Method for preparing ethers of cycloaliphatic or araliphatic diols

Patent metadata

Field	Value
Publication number	US-11078146-B2
Application number	US-201816769716-A
Country	US
Kind code	B2
Filing date	Dec 3, 2018
Priority date	Dec 4, 2017
Publication date	Aug 3, 2021
Grant date	Aug 3, 2021

Abstract

The present invention relates to a method for preparing a dialkyi or dialkenyl ether of a cycloaliphatic or araliphatic diol, which comprises (i) reacting the cycloaliphatic or araliphatic diol with metallic sodium in an aprotic organic solvent in the presence of a catalytic amount of at least one monoether-monoalcohol of formula (I) wherein Y is identical or different and selected from C 2 -C 4 -alkylene, n is an integer in the range from 1 to 10, and R 1 is C 1 -C 4 -Alkyl, whereby the corresponding disodium dialcoholate is obtained, reacting the disodium dialcoholate obtained in step (i) with an alkylation alkenylation reagent.

First claim

The invention claimed is:

1. A method for preparing a dialkyl or dialkenyl ether of a cycloaliphatic or araliphatic diol, which comprises
(i) reacting the cycloaliphatic or araliphatic diol with metallic sodium in an aprotic organic solvent in the presence of a catalytic amount of at least one monoether-monoalcohol of formula (I)

wherein
Y is identical or different and selected from C 2 -C 4 -alkylene,
n is an integer in the range from 1 to 10, and
R 1 is C 1 -C 4 -alkyl,
whereby the corresponding disodium dialcoholate is obtained,

(ii) reacting the disodium dialcoholate obtained in step (i) with an alkylation or alkenylation reagent.

2. The method of claim 1 , where the amount of the at least one monoether-monoalcohol (I) used in step (i) is in the range of 1 to 10 mol-%, based on the amount of the cycloaliphatic or araliphatic diol.

3. The method of claim 1 , where the monoether-monoalcohol of formula (I) is selected from the group consisting of
2-methoxyethanol, 2-ethoxyethanol, 3-methoxy-1-propanol, 3-ethoxy-1-propanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 2-methoxy-1-propanol, 2-ethoxy-1-propanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 3-(3-methoxy-1-propoxy)-1-propanol, 3-(3-ethoxy-1-propoxy)-1-propanol, 1-(2-methoxy-1-methylethoxy)-2-propanol, 1-(2-ethoxy-1-methylethoxy)-2-propanol, 1-(2-methoxypropoxy)-2-propanol, 1-(2-ethoxypropoxy)-2-propanol, 2-(2-methoxypropoxy)-1-propanol, 2-(2-ethoxypropoxy)-1-propanol, 2-(2-methoxy-1-methylethoxy)-1-propanol, 2-(2-ethoxy-1-methylethoxy)-1-propanol, 2-[2-(2-methoxyethoxy)ethoxy]-ethanol, 2-[2-(2-ethoxyethoxy)ethoxy]-ethanol, 3-[3-(3-methoxypropoxy)propoxy]propan-1-ol, 3-[3-(3-ethoxypropoxy)propoxy]propan-1-ol, 2-[2-(2-methoxypropoxy)propoxy]-1-propanol, 2-[2-(2-ethoxypropoxy)propoxy]-1-propanol, and mixtures thereof.

4. The method of claim 1 , where the molar ratio of metallic sodium to cycloaliphatic or araliphatic diol is in the range of from 1.8:1 to 4:1.

5. The method of claim 1 , where the alkylation or alkenylation reagent is a compound of the formula (II)
R 2 —X  (II)

wherein
R 2 is selected from the group consisting of C 1 -C 10 -alkyl and C 2 -C 4 -alkenyl, and
X represents a leaving group, selected from halogen, O—CO—O—R 2 , O—SO 2 —O—R 2 and O—S(O 2 )R 2a , where R 2a is selected from the group consisting of phenyl, which is unsubstituted or carries 1, 2 or 3 C 1 -C 3 -alkyl radicals, C 1 -C 4 -alkyl and C 1 -C 4 -fluoroalkyl.

6. The method of claim 5 , where in step (ii) R 2 —O—SO 2 —O—R 2 is used as the alkylation or alkenylation reagent.

7. The method of claim 5 , where in formula (II) the radical R 2 is C 1 -C 3 -alkyl.

8. The method of claim 1 , where the cycloaliphatic or araliphatic diol is selected from a compound of the formula (III)

wherein
A is selected from the group consisting of C 5 -C 10 -cycloalkylene and C 6 -C 12 -arylene, wherein C 5 -C 10 -cycloalkylene and C 6 -C 12 -arylene are, independently of each other, unsubstituted or substituted by 1, 2, 3, 4 or 5 radicals selected from C 1 -C 4 -alkyl, and
L 1 and L 2 , independently of one another, are selected from the group consisting of a chemical bond and C 1 -C 3 -alkylene, where C 1 -C 3 -alkylene is unsubstituded or substituted by 1 or 2 radicals selected from C 1 -C 4 -alkyl and cyclopropyl.

9. The method of claim 8 , where the compound of formula (III) is selected from one of the following compounds of the general formulae (III.a) to (III.g),

10. The method of claim 1 , where in step (i) the metallic sodium is first emulsified in the inert organic solvent comprising a catalytic amount of the monoether-monoalcohol of formula (I) followed by the addition of the cycloaliphatic or araliphatic diol to the emulsified metallic sodium.

11. The method of claim 10 , where the cycloaliphatic or araliphatic diol is added to the metallic sodium, which is emulsified in the inert organic solvent comprising a catalytic amount of the monoether-monoalcohol of the formula (I), over a period of from 5 minutes to 5 hours.

12. The method according to claim 1 , where in step (i) the cycloaliphatic or araliphatic diol is first emulsified in the inert organic solvent comprising a catalytic amount of the monoether-monoalcohol of formula (I) followed by the addition of the metallic sodium to the emulsified cycloaliphatic or araliphatic diol.

13. The method according to claim 12 , where the metallic sodium is added to the cycloaliphatic or araliphatic diol, which is emulsified in the inert organic solvent comprising a catalytic amount of the monoether-monoalcohol (I), over a period of from 5 minutes to 5 hours.

14. The method according to claim 1 , where the aprotic organic solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic ethers and mixtures thereof.

15. The method according to claim 1 , where the aprotic organic solvent is selected from aromatic hydrocarbons, alkylene glycol dialkyl ethers, dialkylene glycol dialkyl ethers, polyalkylene glycol dialkyl ethers, and mixtures thereof.

Assignees

• Basf Se

Inventors

• Weingarten Melanie
• Siegel Wolfgang
• Pelzer Ralf
• Garlichs Florian

Classifications

• C07C41/16 Primary

  by reaction of esters of mineral or organic acids with hydroxy or O-metal groups · CPC title

• C07C29/70

  by converting hydroxy groups to O-metal groups {(C07C29/09 takes precedence)} · CPC title

• C07C2601/04

  with a four-membered ring · CPC title

• C07C41/01

  Preparation of ethers · CPC title

• C07C41/06 Primary

  by addition of organic compounds only · CPC title