Pentyl nitrite → Amyl Acetate

HRID 1719403Notes

Reaction equation

HRID 1719403 reaction equation
[CH3:1][CH2:2][CH2:3][CH2:4][CH2:5][O:6]N=O.[CH2:9]=[C:10]=[O:11].[C]=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.CN1CCCC1=O.ClC1C=CC=CC=1>[CH3:1][CH2:2][CH2:3][CH2:4][CH2:5][O:6][C:10]([CH3:9])=[O:11]

Participants

8

Reactant 4

HCID 10026Pentyl nitriteHCID 10038KeteneHCID 11776TriphenylphosphineHCID 178418416HCID 178418416, compound

Product 1

HCID 12348Amyl AcetateYield 14.7%

Reagents, catalysts & solvents 3

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 7964ChlorobenzeneSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

To the same reaction vessel as in Example 9 were charged bistriphenylphosphinedibromopalladium (0.198 g, 0.25 mmole), stannous chloride (0.095 g, 0.5 mmole), tetra-n-butylammonium chloride (0.139 g, 0.5 mmole) and n-amyl nitrite (60 ml, 406.6 mmoles), together with monochlorobenzene (200 ml). Then, ketene, carbon monooxide and nitrogen were introduced to the mixture at the rate of 10.4 ml/min (0.46 mmole/min), 300 ml/min and 100 ml/min, respectively, and the reaction was effected for 5 hours. During the reaction, 10 ml of a solution of triphenylphosphine and stannous chloride (0.25 mmole each) in N-methylpyrrolidone was added to the reaction system in 2.5 ml portions every 1 hour. The reaction proceeded smoothly for 5 hours without termination of the reaction to give di-n-amyl malonate (116.2 mmoles, 83.8%) and n-amyl acetate (20.5 mmoles, 14.7%).

Workup

  1. additionwas added to the reaction system in 2.5 ml portions every 1 hour
  2. customThe reaction proceeded smoothly for 5 hours without termination of the reaction

Sources & evidence

ORD record
ord-1c3112c75e0a493090429f7907a1e23c
Source dataset
uspto-grants-1985_09
Patent number
US04539423

Reaction notes

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