# US 5,710,289 A · Process for the preparation of dihalotetrahydrofurans from dihydrofuran > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,710,289 A - Document ID: US5710289A - Status: Granted - Kind: A - Application number: 08/779,758 - Filed: 1997-01-07 - Granted: 1998-01-20 - Earliest claimed: 1997-01-07 - Assignees: Eastman Chemical Company - Inventors: Stephen N. Falling; Patricia Lopez - Web page: https://patentgrep.com/patent/US5710289A ## CPC - C07D 307/18: with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) ## Abstract Disclosed is a process for the preparation of 3,4-dichlorotetrahydrofuran, 3,4-dibromotetrahydrofuran, 2,3-dichlorotetrahydrofuran, and 2,3-dibromotetrahydrofuran by the reaction of 2,5- or 2,3-dihydrofuran with chlorine or bromine in the presence of a quaternary onium halide compound. The reaction preferably is carried out by the addition of the dihydrofuran and chlorine or bromine to an organic, halogenation solvent containing chlorine or bromine and the quaternary onium halide compound. ## Claims ### Claim 1 Process for the preparation of a dihalotetrahydrofuran which comprises reacting a dihydrofuran with X.sub.2 in the presence of a quaternary onium halide compound; wherein the dihalotetrahydrofuran is 3,4-dichlorotetrahydrofuran, 3,4-dibromotetrahydrofuran, 2,3-dichlorotetrahydrofuran, or 2,3-dibromotetrahydrofuran; the dihydrofuran is 2,5- or 2,3-dihydrofuran; and X.sub.2 is chlorine or bromine. ### Claim 2 (depends on 1) Process according to claim 1 wherein the quaternary onium halide has the formula ##STR3## wherein each R is a hydrocarbyl group; Y is a nitrogen or phosphorus atom; Z.sup.- is a halide. ### Claim 3 (depends on 1) Process according to claim 1 for the preparation of a dichlorotetrahydrofuran which comprises reacting a dihydrofuran and Cl.sub.2 at a temperature of about -10.degree. to 20.degree. C. in the presence of a quaternary nitrogen or phosphorus onium chloride compound containing a total of about 8 to 32 carbon atoms and having the formula ##STR4## and an organic, halogenation solvent; wherein each R is a hydrocarbyl group, Y is a nitrogen or phosphorus atom; the dichlorotetrahydrofuran is 3,4-dichlorotetrahydrofuran or 2,3-dichlorotetrahydrofuran, and the dihydrofuran is 2,5- or 2,3-dihydrofuran. ### Claim 4 (depends on 3) Process according to claim 3 wherein the onium chloride is tetra-n-butylphosphonium chloride or tetraethylammonium hloride and the solvent is 4-chlorobenzo-trifluoride, chlorobenzene or dichloromethane. ### Claim 5 (depends on 3) Process according to claim 3 wherein the onium chloride is tetra-n-butylphosphonium chloride or tetraethylammonium chloride and the solvent is 4-chlorobenzotrifluoride, chlorobenzene or dichloromethane, the dichlorotetrahydrofuran is 3,4-dichlorotetrahydrofuran and the dihydrofuran is 2,5-dihydrofuran. ### Claim 6 (depends on 1) Process according to claim 1 for the preparation of a dibromotetrahydrofuran which comprises reacting a dihydrofuran and Br.sub.2 at a temperature of about 0.degree. to 50.degree. C. in the presence of a quaternary nitrogen or phosphorus onium bromide compound containing a total of about 8 to 32 carbon atoms and having the formula ##STR5## and an organic, halogenation solvent; wherein each R is a hydrocarbyl group and Y is a nitrogen or phosphorus atom; the dibromotetrahydrofuran is 3,4-dibromotetrahydrofuran or 2,3-dibromotetrahydrofuran, and the dihydrofuran is 2,5- or 2,3-dihydrofuran. ### Claim 7 (depends on 6) Process according to claim 6 wherein the onium bromide is tetra-n-butylphosphonium bromide or tetra-ethylammonium bromide and the solvent is 4-chlorobenzo-trifluoride, chlorobenzene or dichloromethane. ### Claim 8 (depends on 6) Process according to claim 6 wherein the onium bromide is tetra-n-butylphosphonium bromide or tetra-ethylammonium bromide and the solvent is 4-chlorobenzotrifluoride, chlorobenzene or dichloromethane, the dibromotetrahydrofuran is 3,4-dibromotetrahydrofuran and the dihydrofuran is 2,5-dihydrofuran. ### Claim 9 Process for the preparation of a dihalotetrahydrofuran which comprises adding a dihydrofuran and X.sub.2 to a solution of X.sub.2 and a quaternary onium halide in an organic, halogenation solvent; wherein the dihalotetrahydrofuran is 3,4-dichlorotetrahydrofuran, 3,4-dibromotetrahydrofuran, 2,3-dichlorotetrahydrofuran, or 2,3-dibromotetrahydrofuran; the dihydrofuran is 2,5- or 2,3-dihydrofuran; and X.sub.2 is chlorine or bromine. ### Claim 10 (depends on 9) Process according to claim 9 for the preparation of a dichlorotetrahydrofuran compound which comprises adding a dihydrofuran and Cl.sub.2 to a solution of Cl.sub.2 and a quaternary nitrogen or phosphorus onium chloride compound containing a total of about 8 to 32 carbon atoms and having the formula ##STR6## in an organic, halogenation solvent at a temperature of about -10.degree. to 20.degree. C., wherein each R is a hydrocarbyl group, Y is a nitrogen or phosphorus atom, the dichlorotetrahydrofuran is 3,4-dichlorotetrahydrofuran or 2,3-dichlorotetrahydrofuran, and the dihydrofuran is 2,5- or 2,3-dihydrofuran. ### Claim 11 (depends on 10) Process according to claim 10 wherein the onium chloride is tetra-n-butylphosphonium chloride or tetraethylammonium chloride, the solvent is 4-chlorobenzotrifluoride, chlorobenzene or dichloromethane, the dichlorotetrahydrofuran is 3,4-dichlorotetrahydrofuran and the dihydrofuran is 2,5-dihydrofuran. ### Claim 12 (depends on 9) Process according to claim 9 for the preparation of a dibromotetrahydrofuran compound which comprises adding a dihydrofuran and Br.sub.2 to a solution of Br.sub.2 and a quaternary nitrogen or phosphorus onium bromide compound containing a total of about 8 to 32 carbon atoms and having the formula ##STR7## in an organic, halogenation solvent at a temperature of about 0.degree. to 50.degree. C., wherein each R is a hydrocarbyl group, Y is a nitrogen or phosphorus atom, the dibromotetrahydrofuran is 3,4-dibromotetrahydrofuran or 2,3-dibromotetrahydrofuran, and the dihydrofuran is 2,5- or 2,3-dihydrofuran. ### Claim 13 (depends on 12) Process according to claim 12 wherein the onium bromide is tetra-n-butylphosphonium bromide or tetraethylammonium bromide, the solvent is 4-chlorobenzotrifluoride, chlorobenzene or dichloromethane, the dibromotetrahydrofuran is 3,4-dibromotetrahydrofuran and the dihydrofuran is 2,5-dihydrofuran.