Acetic Anhydride → 1-Tridecene

HRID 1461893Notes

Reaction equation

HRID 1461893 reaction equation
[C:1](O)(=O)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13]C.C(OC(=O)C)(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Pd].O1CCCC1>[CH2:1]=[CH:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH3:13]

Participants

7

Reactant 3

HCID 7918Acetic AnhydrideHCID 11005Myristic Acid2×HCID 11776Triphenylphosphine

Product 1

HCID 170951-TrideceneYield 1,308.4%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
255 °C

Procedure

A mixture of myristic acid (90.0 g, 0.394 mol) and acetic anhydride (40.2 g, 0.394 mol) was heated under reduced pressure (150 torr) using an oil bath maintained at 255° C. A small amount of a tetrahydrofuran solution containing dichlorobis(triphenylphosphine)palladium (0.453 g, 6.45×10-4 mol) and triphenylphosphine (2.97 g, 0.0113 mol) was then added to the reactor in order to initiate the decarbonylation reaction. The olefin product immediately distilled from the reaction mixture into a receiver. As material distilled from the reactor, it was continuously replaced with an equimolar mixture of myristic acid and acetic anhydride at a rate that maintained the initial level of the reactor contents throughout the course of the entire reaction. The solution of Pd-catalyst was added in a slow, continuous manner in order to keep the reaction temperature between ca. 215°-220° C. The decarbonylation reaction proceeded rapidly until the catalyst supply was exhausted, whereupon the reaction temperature gradually reached ca. 245° C. and conversion of myristic acid ceased. The combined product was washed with water and distilled to afford 940 g of 1-tridecene (bp 90° C./10 torr), which GC analysis showed to be 96.3% of the αolefin. TON=7985.

Workup

  1. temperaturewas heated under reduced pressure (150 torr)
  2. additionwas then added to the reactor in order
  3. customthe decarbonylation reaction
  4. distillationThe olefin product immediately distilled from the reaction mixture into a receiver
  5. distillationAs material distilled from the reactor, it
  6. additionwas continuously replaced with an equimolar mixture of myristic acid and acetic anhydride at a rate
  7. temperaturethat maintained the initial level of the reactor contents
  8. customthroughout the course of the entire reaction
  9. custombetween ca. 215°-220° C
  10. customThe decarbonylation reaction
  11. washThe combined product was washed with water
  12. distillationdistilled

Sources & evidence

ORD record
ord-726a75cf432647779b6bbeae9c62135d
Source dataset
uspto-grants-1991_12
Patent number
US05077447

Reaction notes

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