Nitric Acid → 2,3-Dichloro-6-nitrobenzaldehyde

HRID 2178728Notes

Reaction equation

HRID 2178728 reaction equation
S(=O)(=O)(O)O.[Cl:6][C:7]1[C:14]([Cl:15])=[CH:13][CH:12]=[CH:11][C:8]=1[CH:9]=[O:10].[N+:16]([O-])([OH:18])=[O:17]>C(OC)(C)(C)C>[Cl:6][C:7]1[C:14]([Cl:15])=[CH:13][CH:12]=[C:11]([N+:16]([O-:18])=[O:17])[C:8]=1[CH:9]=[O:10]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 357452,3-Dichlorobenzaldehyde

Product 1

HCID 112182712,3-Dichloro-6-nitrobenzaldehydeYield 29%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
42 °C

Procedure

Concentrated sulphuric acid (450 Kg) was added to 2,3-dichlorobenzaldehyde (59 Kg) and the mixture was heated to 40-44° C. for 2 hours, with stirring, to dissolve all the solids then cooled to 20-25° C. over a period of 95 minutes. Nitric acid (70% w/w, 34.5 Kg) was added to the solution, maintaining the temperature between 16 and 28° C., over a period of 110 minutes. The reaction mixture was stirred for 130 minutes, at between 21-25° C., and then quenched by controlled addition over 225 minutes into 1080 Kg of water (pre-cooled to 0-5° C.), maintaining the temperature between 2-20° C., including a vessel rinse of concentrated sulphuric acid (9.2 Kg). The resulting suspension was stirred for 180 minutes at between 10-14° C. then isolated by filtration and washed with pre-cooled (0-15° C.) water (2×297 Kg). The isolated crude solid (151.3 Kg crude, 51.6 kg active weight) was dissolved in methyl tert-butyl ether (590 L) and washed with water (165 L), 10% w/w sodium carbonate solution (165 L) and then water (1654 Solvent was removed by reduced pressure distillation at 17-20° C. until a volume of 160 L was reached, whereupon heptane (1140 L) was added. The resulting slurry was heated to 60° C. over 54 minutes and stirred at between 60-65° C. for 110 minutes, then cooled to 15-20° C. over 11.5 hours. Material was isolated by filtration and washed with heptane 90 L) then dried in vacuo at 40-45° C. to give 2,3-dichloro-6-nitrobenzaldehyde (21.3 Kg) with 96.3% purity (HPLC) in 29% yield.

Workup

  1. dissolutionto dissolve all the solids
  2. temperaturethen cooled to 20-25° C. over a period of 95 minutes
  3. temperaturemaintaining the temperature between 16 and 28° C.
  4. stirringThe reaction mixture was stirred for 130 minutes, at between 21-25° C.
  5. customquenched by controlled addition over 225 minutes into 1080 Kg of water (pre-cooled to 0-5° C.)
  6. temperaturemaintaining the temperature between 2-20° C.
  7. washrinse of concentrated sulphuric acid (9.2 Kg)
  8. stirringThe resulting suspension was stirred for 180 minutes at between 10-14° C.
  9. customthen isolated by filtration
  10. washwashed
  11. temperaturewith pre-cooled (0-15° C.) water (2×297 Kg)
  12. customThe isolated crude solid (151.3 Kg crude, 51.6 kg active weight)
  13. washwashed with water (165 L), 10% w/w sodium carbonate solution (165 L)
  14. customwater (1654 Solvent was removed by reduced pressure distillation at 17-20° C. until a volume of 160 L
  15. additionwhereupon heptane (1140 L) was added
  16. temperatureThe resulting slurry was heated to 60° C. over 54 minutes
  17. stirringstirred at between 60-65° C. for 110 minutes
  18. temperaturecooled to 15-20° C. over 11.5 hours
  19. customMaterial was isolated by filtration
  20. washwashed with heptane 90 L)
  21. customthen dried in vacuo at 40-45° C.

Sources & evidence

ORD record
ord-5ed9632b11094b7a82afc5df1197c7a2
Source dataset
uspto-grants-2015_06
Patent number
US09067944B2

Reaction notes

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