Acetic Anhydride → 1-Tridecene

HRID 1461893ノート

反応式

HRID 1461893 の反応式
[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]

参加物

7

反応物 3

HCID 7918Acetic AnhydrideHCID 11005Myristic Acid2 回HCID 11776Triphenylphosphine

生成物 1

HCID 170951-Tridecene収率 1,308.4%

試薬・触媒・溶媒 3

HCID 23938Palladium触媒HCID 178418476HCID 178418476、化合物触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
255 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-726a75cf432647779b6bbeae9c62135d
出典データセット
uspto-grants-1991_12
特許番号
US05077447

反応ノート

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