# US 11,078,146 B2 · Method for preparing ethers of cycloaliphatic or araliphatic diols > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,078,146 B2 - Document ID: US11078146B2 - Status: Granted - Kind: B2 - Application number: 16/769,716 - Filed: 2018-12-03 - Published: 2021-06-10 - Granted: 2021-08-03 - Earliest claimed: 2017-12-04 - Assignees: BASF SE - Applicants: BASF SE - Inventors: Melanie Weingarten; Wolfgang Siegel; Ralf Pelzer; Florian Garlichs - Web page: https://patentgrep.com/patent/US11078146B2 ## CPC - C07C 41/06: by addition of organic compounds only - C07C 41/16: by reaction of esters of mineral or organic acids with hydroxy or O-metal groups - C07C 29/70: by converting hydroxy groups to O-metal groups {(C07C29/09 takes precedence)} - C07C 41/01: Preparation of ethers - C07C 41/05: by addition of compounds to unsaturated compounds - C07C 2601/04: with a four-membered ring - C07C 2601/14: The ring being saturated - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## 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 C2-C4-alkylene, n is an integer in the range from 1 to 10, and R1 is C1-C4-Alkyl, whereby the corresponding disodium dialcoholate is obtained, reacting the disodium dialcoholate obtained in step (i) with an alkylation alkenylation reagent. ## Claims ### Claim 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 C2-C4-alkylene, n is an integer in the range from 1 to 10, and R1 is C1-C4-alkyl, whereby the corresponding disodium dialcoholate is obtained, (ii) reacting the disodium dialcoholate obtained in step (i) with an alkylation or alkenylation reagent. ### Claim 2 (depends on 1) 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. ### Claim 3 (depends on 1) 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. ### Claim 4 (depends on 1) 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. ### Claim 5 (depends on 1) The method of claim 1, where the alkylation or alkenylation reagent is a compound of the formula (II) R2—X (II) wherein R2 is selected from the group consisting of C1-C10-alkyl and C2-C4-alkenyl, and X represents a leaving group, selected from halogen, O—CO—O—R2, O—SO2—O—R2 and O—S(O2)R2a, where R2a is selected from the group consisting of phenyl, which is unsubstituted or carries 1, 2 or 3 C1-C3-alkyl radicals, C1-C4-alkyl and C1-C4-fluoroalkyl. ### Claim 6 (depends on 5) The method of claim 5, where in step (ii) R2—O—SO2—O—R2 is used as the alkylation or alkenylation reagent. ### Claim 7 (depends on 5) The method of claim 5, where in formula (II) the radical R2 is C1-C3-alkyl. ### Claim 8 (depends on 1) 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 C5-C10-cycloalkylene and C6-C12-arylene, wherein C5-C10-cycloalkylene and C6-C12-arylene are, independently of each other, unsubstituted or substituted by 1, 2, 3, 4 or 5 radicals selected from C1-C4-alkyl, and L1 and L2, independently of one another, are selected from the group consisting of a chemical bond and C1-C3-alkylene, where C1-C3-alkylene is unsubstituded or substituted by 1 or 2 radicals selected from C1-C4-alkyl and cyclopropyl. ### Claim 9 (depends on 8) 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), ### Claim 10 (depends on 1) 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. ### Claim 11 (depends on 10) 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. ### Claim 12 (depends on 1) 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. ### Claim 13 (depends on 12) 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. ### Claim 14 (depends on 1) The method according to claim 1, where the aprotic organic solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic ethers and mixtures thereof. ### Claim 15 (depends on 1) 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.