Hydrochloric Acid → HCID 21568994, compound

HRID 1579609Notes

Reaction equation

HRID 1579609 reaction equation
N[C:2]1[CH:3]=[C:4]([C:8]([F:11])([F:10])[F:9])[CH:5]=[CH:6][CH:7]=1.Cl.N([O-])=O.[Na+].[CH3:17][C:18]([C:20]1[O:21][CH:22]=[CH:23][CH:24]=1)=[O:19]>O.C(#N)C>[CH3:17][C:18]([C:20]1[O:21][C:22]([C:2]2[CH:7]=[CH:6][CH:5]=[C:4]([C:8]([F:11])([F:10])[F:9])[CH:3]=2)=[CH:23][CH:24]=1)=[O:19]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 73753-(Trifluoromethyl)anilineHCID 145052-AcetylfuranHCID 23668193Sodium Nitrite

Product 1

HCID 21568994HCID 21568994, compoundYield 24%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent4×HCID 6342AcetonitrileSolvent

Procedure

A mixture of 322 g (2.0 moles) of 3-aminobenzotrifluoride, 690 ml of concentrated hydrochloric acid and 260 ml of water was heated with steam for 20 minutes at 80° and then cooled to 0°. An additional 200 ml of water was added to aid in stirring. A solution of 138 g (2.0 moles) of sodium nitrite in 500 ml of water was added dropwise while maintaining the temperature between 0°-5° by means of an ice bath. The reaction mixture was stirred for 30 minutes and then filtered to remove a small amount of solid which was discarded. The pH of the solution was adjusted to ca. 4 by the addition of 900 ml of saturated sodium acetate solution. A solution of 220 g (2.0 moles) of methyl-2-furyl ketone in 200 ml of acetonitrile was added followed by a solution of 40 g of CuCl2 . 2H2O in 100 ml of water. The reaction was stirred at 5°-15° for 1 hour and then warmed to room temperature becoming slightly exothermic. The reaction mixture was controlled below 33° by means of an ice bath. After 11/4 hour the reaction was no longer exothermic and was stirred at room temperature overnight. The oil mixture was extracted with 2 × 750 ml and 1 × 500 ml portions of ether. The ethereal extracts were combined and washed with 2000 ml of 5% sodium carbonate solution, with 1500 ml of water and then dried over magnesium sulfate. The ether was removed on the calab evaporator and the residue refrigerated for 72 hours. The solid which was formed was filtered, washed with pet ether and air-dried to yield 174 g. The crude product was recrystallized from 2500 ml of hexane/charcoal to yield 112 g (24%) of 5-(m-trifluoromethylphenyl)-2-furyl methyl ketone. An analytical sample was prepared by recrystallizing a sample of crude product twice from hexane/charcoal, m.p. 105°-109°.

Workup

  1. temperaturewas heated with steam for 20 minutes at 80°
  2. temperaturecooled to 0°
  3. temperaturewhile maintaining the temperature between 0°-5° by means of an ice bath
  4. stirringThe reaction mixture was stirred for 30 minutes
  5. filtrationfiltered
  6. customto remove a small amount of solid which
  7. additionby the addition of 900 ml of saturated sodium acetate solution
  8. stirringThe reaction was stirred at 5°-15° for 1 hour
  9. customThe reaction mixture was controlled below 33° by means of an ice bath
  10. custom4 hour
  11. stirringwas stirred at room temperature overnight
  12. extractionThe oil mixture was extracted with 2 × 750 ml and 1 × 500 ml portions of ether
  13. washwashed with 2000 ml of 5% sodium carbonate solution, with 1500 ml of water
  14. dry with materialdried over magnesium sulfate
  15. customThe ether was removed on the calab evaporator
  16. customThe solid which was formed
  17. filtrationwas filtered
  18. washwashed with pet ether
  19. customair-dried
  20. customto yield 174 g
  21. customThe crude product was recrystallized from 2500 ml of hexane/charcoal

Sources & evidence

ORD record
ord-10275a47568544468455c66a8e4dae3f
Source dataset
uspto-grants-1976_01
Patent number
US03931247

Reaction notes

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