Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/04—Saturated ethers
  • C07C43/12—Saturated ethers containing halogen
  • C07C43/123—Saturated ethers containing halogen both carbon chains are substituted by halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/04—Saturated ethers
  • C07C43/12—Saturated ethers containing halogen
  • C07C43/126—Saturated ethers containing halogen having more than one ether bond

Definitions

• the present disclosure broadly relates to fluorinated ethers, methods for making fluorinated ethers, and uses thereof.
• hydro fluoro ether as used in the art, commonly refers to those ethers having partial substitution of hydrogen atoms by fluorine atoms.
• hydrofiuoroethers are commercially available. Examples include those hydro fluoroethers available under the trade designations 3M NOVEC ENGINEERED FLUID 7000, 7100, 7200, 7300, 7500, and 7600 from 3M Company of Saint Paul, Minnesota.
• the present disclosure provides a method of making a fluorinated ether, the method comprising: combining in a polar aprotic solvent: a fluorinated alcohol represented by the formula
• RfI is selected from the group consisting of perfiuorinated alkylene groups having from 1 to 10 carbon atoms, partially fluorinated alkylene groups having from 1 to 10 carbon atoms, and derivatives thereof wherein one or more carbon atoms are replaced by catenated heteroatoms, wherein if RfI contains at least two carbon atoms, then RfI contains at most two hydrogen atoms; and X represents H, F, or an HOCH 2 - group; a fluorinated sulfonate ester represented by the formula
• Rf 2 is selected from the group consisting of perfiuorinated alkyl groups having from 1 to 10 carbon atoms and partially fluorinated alkyl groups having from 1 to 10 carbon atoms, and derivatives thereof wherein one or more carbon atoms are replaced by catenated heteroatoms, and wherein if Rf 2 contains at least two carbon atoms then Rf 2 contains at most three hydrogen atoms; and Rf 3 is selected from the group consisting of perfiuorinated alkyl groups having from 1 to 4 carbon atoms; and base; and obtaining at least one fluorinated ether represented by the formula
• Y-R ⁇ -CH 2 OCH 2 Rf 2 wherein Y represents H, F, or an Rf 2 CH 2 OCH 2 - group.
• the present disclosure provides a fluorinated ether represented by the formula
• RfI is selected from the group consisting of perfiuorinated alkylene groups having from 1 to 10 carbon atoms, partially fluorinated alkylene groups having from 1 to 10 carbon atoms, and derivatives thereof wherein one or more carbon atoms are replaced by catenated heteroatoms, wherein if RfI contains at least two carbon atoms, then RfI contains at most two hydrogen atoms; and Y represents H, F, or an Rf 2 CH 2 OCH 2 - group, wherein
• Rf2 is selected from the group consisting of perfluorinated alkyl groups having from 1 to 10 carbon atoms and partially fluorinated alkyl groups having from 1 to 10 carbon atoms, and derivatives thereof wherein one or more carbon atoms are replaced by catenated heteroatoms, wherein if Rf ⁇ contains at least two carbon atoms, then Rf ⁇ contains at most three hydrogen atoms; and wherein if Y is F and RfI and Rf ⁇ are both perfluorinated groups, then at least one of RfI or Rf ⁇ has at least 3 carbon atoms, and if Y-RfI- contains an HCF2- group then Rf ⁇ does not contain a -CF2H group.
• the present disclosure provides a method of making a fluorinated ether, the method comprising: combining in a polar aprotic solvent: a fluorinated alcohol represented by the formula Z-Rf 1 -CH2 ⁇ H wherein:
• Z represents H or F
• At least one of Rf 1 or Rf 2 contains a secondary carbon atom having one hydrogen atom and one fluorine atom bonded thereto. In some embodiments, at least one of Rf 1 or Rf 2 has from 3 to 8 carbon atoms. In some embodiments, at least one of
• Rf 1 or Rf ⁇ has from 3 to 5 carbon atoms.
• Compounds according to the present disclosure are useful, for example, in cleaning solvents, in fire extinguishing compositions, in blowing agents used in the manufacture of foamed plastics, as coating solvents, as polymerization media, for drying substrates, and in working fluids for cutting or abrading processes.
• the present disclosure provides a method of using a fluorinated ether, the method comprising cleaning a workpiece with a composition comprising a fluorinated ether represented by the formula
• Rf 1 is selected from the group consisting of perfluorinated alkylene groups having from 1 to 10 carbon atoms, partially fluorinated alkylene groups having from 1 to 10 carbon atoms, and derivatives thereof wherein one or more carbon atoms are replaced by catenated heteroatoms, wherein if Rf 1 contains at least two carbon atoms, then Rf 1 contains at most two hydrogen atoms; and Y represents H, F, or an Rf 2 CH 2 OCH 2 - group, wherein Rf 2 is selected from the group consisting of perfluorinated alkyl groups having from 1 to 10 carbon atoms and partially fluorinated alkyl groups having from 1 to 10 carbon atoms, and derivatives thereof wherein one or more carbon atoms are replaced by catenated heteroatoms, wherein if Rf ⁇ contains at least two carbon atoms, then Rf ⁇ contains at most three hydrogen atoms.
