Hydrochloric Acid → HCID 10934323, compound

HRID 1871070Notes

Reaction equation

HRID 1871070 reaction equation
[OH-].[K+].[N+:3]([CH2:6][CH3:7])([O-:5])=[O:4].Cl[C:9]1[CH:14]=[CH:13][C:12]([C:15]([F:18])([F:17])[F:16])=[CH:11][C:10]=1[N+:19]([O-:21])=[O:20].Cl>O.CS(C)=O>[N+:19]([C:10]1[CH:11]=[C:12]([C:15]([F:18])([F:17])[F:16])[CH:13]=[CH:14][C:9]=1[CH:6]([N+:3]([O-:5])=[O:4])[CH3:7])([O-:21])=[O:20]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 6587NitroethaneHCID 84624-Chloro-alpha,alpha,alpha-trifluoro-3-nitrotolueneHCID 14797Potassium Hydroxide

Product 1

HCID 10934323HCID 10934323, compound

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent

Conditions

Temperature
19 °C

Procedure

Potassium hydroxide pellets (8.42 g; 0.150 mol; 3 equiv) were crushed and placed in a 250-mL 3-necked flask equipped with a thermometer and an addition funnel. Reagent-grade DMSO (25 mL) was added and the mixture vigorously stirred. An ice-water cooling bath was then applied and when the temperature of the reaction mixture had cooled to 19° C. a mixture of nitroethane (3.95 mL; 0.055 mol; 1.1 equiv) and 4-chloro-3-nitrobenzotrifluoride (1; 7.46 mL; 0.050 mol) were added to the reaction mixture (addition funnel) over 15 min at a rate such that a temperature of 15-20° C. was maintained. After the addition was complete, the reaction mixture was cooled to 15° C. and the ice bath was replaced with a cool water bath (10-15° C.) and the reaction mixture was allowed to warm to 20° C. over 2 h, at which time GC analysis indicated >98% consumption of 1 and a ratio of 2:3 of 98:2. Toluene (25 mL) was added and the reaction mixture was cooled in ice-water. Aqueous hydrochloric acid (6 N; 15 mL; 0.090 mol) was added dropwise with vigorous stirring at such a rate that the temperature remained below 20° C. Water (40 mL) was then added and the layers were allowed to separate for 10 min. The bottom aqueous layer was decanted, and the top organic solution was used directly for the next step. An aliquot of this organic solution was analyzed by 1H NMR and indicated a 96:4 ratio of 2:3. 2: 1H NMR (CDCl3) δ 8.349 (s, 1H); 7.976 (dd, 1 H, J=1.71, 8.24 Hz); 7.788 (d, 1H, J=8.24 Hz); 6.296 (q, 1H, J=6.96 Hz); 2.036 (d, 3H, J=6.78 Hz). GC (30 m DB-17, 100° C., 3 min; 100-280° C., 15/min; 280° C., 1 min): tR 10.71 min 3: 1H NMR (CDCl3) δ 10.815 (s, 1H); 8.435 (d, 1H, J=1.77 Hz); 7.830 (dd, 1H, J=2.19, 8.79 Hz); 7.315 (d, 1H, J=8.91 Hz). GC (30 m DB-17, 100° C., 3 min; 100-280° C., 15°/min; 280° C., 1 min): tR 5.53 min.

Workup

  1. customplaced in a 250-mL 3-necked flask
  2. customequipped with a thermometer and an addition funnel
  3. customAn ice-water cooling bath was then applied
  4. additionwere added to the reaction mixture (addition funnel) over 15 min at a rate such that a temperature of 15-20° C.
  5. temperaturewas maintained
  6. additionAfter the addition
  7. temperaturethe reaction mixture was cooled to 15° C.
  8. custom(10-15° C.)
  9. temperatureto warm to 20° C. over 2 h, at which time GC analysis
  10. custom>98% consumption of 1
  11. additionToluene (25 mL) was added
  12. temperaturethe reaction mixture was cooled in ice-water
  13. stirringwith vigorous stirring at such a rate that the temperature
  14. customremained below 20° C
  15. customto separate for 10 min
  16. customThe bottom aqueous layer was decanted
  17. customGC (30 m DB-17, 100° C., 3 min; 100-280° C., 15/min; 280° C., 1 min)
  18. customGC (30 m DB-17, 100° C., 3 min; 100-280° C., 15°/min; 280° C., 1 min)

Sources & evidence

ORD record
ord-aab201e1dc0d4056bddb0ca914a62e32
Source dataset
uspto-grants-2000_08
Patent number
US06100431

Reaction notes

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