Toluene → Ethyl phenylcyanoacetate

HRID 13885

Reaction equation

HRID 13885 reaction equation
P([O-])([O-])([O-])=O.[Na+].[Na+].[Na+].C1(C)C=CC=CC=1.Cl[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.[C:23]([CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27])#[N:24]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1([B-](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C.O>[CH2:29]([O:28][C:26](=[O:27])[CH:25]([C:23]#[N:24])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[CH3:30]

Participants

8

Reactant 4

HCID 1140TolueneHCID 7764Ethyl cyanoacetateHCID 7964ChlorobenzeneHCID 24243Trisodium Phosphate

Product 1

HCID 95298Ethyl phenylcyanoacetateYield 53%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 23136663Tri-tert-butylphosphonium TetraphenylborateCatalystHCID 962WaterSolvent

Procedure

A 30-ml four-necked flask was equipped with a stirrer, a thermometer and a reflux condenser. 0.022 g (0.1 mmol) of palladium (II) acetate, 2.459 g (15 mmol) of sodium phosphate and 15 ml of toluene were weighed in the flask, followed by stirring. Further, 0.105 g (0.2 mmol) of tri-tert-butylphosphonium tetraphenylborate obtained in Example A-1 was weighed in air and added into the flask. The flask was purged with argon, followed by stirring at 25° C. for 30 minutes. 0.563 g (5 mmol) of chlorobenzene was added, followed by stirring at 25° C. for 30 minutes. 0.622 g (5.5 mmol) of ethyl cyanoacetate was added, followed by stirring at 100° C. for 12 hours. After the completion of the reaction, 5 ml of water was added, followed by separation. The organic phase was purified by column chromatography to afford 0.501 g of ethyl-2-phenylcyanoacetate (yield: 53 mol % based on chlorobenzene). The identification of the product was made by mass spectroscopy, 1H-NMR and 13C-NMR.

Workup

  1. customA 30-ml four-necked flask was equipped with a stirrer
  2. additionadded into the flask
  3. customThe flask was purged with argon
  4. stirringby stirring at 25° C. for 30 minutes
  5. stirringby stirring at 25° C. for 30 minutes
  6. stirringby stirring at 100° C. for 12 hours
  7. additionwas added
  8. customfollowed by separation
  9. customThe organic phase was purified by column chromatography

Sources & evidence

ORD record
ord-c4304a0840df48b08e42a5963d3eae15
Source dataset
uspto-grants-2010_06
Patent number
US07728176B2

Linked notes

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