Catalytic process for synthesizing ester compounds and amide compounds

Patent metadata

Field	Value
Publication number	US-9745247-B1
Application number	US-201615235169-A
Country	US
Kind code	B1
Filing date	Aug 12, 2016
Priority date	Aug 12, 2016
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

A catalytic process for synthesizing an ester compound, and a catalytic process for synthesizing an amide compound, wherein a solid-supported palladium catalyst is used to catalyze an alkoxycarbonylation reaction of an aryl halide to form the ester compound, or to catalyze an aminocarbonylation reaction of an aryl halide to form the amide compound. Various embodiments of each of the processes are also provided.

First claim

The invention claimed is:

1. A process for synthesizing an aryl ester compound, comprising:
mixing an aryl halide compound, an alcohol, a base, and a catalyst in a reaction chamber;
pressurizing the reaction chamber with carbon monoxide; and
heating the reaction chamber to react the aryl halide compound with carbon monoxide and the alcohol in the presence of the catalyst via an alkoxycarbonylation reaction to form the aryl ester compound,
wherein the catalyst has a structure of formula (I):

wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently a hydrogen, an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted cycloalkylalkyl, an optionally substituted arylalkyl, an optionally substituted heteroaryl, an optionally substituted aryl, an optionally substituted heterocyclyl, an optionally substituted alkylthio, an optionally substituted alkanoyl, an optionally substituted aroyl, an optionally substituted aralkyl, an optionally substituted heteroarylcarbonyl, an optionally substituted hydrocarbyl, an optionally substituted aryl halide, an optionally substituted arylolefin, an optionally substituted arylalkylcarboxylic acid, an optionally substituted benzyl, or an optionally substituted vinyl,
SS is a solid support, and
X is selected from the group consisting of Cl, F, Br, I, OAc, and OTf.

2. The process of claim 1 , wherein the catalyst has a structure of formula (II):

wherein SS is a solid support, and X is selected from the group consisting of Cl, F, Br, I, OAc, and OTf.

3. The process of claim 1 , wherein the catalyst has a structure of formula (II):

wherein SS is a Merrifield resin, and X is selected from the group consisting of Cl, F, Br, I, OAc, and OTf.

4. The process of claim 1 , wherein the catalyst has a structure of formula (III):

wherein SS is a Merrifield resin.

5. The process of claim 1 , wherein the catalyst is in the form of spherical particles having an average diameter within the range of 1-50 nm.

6. The process of claim 1 , further comprising:
separating the catalyst from the aryl ester compound; and
recycling the catalyst,
wherein the catalyst loses less than 5 wt % of the palladium metal after at least 10 cycles.

7. The process of claim 6 , wherein a turnover number of the catalyst in the alkoxycarbonylation reaction after at least 10 cycles is within the range of 1,800 to 10,000.

8. The process of claim 6 , wherein a turnover frequency of the catalyst in the alkoxycarbonylation reaction after at least 10 cycles is within the range of 300-2,000 per hour.

9. The process of claim 1 , wherein the alkoxycarbonylation reaction is conducted at a temperature in the range 25-200° C., and a pressure in the range of 80-150 psi.

10. The process of claim 9 , wherein a formation yield of the aryl ester compound is at least 80%, with the formation yield being relative to an initial molar weight of the aryl halide compound.

11. The process of claim 1 , wherein the base is at least one selected from the group consisting of an alkali metal hydroxide, an alkali metal carbonate, and an amine.

12. The process of claim 1 , wherein the aryl halide compound is a limiting reactant in the alkoxycarbonylation reaction.

13. A process for synthesizing an amide compound, comprising:
mixing an aryl halide compound, an amine, a base, an organic solvent, and a catalyst in a reaction chamber;
pressurizing the reaction chamber with carbon monoxide; and
heating the reaction chamber to react the aryl halide compound with carbon monoxide and the amine in the presence of the catalyst via an aminocarbonylation reaction to form the amide compound,
wherein the catalyst has a structure of formula (I):

wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently a hydrogen, an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted cycloalkylalkyl, an optionally substituted arylalkyl, an optionally substituted heteroaryl, an optionally substituted aryl, an optionally substituted heterocyclyl, an optionally substituted alkylthio, an optionally substituted alkanoyl, an optionally substituted aroyl, an optionally substituted aralkyl, an optionally substituted heteroarylcarbonyl, an optionally substituted hydrocarbyl, an optionally substituted aryl halide, an optionally substituted arylolefin, an optionally substituted arylalkylcarboxylic acid, an optionally substituted benzyl, or an optionally substituted vinyl,
SS is a solid support, and
X is selected from the group consisting of Cl, F, Br, I, OAc, and OTf.

14. The process of claim 13 , wherein the catalyst has a structure of formula (II):

wherein SS is a solid support, and X is selected from the group consisting of Cl, F, Br, I, OAc, and OTf.

15. The process of claim 13 , wherein the catalyst has a structure of formula (II):

wherein SS is a Merrifield resin, and X is selected from the group consisting of Cl, F, Br, I, OAc, and OTf.

16. The process of claim 13 , wherein the catalyst has a structure of formula (III):

wherein SS is a Merrifield resin.

17. The process of claim 13 , wherein the aminocarbonylation reaction is conducted at a temperature in the range 25-200° C., and a pressure in the range of 100-250 psi.

18. The process of claim 13 , wherein the amine comprises one or more of a primary amine and a secondary amine.

19. A process for synthesizing a carboxylic acid compound, comprising:
mixing an aryl halide compound, water, a base, and a catalyst in a reaction chamber;
pressurizing the reaction chamber with carbon monoxide; and
heating the reaction chamber to react the aryl halide compound with carbon monoxide and water in the presence of the catalyst via a hydroxycarbonylation reaction to form the carboxylic acid compound,
wherein the catalyst has a structure of formula (I):

wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently a hydrogen, an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted cycloalkylalkyl, an optionally substituted arylalkyl, an optionally substituted heteroaryl, an optionally substituted aryl, an optionally substituted heterocyclyl, an optionally substituted alkylthio, an optionally substituted alkanoyl, an optionally substituted aroyl, an optionally substituted aralkyl, an optionally substituted heteroarylcarbonyl, an optionally substituted hydrocarbyl, an optionally substituted aryl halide, an optionally substituted arylolefin, an optionally substituted arylalkylcarboxylic acid, an optionally sub

Assignees

• Univ King Fahd Pet & Minerals

Inventors

• El Ali Bassam M
• Ibrahim Mansur B
• Suleiman Rami K

Classifications

• B01J31/06

  containing polymers {(organometallic polymers B01J31/123; polymer-bound organometallic complexes B01J31/165; coordination polymers B01J31/1691)} · CPC title

• C07C231/10

  from compounds not provided for in groups C07C231/02 - C07C231/08 · CPC title

• B01J2531/824

  Palladium · CPC title

• B01J2231/34

  Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N · CPC title

• C07C2601/14

  The ring being saturated · CPC title