Method for producing α-allylated cycloalkanone

Patent metadata

Field	Value
Publication number	US-11685705-B2
Application number	US-202017440564-A
Country	US
Kind code	B2
Filing date	Mar 17, 2020
Priority date	Mar 18, 2019
Publication date	Jun 27, 2023
Grant date	Jun 27, 2023

Abstract

Provided is a method with which an α-allylated cycloalkanone is obtained from a macroyclic compound used as a starting material. The method is a method for producing an α-allylated cycloalkanone represented by General Formula (IV), and the method includes a step of reacting a compound represented by General Formula (I) and/or a compound represented by General Formula (II) with a compound represented by General Formula (III) in the presence of an acid catalyst to produce an α-allylated cycloalkanone represented by General Formula (IV), the acid catalyst including an acid catalyst that includes an ammonium cation and an anion.

where R 1 , R 2 , and R 3 are the same or different and each of them is an alky group having 1 or mom and 4 or less of carbon atoms, the group -A 1 - (it should be noted that the front bond refers to a bond that binds to the carbon atom C 1 and the back bond refers to a bond that binds to the carbon atom C 2 ) is an alkylene group having 4 or more and 20 or les of carbon atoms that optionally contains a hetero atom and optionally has a substituent, and R 4 is a hydrogen atom or an alkyl group having 1 or more and 4 or less of carbon atoms.

First claim

The invention claimed is:

1. A method for producing an α-allylated cycloalkanone represented by Formula (IV), the method comprising
reacting a compound represented by Formula (I) and/or a compound represented by Formula (II) with a compound represented by Formula (III) in the presence of an acid catalyst to produce an α-allylated cycloalkanone represented by Formula (IV),
wherein the acid catalyst includes an acid catalyst that consists of an ammonium cation and an anion

where R 1 , R 2 , and R 3 are the same or different and each of them is an alkyl group having 1 or more and 4 or less of carbon atoms, the group -A 1 - is an alkylene group having 4 or more and 20 or less of carbon atoms that optionally contains a hetero atom and optionally has a substituent, and where the front bond of the group -A 1 - refers to a bond that binds to the carbon atom C 1 and the back bond of the group -A 1 - refers to a bond that binds to the carbon atom C 2 and R 4 is a hydrogen atom or an alkyl group having 1 or more and 4 or less of carbon atoms,
the ammonium canon is represented b Formula (X) or Formula (XI);

where R 11 , R 12 , R 13 , and R 14 are the same or different and each of them is a hydrogen atom or an alkyl group having 1 or more and 5 or less of carbon atoms,
the anion is a sulfonate anion represented by Formula (XII) or a halide ion:

where R 21 is a hydrogen atom or an alkyl group having 1 or more and 5 or less of carbon atoms.

2. The method according to claim 1 , wherein the group -A 1 - is an alkylene group having 10 or more and 14 or less of carbon atoms that optionally has a substituent.

3. The method according to claim 1 , wherein the group -A 1 - is an alkylene group having 10 or more and 12 or less of carbon atoms.

4. The method according to claim 1 , wherein an amount of the acid catalyst that is used is 10 −5 equivalents or more and 1 equivalent or less relative to a total amount of the compound of Formula (I) and the compound of Formula (II).

5. The method according to claim 1 , wherein the reacting a compound represented by Formula (I) and/or a compound represented by Formula (II) with a compound represented by Formula (III) in the presence of an acid catalyst is performed at a temperature of 120° C. or higher and 150° C. or lower.

6. The method according to claim 1 , wherein the reacting is performed using a rectification column.

7. The method according to claim 1 , further comprising reacting a compound represented by Formula (V) with an alcohol having 1 or more and 4 or less of carbon atoms in the presence of a second acid catalyst to produce the compound represented by Formula (I) and/or the compound represented by Formula (II),

where R 1 , R 2 , and R 3 are the same or different and each of them is an alkyl group having 1 or more and 4 or less of carbon atoms, and the group -A 1 - is an alkylene group having 4 or more and 20 or less of carbon atoms that optionally contains a hetero atom and optionally has a substituent, and where the front bond of the group -A 1 - refers to a bond that binds to the carbon atom C 1 and the back bond of the group -A 1 - refers to a bond that binds to the carbon atom C 2 .

8. The method according to claim 7 , wherein the second acid catalyst is one or more selected from the group consisting of p-toluenesulfonic acid, montmorillonite, and pyridinium p-toluenesulfonate.

9. The method according to claim 7 , wherein the second acid catalyst comprises the catalyst which is the same as the acid catalyst.

10. The method according to claim 7 , wherein the group -A 1 - is an alkylene group having 10 or more and 14 or less of carbon atoms that optionally has a substituent.

11. The method according to claim 7 , wherein the group -A 1 - is an alkylene group having 10 or more and 12 or less of carbon atoms.

12. The method according to claim 7 , wherein the reacting of a compound represented by Formula (V) with an alcohol having 1 or more and 4 or less of carbon atoms in the presence of a second acid catalyst is performed at a temperature of 120° C. or higher and 150° C. or lower.

13. The method according to claim 1 , wherein the Formula (I) is Formula (I-1) below, the Formula (II) is Formula (II-1) below, and the Formula (IV) is Formula (IV-1) below:

14. A method for synthesizing muscenone, the method comprising:
reacting a compound represented by Formula (I-1) and/or a compound represented by Formula (II-1) with β-methallyl alcohol in the presence of an acid catalyst to produce an α-allylated cycloalkanone represented by Formula (IV-1),
wherein the acid catalyst includes an acid catalyst that consists of an ammonium cation and an anion;
(i) cyclization of the α-allylated cycloalkanone represented by General Formula (IV-1);

(ii) hydrogenation;
(iii) oxidative cleavage,
(iv) reduction; and
(v) ring-opening
the ammonium cation is represented by General Formula (X) or Formula (XI);

where R 11 , R 12 , R 13 , and R 14 are the same or different and each of them is a hydrogen atom or an alkyl group having 1 or more and 5 or less of carbon atoms,
the anion is a sulfonate anion represented by General Formula (XII) or a halide ion:

where R 21 is a hydrogen atom or an alkyl group having 1 or more and 5 or less of carbon atoms.

15. The method according to claim 14 , wherein an amount of the acid catalyst that is used is 10 −5 equivalents or more and 1 equivalent or less relative to a total amount of the compound of Formula (I-1) and the compound of Formula (II-1).

16. The method according to claim 14 , wherein the reacting a compound represented by Formula (I-1) and/or a compound represented by Formula (II-1) in the presence of an acid catalyst is performed at a temperature of 120° C. or higher and 150° C. or lower.

17. The method according to claim 14 , wherein the reacting is performed using a rectification column.

Assignees

• Kao Corp

Inventors

• Deguchi Jun
• Sakakibara Makoto
• SAKODA Daichi

Classifications

• C07C45/513 Primary

  the singly bound functional group being an etherified hydroxyl group · CPC title

• C07C45/66

  by dehydration · CPC title

• C07C2601/20

  the ring being twelve-membered · CPC title

• C07C45/515 Primary

  the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group (cyclic acetals or ketals C07C45/59, C07C45/60) · CPC title

• C07B61/00 Primary

  Other general methods · CPC title