Nitric Acid → HCID 21783433, compound
Reaction equation
[C:1]([O:4][C:5]1[C:12]([O:13][CH3:14])=[CH:11][CH:10]=[CH:9][C:6]=1[CH:7]=[O:8])(=[O:3])[CH3:2].S(=O)(=O)(O)O.[N+:20]([O-])([OH:22])=[O:21]>>[C:1]([O:4][C:5]1[C:12]([O:13][CH3:14])=[C:11]([N+:20]([O-:22])=[O:21])[CH:10]=[CH:9][C:6]=1[CH:7]=[O:8])(=[O:3])[CH3:2]Participants
Conditions
- Temperature
- -15 °C
Procedure
42 (42.0 g, 0.22 mol) was added portionwise as a finely ground powder over 1 h to a solution of concentrated sulphuric acid (28 mL) in 100% nitric acid (140 mL) at −20° C. During the addition, the reaction temperature was maintained at around −15° C. The reaction mixture was stirred at −5° C. for a further 40 min, then poured into to ice/water (1 L) and extracted rapidly with toluene (2×). The organic phase was washed successively with 0.25 M NaHCO3 aq. water and brine, dried (Na2SO4) and evaporated to dryness to give crude product (19.8 g) as a yellow oil, which was shown by NMR to contain ˜60% nitro-compounds. Purification of 8 g of this material by column chromatography (three times, SiO2, first eluting with 1:9 EtOAc:cyclohexane, then with 3:7 EtOAc:cyclohexane and finally with 1:1 EtOAc:cyclohexane) gave 43 (2.53 g) in (˜80% purity) together with 2-hydroxy-3-methoxy-4-nitrobenzaldehyde (˜10%). The product was used as such in the next step.
Workup
- additionDuring the addition
- extractionextracted rapidly with toluene (2×)
- washThe organic phase was washed successively with 0.25 M NaHCO3 aq. water and brine
- dry with materialdried (Na2SO4)
- customevaporated to dryness
- customto give crude product (19.8 g) as a yellow oil, which
- customPurification of 8 g of this material by column chromatography (three times, SiO2
- washfirst eluting with 1:9 EtOAc
Sources & evidence
- ORD record
- ord-dfe6e49bf0174b03ac455a26bf1deeda
- Source dataset
- uspto-grants-2012_06
- Patent number
- US08198302B2
Reaction notes
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