Toluene → HCID 178500902, compound

HRID 50102Notes

Reaction equation

HRID 50102 reaction equation
[C:1]([CH2:6][C:7]([O:9][CH3:10])=[O:8])(=[O:5])[CH:2]([CH3:4])[CH3:3].[F:11][C:12]1[CH:19]=[CH:18][C:15]([C:16]#[N:17])=[CH:14][CH:13]=1.C1(C)C=CC=CC=1.[Sn](Cl)(Cl)(Cl)Cl>CCCCCC>[NH2:17][C:16](=[C:6]([C:1](=[O:5])[CH:2]([CH3:4])[CH3:3])[C:7]([O:9][CH3:10])=[O:8])[C:15]1[CH:18]=[CH:19][C:12]([F:11])=[CH:13][CH:14]=1

Participants

6

Reactant 4

HCID 1140TolueneHCID 145174-FluorobenzonitrileHCID 24287Tin tetrachlorideHCID 2759969Methyl 4-methyl-3-oxopentanoate

Product 1

HCID 178500902HCID 178500902, compoundYield 75.2%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Conditions

Temperature
80 °C

Procedure

75.09 g of methyl isobutyrylacetate (0.50 mol, concentration 96%) and 61.80 g of 4-fluorobenzonitrile (0.50 mol, concentration 98%) were introduced into [500 ml of toluene and treated with 144.7 g of tin tetrachloride (0.55 mol, concentration 99%) at room temperature over the course of 16 min. After half an hour at room temperature, the thick suspension was heated to 80° C. After. 3 h, 175 ml of toluene were distilled off at normal pressure, and the mixture was cooled to room temperature and treated with 450 ml of saturated sodium carbonate and 300 ml of ethyl acetate. The organic phase was separated off and the aqueous phase (after dilution with 300 ml of water) was again extracted with 300 ml of ethyl acetate. After drying the combined organic phases over sodium sulphate, the solvent was removed in vacuo (40° C./25 mbar). 127.2 g of crude product were obtained in the form of a slightly yellowish solid, which was dissolved in 160 ml of n-hexane (slightly turbid solution). After hot filtration and subsequent cooling in an ice bath, 99.8 g of methyl 2-[1-amino-1-(4-fluorophenyl)-methylene]-4-methyl-3-oxopentanoate were obtained after filtration in the form of a pale yellow solid.

Workup

  1. waitAfter half an hour at room temperature
  2. distillation3 h, 175 ml of toluene were distilled off at normal pressure
  3. temperaturethe mixture was cooled to room temperature
  4. additiontreated with 450 ml of saturated sodium carbonate and 300 ml of ethyl acetate
  5. customThe organic phase was separated off
  6. extractionthe aqueous phase (after dilution with 300 ml of water) was again extracted with 300 ml of ethyl acetate
  7. dry with materialAfter drying the combined organic phases over sodium sulphate
  8. customthe solvent was removed in vacuo (40° C./25 mbar)
  9. custom127.2 g of crude product were obtained in the form of a slightly yellowish solid, which
  10. filtrationAfter hot filtration
  11. temperaturesubsequent cooling in an ice bath

Sources & evidence

ORD record
ord-1f1b485b281146ec8dd6dd9e597da9cf
Source dataset
uspto-grants-2004_03
Patent number
US06710178B2

Reaction notes

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