Method for producing unsaturated acid ester or unsaturated acid

Patent metadata

Field	Value
Publication number	US-9598345-B2
Application number	US-201614991393-A
Country	US
Kind code	B2
Filing date	Jan 8, 2016
Priority date	Jul 12, 2013
Publication date	Mar 21, 2017
Grant date	Mar 21, 2017

Abstract

The present invention relates to a method for producing an unsaturated-acid ester or an unsaturated acid, containing a step of reacting a compound (1) represented by the following formula (1) with a compound represented by the following formula (2) (excluding the compound (1)) in the presence of a Lewis acid catalyst at a temperature of the boiling point of the compound (1) or higher and 350° C. or lower, thereby obtaining products including a compound represented by the following formula (3):

(in formula (1) and formula (3), R 1 , R 2 and R 4 each independently may be hydrogen atom or an alkyl group, R 3 and R 5 each independently are hydrogen atom or a deuterium atom, and X is a halogen atom; in formula (2) and formula (3), R 6 may be hydrogen atom, an alkyl group or an aryl group, and R 7 is hydrogen atom or a deuterium atom).

First claim

The invention claimed is:

1. A method for producing an unsaturated-acid ester or an unsaturated acid, the method comprising
reacting a compound (1) of the formula (1) with a compound (2) of the formula (2), which is different from the compound of the formula (1), in the presence of a Lewis acid catalyst at a temperature within a range from 170° C. to 350° C., thereby obtaining a reaction product comprising a compound (3) of the formula (3)

wherein R 1 , R 2 , and R 4 each independently are selected from the group consisting of a hydrogen atom, a deuterium atom, and an alkyl group which has a carbon number of from 1 to 3 and may be optionally substituted with a halogen atom and/or a deuterium atom, R 3 and R 5 each independently are selected from the group consisting of a hydrogen atom and a deuterium atom, and X is a chlorine atom, a fluorine atom, a bromine atom, or an iodine atom;
R 6 —OR 7   (2),

wherein R 6 is selected from the group consisting of a hydrogen atom, a deuterium atom, and an alkyl group which has a carbon number of from 1 to 11 and may be optionally substituted with a halogen atom and/or a deuterium atom, or an aryl group and may be optionally substituted with a halogen atom and/or a deuterium atom, and R 7 is a hydrogen atom or a deuterium atom; and

wherein R 1 , R 2 , and R 4 are the same as defined with regard to the formula (1), and R 6 is the same as defined with regard to the formula (2); wherein the Lewis acid catalyst is at least one selected from the group consisting of ZnO—ZrO 2 , ZnO—Al 2 O 3 , ZnO—TiO 2 , In 2 O 3 —ZrO 2 , NiO—ZrO 2 , CoO—ZrO 2 , MnO—ZrO 2 , silica gel, γ-alumina, ZrO 2 , ZnO—SiO 2 , Zr PbO x , Al 2 O 3 —ZrO 2 , MgO—ZrO 2 , ZnO—Cr 2 O 3 , TiO 2 , and Zr—NiOx, and wherein the Lewis acid catalyst is fixed to a support.

2. The method according to claim 1 , wherein the Lewis acid catalyst is a solid acid.

3. The method according to claim 1 , wherein the reaction is conducted in a gas phase.

4. The method according to claim 1 , wherein an amount of the compound (2) is from 0.5 to 20 mol, per 1 mol of the compound (1).

5. The method according to claim 1 , wherein an amount of the compound (2) is from 1 to 10 mol, per 1 mol of the compound (1).

6. The method according to claim 1 , wherein an amount of the Lewis acid catalyst, per 1 mol of the compound (1) present in a reaction vessel, is from 0.001 to 1 mol.

7. The method according to claim 1 , wherein an amount of the Lewis acid catalyst, per 1 mol of the compound (1) present in a reaction vessel in a batch mode or per 1 mol of the compound (1) residing in a reaction vessel in a continuous mode, is from 0.01 to 0.2 mol.

8. The method according to claim 1 , wherein the reacting temperature is from 200 to 300° C.

9. The method according to claim 1 , wherein the reaction is conducted in a liquid phase.

10. The method according to claim 1 , wherein in the reaction a compound or gas which does not chemically react with starting materials and the reaction product is used as a solvent or a diluent gas,
wherein the solvent is selected from the group consisting of pentane, hexane, heptane, petroleum ether, dimethyl ether, diethyl ether, tetrahydrofuran, 1,2-dimethyoxyethane, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, acetic acid, benzoic acid, acetic anhydride, ethyl acetate, acetone, 2-butanone, acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, benzene, toluene, chlorobenzene, dichlorobenzene, benzonitrile, nitromethane, nitrobenzene, and a mixture thereof, and
wherein the diluent gas is selected from the group consisting of nitrogen, helium, argon, and a mixture thereof.

11. The method according to claim 10 , wherein an amount of the solvent or the diluent gas is in a range that a concentration of the compound (1) is kept at 5% by mass or higher.

12. The method according to claim 1 , wherein the reaction is conducted in a continuous mode and a space velocity is from 1 to 500,000 h −1 .

13. The method according to claim 1 , wherein a reaction pressure is from 0 MPa to 10 MPa.

14. The method according to claim 1 , wherein a reaction pressure is from 0.05 MPa to 2 MPa.

15. The method according to claim 1 , wherein when the reacting is conducted in a batch mode, a reaction time is from 10 minutes to 12 hours, and when the reacting is conducted in a continuous mode, a reaction time is from 0.1 second to 60 minutes.

Assignees

• Asahi Glass Co Ltd

Inventors

• Fujita Tomoyuki
• Murata Koichi
• Shirota Naoko
• Suzuki Yusuke
• Jomuta Daisuke

Classifications

• C07C67/10 Primary

  by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond (preparation from carboxylic acid halides C07C67/14) · CPC title

• C07C57/04

  Acrylic acid; Methacrylic acid · CPC title

• C07C51/093

  by hydrolysis of —CX3 groups, X being halogen · CPC title

• C07C67/00 Primary

  Preparation of carboxylic acid esters · CPC title

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title