# US 4,377,712 A · Preparation of meta-substituted diaryl ethers > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,377,712 A - Document ID: US4377712A - Status: Granted - Kind: A - Application number: 06/237,194 - Filed: 1981-02-23 - Granted: 1983-03-22 - Earliest claimed: 1979-04-09 - Assignees: Occidental Chemical Corporation - Inventors: Arthur M. Foster; James J. Maul - Web page: https://patentgrep.com/patent/US4377712A ## CPC - C07C 41/16: by reaction of esters of mineral or organic acids with hydroxy or O-metal groups - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract A process for the preparation of meta-substituted diaryl ethers comprises reacting an ortho-haloaryl compound with a phenol compound in a non-aqueous medium in the presence of an alkaline metal base. In a specific embodiment m-phenoxytoluene is prepared by reacting orthochlorotoluene with phenol in the presence of an alkaline metal hydroxide in a substantially non-aqueous liquid medium. ## Claims ### Claim 1 A process for the preparation of meta-substituted diaryl ethers of the formula ##STR4## wherein R.sub.1 is selected from the group consisting of alkyl and alkoxy of 1 to 30 carbon atoms, aryl and aryloxy of 6 to 14 carbon atoms and 2-(1,3)dioxolyl; R.sub.2 and R.sub.3 are independently selected from the group consisting of hydrogen, alkyl and alkoxy of 1 to 30 carbon atoms, aryl and aryloxy of 6 to 14 carbon atoms; R.sub.5, R.sub.6, and R.sub.7 are independently selected from the group consisting of hydrogen nitro, alkyl and alkoxy of 1 to 30 carbon atoms, aryl and aryloxy of 6 to 14 carbon atoms; R.sub.4 and R.sub.8 are independently selected from the group consisting of hydrogen, nitro, and linear alkyl and alkoxy of 1 to 14 carbon atoms, with the proviso that if either R.sub.4 or R.sub.8 is a substituent of more than 2 carbon atoms the other substituent is hydrogen; comprising reacting at atmospheric pressure an ortho-halo aryl compound of the formula ##STR5## wherein R.sub.1, R.sub.2 and R.sub.3 are as previously defined, and halogen is chlorine or bromine; with a phenol compound of the formula ##STR6## wherein R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are as previously defined, and X is hydrogen or an alkali metal; in an aprotic, substantially non-nucleophilic, polar solvent at a temperature of about 110.degree. Celsius to about the reflux temperature of the reaction medium, in the presence of an alkali metal base selected from an alkali metal hydroxide and alkali metal carbonate in a molar ratio of alkali metal base: phenol compound of greater than about 1.0 to about 4.0 when X is hydrogen and greater than about 0 to about 3.0 when X is an alkali metal. ### Claim 2 (depends on 1) A process according to claim 1 wherein the base is an alkali metal hydroxide. ### Claim 3 (depends on 1) A process according to claim 1 wherein the halogen of the ortho-haloaryl compound is chlorine. ### Claim 4 (depends on 3) A process according to claim 3 wherein the ortho-haloaryl compound is orthochlorotoluene. ### Claim 5 (depends on 4) A process according to claim 4 wherein the phenol compound is phenol. ### Claim 6 (depends on 4) A process according to claim 4 wherein the phenol compound is an alkali metal phenoxide. ### Claim 7 (depends on 1) A process according to claim 1 wherein the alkali metal base is sodium hydroxide. ### Claim 8 (depends on 1) A process according to claim 1 wherein the alkali metal base is potassium hydroxide. ### Claim 9 (depends on 1) A process according to claim 1 wherein the solvent is selected from the group consisting of dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropylsulfone, tetramethylsulfone, quinoline and pyridine. ### Claim 10 (depends on 6) A process according to claim 6 wherein the molar ratio of alkali metal hydroxide:phenoxide is in the range of greater than 0 to about 3.0. ### Claim 11 (depends on 10) A process according to claim 10 wherein the alkali metal phenoxide is sodium phenoxide and the alkali metal hydroxide is sodium hydroxide. ### Claim 12 (depends on 10) A process according to claim 10 wherein the alkali metal phenoxide is potassium phenoxide and the alkali metal hydroxide is potasssium hydroxide. ### Claim 13 (depends on 10) A process according to claim 10 wherein the solvent is selected from the group consisting of dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropysulfone, tetramethylsulfone, quinoline and pyridine. ### Claim 14 A process for the preparation of meta-substituted diaryl ethers of the formula ##STR7## wherein R.sub.1 is selected from the group consisting of alkyl and alkoxy of 1 to 30 carbon atoms, aryl and aryloxy of 6 to 14 carbon atoms and 2-(1,3)dioxolyl; R.sub.2 and R.sub.3 are independently selected from the group consisting of hydrogen, alkyl and alkoxy of 1 to 30 carbon atoms, aryl and aryloxy of 6 to 14 carbon atoms; R.sub.5, R.sub.6, and R.sub.7 are independently selected from the group consisting of hydrogen, nitro, alkyl and alkoxy of 1 to 30 carbon atoms, aryl and aryloxy of 6 to 14 carbon atoms; R.sub.4 and R.sub.8 are independently selected from the group consisting of hydrogen, nitro, and linear alkyl and alkoxy of 1 to 14 carbon atoms, with the proviso that if either R.sub.4 or R.sub.8 is a substituent of more than 2 carbon atoms the other substituent is hydrogen; comprising reacting at autogenous pressure an ortho-halo aryl compound of the formula ##STR8## wherein R.sub.1, R.sub.2 and R.sub.3 are as previously defined, and halogen is chlorine or bromine; with a phenol compound of the formula ##STR9## wherein R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are as previously defined, and X is hydrogen or an alkali metal; at a temperature of from about reflux temperature to about 400.degree. Celsius, in the presence of an alkali metal base selected from an alkali metal hydroxide and an alkali metal carbonate in a molar ratio of alkali metal base: phenol compound of greater than about 1.0 to about 4.0 when X is hydrogen and greater than about 0 to about 3.0 when X is an alkali metal. ### Claim 15 (depends on 14) A process according to claim 14 wherein the base is an alkali metal hydroxide. ### Claim 16 (depends on 15) A process according to claim 15 wherein the halogen of the ortho-haloaryl compound is chlorine. ### Claim 17 (depends on 16) A process according to claim 16 wherein the ortho-haloaryl compound is orthochlorotoluene. ### Claim 18 (depends on 17) A process according to claim 17 wherein the phenol compound is phenol. ### Claim 19 (depends on 17) A process according to claim 17 wherein the phenol compound is an alkali metal phenoxide. ### Claim 20 (depends on 15) A process according to claim 15 wherein the alkali metal hydroxide is potassium hydroxide. ### Claim 21 (depends on 19) A process according to claim 19 wherein the molar ratio of alkali metal hydroxide:phenoxide is in the range of greater than 0 to about 3.0. ### Claim 22 (depends on 21) A process according to claim 21 wherein the alkali metal phenoxide is sodium phenoxide and the alkali metal hydroxide is sodium hydroxide. ### Claim 23 (depends on 21) A process according to claim 21 wherein the alkali metal phenoxide is potassium phenoxide and the alkali metal hydroxide is potassium hydroxide.