670482B2

Reaction notes

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