Acrylonitrile → Tri-o-tolylphosphine

HRID 1284856Notes

Reaction equation

HRID 1284856 reaction equation
[C:1]([O-:4])(=[O:3])[CH3:2].[Pd+2:5].[C:6]([O-:9])(=[O:8])[CH3:7].[Pd].[C:11]1([CH3:32])[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[P:17]([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=1[CH3:31])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[CH3:24].Br[C:34]1[CH:41]=[CH:40][C:37]([CH:38]=[O:39])=[CH:36][CH:35]=1.[C:42](#[N:45])[CH:43]=[CH2:44].C([O-])(=O)C.[Na+]>CN(C)C=O.O>[C:1]([O-:4])(=[O:3])[CH3:2].[Pd+2:5].[C:6]([O-:9])(=[O:8])[CH3:7].[C:11]1([CH3:32])[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[P:17]([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=1[CH3:31])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[CH3:24].[CH:38]([C:37]1[CH:40]=[CH:41][C:34]([CH:44]=[CH:43][C:42]#[N:45])=[CH:35][CH:36]=1)=[O:39]

Participants

11

Reactant 6

HCID 7855AcrylonitrileHCID 23938PalladiumHCID 707414-BromobenzaldehydeHCID 80271Tri-o-tolylphosphineHCID 167845palladium(II) acetateHCID 517045Sodium Acetate

Product 3

HCID 80271Tri-o-tolylphosphineHCID 167845palladium(II) acetateHCID 54377318HCID 54377318, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
120 °C

Procedure

A stock solution of 0.0561 g (2.5×10-4 mol) of palladium acetate and 0.304 g (10-3 mol) of tri-o-tolylphosphine in 100 ml of N,N-dimethylformamide (DMF) is prepared under argon. 1 ml of stock solution [containing 0.000561 g (2.5×10-6 mol) of palladium acetate, Pd content=0.01 mol %, and 0.00304 g (10-5 mol) of tri-o-tolylphosphine], 4.63 g (25 mmols) of 4-bromobenzaldehyde, 2.08 ml (31.25 mmols) of acrylonitrile and 2.56 g (31.25 mmols) of anhydrous sodium acetate are then added, under argon, to 9 ml of DMF, and the mixture is stirred at 120° C. for 6 hours. The mixture is then poured into 100 ml of water, which is extracted with twice 25 ml of methylene dichloride, and the extract is dried for 15 minutes with 5 g of magnesium sulfate. After the methylene dichloride and a little DMF have been removed on a rotary evaporator, the crude product is distilled in vacuo. 3.2 g (20 mmols) of 4-formylcinnamonitrile are obtained in the form of a nearly white solid; yield 81% of theory (conversion figure 8100); melting point 92°-98° C.; boiling point 157°-163° C./133 Pa. Analysis for C10H7NO (molecular weight 157.17): calculated C 76.42: H 4.49; N 8.91, found C 76.35; H 4.60; N 9.01. The product is a mixture of isomers consisting of approx. 77% of trans-isomer and 23% of cis-isomer.

Workup

  1. extractionis extracted with twice 25 ml of methylene dichloride
  2. dry with materialthe extract is dried for 15 minutes with 5 g of magnesium sulfate
  3. customAfter the methylene dichloride and a little DMF have been removed on a rotary evaporator
  4. distillationthe crude product is distilled in vacuo

Sources & evidence

ORD record
ord-873f54b5d50c486c8f8e94f5ab736e38
Source dataset
uspto-grants-1986_01
Patent number
US04564479

Reaction notes

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