Method for producing alpha-allylated cycloalkanone

Patent metadata

Field	Value
Publication number	US-11524929-B2
Application number	US-202017440284-A
Country	US
Kind code	B2
Filing date	Mar 17, 2020
Priority date	Mar 18, 2019
Publication date	Dec 13, 2022
Grant date	Dec 13, 2022

Abstract

Provided is a method with which an α-allylated cycloalkanone is obtained from a cyclic compound cycloalkanone used as a starting material. The method is a method for producing an α-allylated cycloalkanone represented by General Formula (III), and the method includes: a step 1: reacting a compound represented by General Formula (I) and alcohol having 1 or more and 4 or less of carbon atoms in the presence of a first acid catalyst and optionally a dehydrating agent; and a step 2: reacting a crude product obtained in the step 1 and a compound represented by General Formula (II) in the presence of a second acid catalyst to produce an α-allylated cycloalkanone represented by General Formula (III). The step 1 and the step 2 are consecutively performed. In the formulae above, the group -A1- (it should be noted that the front bond refers to a bond that binds to the carbon atom C1 and the back bond refers to a bond that binds to the carbon atom C2) 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 R4 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 (III-1), comprising:
1: reacting a compound represented by Formula (I-1) and an alcohol having 1 or more and 4 or less of carbon atoms in the presence of a first acid catalyst and optionally a dehydrating agent; and
2: reacting a crude product obtained in the reacting 1 and a compound represented by Formula (II) in the presence of a second acid catalyst to produce an α-allylated cycloalkanone represented by Formula (III-1),
wherein the reacting 1 and the reacting 2 are consecutively performed without isolating a compound of Formula (XX) or a compound of Formula (XXI) after said reacting 1

wherein R 4 is alkyl group having 1 carbon atom,

wherein:
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 10 carbon atoms, 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 .

2. The method according to claim 1 , further comprising removing the alcohol having 1 or more and 4 or less of carbon atoms in the presence of the first acid catalyst after reacting 1.

3. The method according to claim 1 , wherein the method in which the reacting 1 and the reacting 2 are consecutively performed comprises no isolation-purification step performed in the course of the method.

4. The method according to claim 1 , wherein the first acid catalyst and the second acid catalyst are independently one or more selected from the group consisting of organic sulfonic acids and salts thereof, and inorganic acid salts of pyridine.

5. The method according to claim 4 , wherein the organic sulfonic acids are aromatic sulfnic acids.

6. The method according to claim 4 , wherein the first acid catalyst and the second acid catalyst are independently selected from the group consisting of compounds represented by Formula (X) below and compounds represented by Formula (XI) below:

where R 21 and R 22 are independently a hydrogen atom or an alkyl group having 1 or more and 5 or less of carbon atoms, and X 4 is represented by Formula (XII) or Formula (XIII), and 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.

7. The method according to claim 1 , wherein the first acid catalyst and the second acid catalyst independently comprises p-toluenesulfonic acid or pyridinium p-toluenesulfonate.

8. The method according to claim 4 , wherein the salts of the organic sulfonic acids are pyridinium salts.

9. The method according to claim 4 , wherein an acid included in the inorganic acid salts of pyridine is one or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sulfurous acid, nitrous acid, hydrobromic acid, hydroiodic acid, acetic acid, and butyric acid.

10. The method according to claim 1 , wherein the first acid catalyst and the second acid catalyst are the same.

11. The method according to claim 1 , wherein an amount of the first 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 General Formula (I) and the compound of General Formula (II).

12. The method according to claim 1 , wherein the reacting 1 and the reacting 2 are performed using a rectification column.

13. The method according to claim 1 , wherein the reacting 1 and the reacting 2 are performed in one pot.

14. A method for synthesizing muscenone, the method comprising:
1: reacting a compound represented by Formula (I-1) and an alcohol having 1 or more and 4 or less of carbon atoms in the presence of a first acid catalyst and optionally a dehydrating agent;
2: reacting a crude product obtained in the reacting 1 and β-methallyl alcohol in the presence of a second acid catalyst to produce an α-allylated cycloalkanone represented by Formula (III-1),
(i) cyclization of the α-allylated cycloalkanone represented by Formula (III-1);
(ii) hydrogenation;
(iii) oxidative cleavage;
(iv) reduction; and
(v) ring-opening,

wherein the reacting 1 and the reacting 2 are consecutively performed without isolating a compound of Formula (XX) or a compound of Formula (XXI) after said reacting 1

wherein
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 10 carbon atoms, 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 .

15. The method according to claim 14 , further comprising removing the alcohol having 1 or more and 4 or less of carbon atoms in the presence of the first acid catalyst after reacting 1.

Assignees

• Kao Corp

Inventors

• Deguchi Jun
• Sakakibara Makoto
• SAKODA Daichi

Classifications

• C07C2601/20

  the ring being twelve-membered · CPC title

• C07C45/515

  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

• C07C45/61

  by reactions not involving the formation of >C = O groups · CPC title

• C07C45/513

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

• C07C41/01 Primary

  Preparation of ethers · CPC title