Stearic Acid → 1-Heptadecene

HRID 1461898Notes

Reaction equation

HRID 1461898 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][CH2:14][CH2:15][CH2:16][CH2:17]C.C(OC(=O)C)(=O)C>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.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:1]=[CH:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH3:17]

Participants

5

Reactant 2

HCID 5281Stearic Acid2×HCID 7918Acetic Anhydride2×

Product 1

HCID 232171-HeptadeceneYield 188.6%

Reagents, catalysts & solvents 2

HCID 11776TriphenylphosphineCatalyst2×HCID 178418476HCID 178418476, compoundCatalyst

Conditions

Temperature
90 °C

Procedure

A mixture of stearic acid (150 g, 0.527 mol), acetic anhydride (54 g, 0.53 mol), and triphenylphosphine (0.921 g, 3.51×10-3 mol) was heated to 220°-230° C. under reduced pressure (55 torr) in a 500 mL flask fitted with a distillation head for product removal. Into this solution was pumped a feed mixture composed of stearic acid (400 g, 1.41 mol), acetic anhydride (150 g, 1.47 mol), dichlorobis(triphenylphosphine)palladium (0.0492 g, 7.03×10-5 mol), and triphenylphosphine (0.921 g, 3.51×10-3 mol) This feed mixture was maintained at ca. 90° C. and introduced into the reactor via a stainless steel tube with the opening positioned below the solution level. As product distilled from the reactor it was continuously replaced with more feed mixture at a rate of introduction that was approximately equal to the rate of product removal in order to maintain a constant level of the reaction mixture. The reaction was continued in this manner until the supply of feed mixture was exhausted (ca. 3.5 hours). At the conclusion of the reaction the level of reactor contents was about the same as at the beginning of the reaction. The distillate product was fractionally distilled to afford 237 g of 1-heptadecene (bp 130°-135° C./0.4 torr) which was found by GC analysis to be 95.6% of the α-olefin. This amount of product corresponds to a catalyst TON of 13,515. Considering the amount of unreacted stearic acid-containing residue recovered in the distillation pot (94 g), the isolated yield of 1-heptadecene relative to the stearic acid in the feed mixture was at least 92%.

Workup

  1. temperaturewas heated to 220°-230° C. under reduced pressure (55 torr) in a 500 mL flask
  2. customfitted with a distillation head for product removal
  3. additionintroduced into the reactor via a stainless steel tube with the opening
  4. distillationAs product distilled from the reactor it
  5. customwas approximately equal to the rate of product removal in order
  6. temperatureto maintain a constant level of the reaction mixture
  7. custom(ca. 3.5 hours)
  8. customAt the conclusion of the reaction the level of reactor contents
  9. customsame as at the beginning of the reaction
  10. distillationThe distillate product was fractionally distilled

Sources & evidence

ORD record
ord-a6a5731b6e974d73bcf924a5f55e2cf1
Source dataset
uspto-grants-1991_12
Patent number
US05077447

Reaction notes

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