Palladium(II)-silica supported catalyst

Patent metadata

Field	Value
Publication number	US-10150109-B2
Application number	US-201815919812-A
Country	US
Kind code	B2
Filing date	Mar 13, 2018
Priority date	Sep 6, 2016
Publication date	Dec 11, 2018
Grant date	Dec 11, 2018

Abstract

A solid-supported palladium(II) complex which catalyzes the Mizoroki-Heck coupling reaction efficiently and a method of employing the solid-supported palladium(II) complex to synthesize cinnamic acid and derivatives thereof. The solid-supported palladium(II) complex is also stable and can be recycled without significantly losing catalytic activity.

First claim

The invention claimed is:

1. A silica-supported catalyst, comprising a reaction product of:
a ligand of formula (I)

a solid silica support;
wherein X is O,
R 1 and R 2 are each independently optionally substituted alkyl,
R 3 , R 4 , R 5 and R 6 are H,
n is 1; and

a palladium(II) salt of the formula PdCl 2 ;
wherein the solid silica support is functionalized to comprise a substituted benzyl group and X is bonded to a carbon atom of the benzyl group in the reaction product;
wherein the reaction product comprises a palladium(II) ion bound to a nitrogen atom in each oxazoline heterocycle in formula (I).

2. The silica-supported catalyst of claim 1 , wherein the solid silica support is in the form of a particle with an average diameter of 1-100 μm.

3. The silica-supported catalyst of claim 1 , which comprises 0.1-1 mmol of palladium per gram of the silica-supported catalyst.

4. The silica-supported catalyst of claim 1 , which has a turnover number in a range of 1,500-2,500 and a turnover frequency in a range of 200-1,500 per hour.

5. A method for synthesizing cinnamic acid or derivatives thereof, the method comprising:
reacting an aryl halide with an acrylic acid or derivatives thereof in the presence of a solvent, a base, and the silica-supported catalyst of claim 1 at a temperature in a range of 35-110° C., thereby forming the cinnamic acid or derivatives thereof.

6. The method of claim 5 , further comprising:
separating the silica-supported catalyst from the cinnamic acid or derivatives thereof; and
reusing the silica-supported catalyst in at least two cycles, wherein the silica-supported catalyst loses less than 5 wt % of the palladium after the at least two cycles.

7. The method of claim 5 , wherein the aryl halide is a limiting reactant.

8. The method of claim 5 , wherein an amount of the silica-supported catalyst is in a range of 0.05-10 mol % relative to a number of moles of the aryl halide.

9. The method of claim 5 , wherein the solvent comprises 5-95% by volume of water and 5-95% by volume of an organic solvent, based on a total volume of the solvent.

10. The method of claim 5 , wherein the base is at least one selected from the group consisting of an alkali metal hydroxide, an alkali metal carbonate, and an amine.

Assignees

• Univ King Fahd Pet & Minerals

Inventors

• ALI Bassam El
• Ibrahim Mansur B

Classifications

• C07C51/09 Primary

  from carboxylic acid esters or lactones · CPC title

• B01J2531/824

  Palladium · CPC title

• C07C51/377

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)} · CPC title

• C07C51/06

  from carboxylic acid amides · CPC title

• C07C59/64

  containing six-membered aromatic rings · CPC title