Method for manufacturing 1,3-dioxane-5-one

Patent metadata

Field	Value
Publication number	US-10870643-B2
Application number	US-201716473065-A
Country	US
Kind code	B2
Filing date	Dec 26, 2017
Priority date	Dec 27, 2016
Publication date	Dec 22, 2020
Grant date	Dec 22, 2020

Abstract

The present invention relates to a method for producing a 1,3-dioxan-5-one by a short-step and simple method from raw materials that are procurable easily and inexpensively, using, as a raw material, a 1,3-dioxane that is a mixture containing a 1,3-dioxolane. Provided is a method for producing a 1,3-dioxan-5-one, including using a mixture of a compound represented by the following formula (I) and a compound represented by the following formula (II) as a raw material, the method including a step of oxidizing the mixture under an oxidative esterification condition (step 2):

wherein, in the formulae (I) and (II), R 1 and R 2 each independently represent a hydrogen atom or a monovalent hydrocarbon group, or R 1 and R 2 are bonded to each other to form a divalent hydrocarbon group for constituting a ring structure.

First claim

The invention claimed is:

1. A method for producing a 1,3-dioxan-5-one, comprising using a mixture of a compound represented by the following formula (I) and a compound represented by the following formula (II) as a raw material, the method comprising a step of oxidizing the mixture under an oxidative esterification condition defined as obtaining one molecule of an ester dimer from two molecules of the same primary alcohol (step 2):

wherein, in the formulae (I) and (II), R 1 and R 2 each independently represent a hydrogen atom or a monovalent hydrocarbon group, or R 1 and R 2 are bonded to each other to form a divalent hydrocarbon group for constituting a ring structure.

2. The method for producing a 1,3-dioxan-5-one according to claim 1 , wherein in the formulae (I) and (II), R 1 is a hydrogen atom.

3. The method for producing a 1,3-dioxan-5-one according to claim 1 , wherein in the step 2, (a) at least one compound selected from an organic nitroxyl radical, an N-hydroxy form thereof, and a salt containing an oxo ammonium cation of an organic nitroxyl radical, (b) an oxidizing agent, and (c) a base are used.

4. The method for producing a 1,3-dioxan-5-one according to claim 3 , wherein the organic nitroxyl radical is a compound represented by the following formula (VIII), a compound represented by the following formula (IX), or a compound represented by the following formula (X):

wherein, in the formula (VIII), R 4 represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, an alkoxy carbonyl group, an amino group, an acylamino group, a sulfonyloxy group, an N-alkylcarbamoyloxy group, a carboxy group, a cyano group, an isocyanato group, an isothiocyanato group, or an oxo group; in the formula (IX), R 5 and R 6 each independently represent a hydrogen atom or a methyl group; and, in the formula (X), R 7 and R 8 each independently represent a hydrogen atom or a methyl group.

5. The method for producing a 1,3-dioxan-5-one according to claim 3 , wherein the oxidizing agent is an oxidizing agent composed of a compound containing chlorine.

6. The method for producing a 1,3-dioxan-5-one according to claim 3 , wherein the base is a heterocyclic aromatic amine having a pyridine skeleton.

7. The method for producing a 1,3-dioxan-5-one according to claim 1 , comprising, after the step 2, a step of separating the 1,3-dioxan-5-one (step 3).

8. The method for producing a 1,3-dioxan-5-one according to claim 7 , wherein the separation in the step 3 is separation through distillation.

9. The method for producing a 1,3-dioxan-5-one according to claim 1 , wherein the mixture of a compound represented by the following formula (I) and a compound represented by the following formula (II) is produced by a method of acetalizing glycerol, and a compound represented by the following formula (V) or a multimer thereof in the presence of an acid catalyst (method 1), or a method of subjecting glycerol and a compound represented by the following formula (VI) to acetal exchange in the presence of an acid catalyst (method 2):

in the formulae (V) and (VI), R 1 and R 2 are synonymous with R 1 and R 2 in the formula (I) or (II), and in the formula (VI), R 3 's each independently represent a monovalent hydrocarbon group.

10. The method for producing a 1,3-dioxan-5-one according to claim 1 , wherein in the step 2, an oxidation method selected from
an oxidation method of using a salt containing an oxo ammonium cation of an organic nitroxyl radical and a base; and
an oxidation method of using a compound selected from an organic nitroxyl radical, an N-hydroxy form thereof, and a salt containing an oxo ammonium cation of an organic nitroxyl radical, an oxidizing agent, and a base.

11. The method for producing a 1,3-dioxan-5-one according to claim 10 , wherein an amount of the compound selected from the organic nitroxyl radical, the N-hydroxy form thereof, and the salt containing an oxo ammonium cation of an organic nitroxyl radical is 0.0001 or more and 0.1 or less in a molar ratio relative to the mixture of the compound represented by the formula (I) and the compound represented by the formula (II).

12. The method for producing a 1,3-dioxan-5-one according to claim 6 , wherein the heterocyclic aromatic amine having a pyridine skeleton is at least one selected from pyridine, 3,5-lutidine, 2,6-lutidine, 3-ethylpyridine, 4-ethylpyridine, and 5-ethyl-2-methylpyridine.

13. The method for producing a 1,3-dioxan-5-one according to claim 1 , wherein in the step 2, a solvent is used, which is selected from acetone, 2-butanone, cyclopentanone, acetonitrile, and dichloromethane.

14. The method for producing a 1,3-dioxan-5-one according to claim 1 , wherein the step of oxidizing the mixture under an oxidative esterification condition (step 2) satisfies the following conditions 1 to 3;
Condition 1: The dioxanone is produced from the dioxane,
Condition 2: The ester dimer is produced from the dioxolane, and
Condition 3: The yield of the formyl dioxolane produced from the dioxolane is 10% or less and 0% or more.

Assignees

• Kao Corp

Inventors

• Aoki Takashi

Classifications

• C07C45/65 Primary

  by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups · CPC title

• C07D319/06

  not condensed with other rings · CPC title

• C07C215/10

  with one amino group and at least two hydroxy groups bound to the carbon skeleton · CPC title

• C07C213/00

  Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton · CPC title

• C07D407/12 Primary

  linked by a chain containing hetero atoms as chain links · CPC title