• alkyl group refers to a monovalent non-aromatic hydrocarbyl group that
• catenated heteroatom refers to a nitrogen atom or an oxygen atom that is bonded to carbon atoms in a carbon chain so as to form a carbon-heteroatom-carbon chain;
• F represents a fluorine atom
• fluorinated alkyl means the at least one H atom of the alkyl group has been replaced by fluorine
• H represents a hydrogen atom
• nonaflate refers to perfluoro-n-butanesulfonate
• perfluorinated means that all H atoms that are bonded to carbon are replaced by F atoms
• trime refers to trifluoromethanesulfonate
• polar aprotic solvent refers to a solvent that is substantially free of -OH and -NH- groups (that is, does not contain -OH and -NH- groups in more than adventitious amounts); and "X", "Y", and "Z" represent variable chemical groups.
• polar aprotic solvents Many such solvents are known and used in the chemical arts. Examples include tetrahydrofuran (THF), acetone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide (HMPA), 7V,7V-dimethylacetamide (DMA), diethylene glycol dimethyl ether, and 7V,7V-dimethylformamide.
• THF tetrahydrofuran
• acetone dimethyl sulfoxide
• HMPA hexamethylphosphoramide
• DMA 7V,7V-dimethylacetamide
• diethylene glycol dimethyl ether diethylene glycol dimethyl ether
• 7V,7V-dimethylformamide diethylene glycol dimethyl ether
• acetone is specifically desirable.
• a first method involves mixing a fluorinated alcohol with a fluorinated sulfonate ester, and base in the polar aprotic solvent under conditions such that a fluorinated ether is formed.
• the fluorinated alcohol may be represented by the formula
• RfI is selected from the group consisting of perfluorinated alkylene groups having from 1 to 10 carbon atoms and partially fluorinated alkylene groups having from 1 to 10 carbon atoms, and derivatives thereof wherein one or more carbon atoms are replaced by catenated heteroatoms, wherein if RfI contains at least two carbon atoms, then RfI contains at most two hydrogen atoms.
• Exemplary divalent groups RfI include: perfluorinated alkylene groups such as, for example, perfluoromethylene, perfluoro ethylene (that is, perfluoroethane-l,2-diyl), perfluoropropane- 1 ,3-diyl, perfluoropropane- 1 ,2-diyl, perfluoro(2-methylpropane- 1 ,3-diyl), perfluoropentane-l,5-diyl, perfluorohexane-l,6-diyl, perfluorocyclohexane-l,4-diyl, and perfluorooctane-l,8-diyl; and partially fluorinated alkyl groups such as, for example, fluoromethylene, 1,1,2,2-tetrafluoroethylene, l,l,2,3,3-pentafluoropropane-l,3-diyl, and l,l
• Exemplary derivatives of perfluorinated and partially fluorinated alkyl groups include fluorinated alkoxyalkyl groups such as -CF 2 CF 2 OCF 2 CF 2 -, -CF 2 CF 2 CF 2 OCF 2 CF 2 -, -CF 2 OCF 2 CF 2 -; -CF 2 CF 2 CF 2 OCF(CF 3 )-; -CF 2 CF 2 CF 2 OCF(CF 3 )CF 2 OCF(CF 3 )-; -CF 2 OC 3 F 6 OCF(CF 3 )-;
• X represents H, F, or an HOCH 2 - group.
• the fluorinated alcohol may be multifunctional, which results in a corresponding poly ether.
• multifunctional fluorinated alcohols include HOCH 2 C 2 F 4 CH 2 OH, HOCH 2 C 3 F 6 CH 2 OH, HOCH 2 C 4 F 8 CH 2 OH, HOCH 2 (CF2CF2 ⁇ ) n CH 2 OH wherein n is a positive integer, and
• HOCH ⁇ F ⁇ WCF ⁇ CF ⁇ OH wherein j and k represent integers in a range of from 1 to 50. In such cases X represents HOCH2-.
• the fluorinated sulfonate ester is represented by the formula wherein Rf ⁇ is selected from the group consisting of perfluorinated alkyl groups having from
• Rf ⁇ contains at least two carbon atoms then Rf ⁇ contains at most three hydrogen atoms.
• Rf ⁇ is chosen from the group consisting of perfluorinated alkyl groups having from 1 to 4 carbon atoms;
• Exemplary groups Rf ⁇ include perfluoromethyl, perfluoro ethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoroisobutyl, perfluoropentyl, perfluorohexyl, perfluorocyclohexyl, and perfiuorooctyl; and partially fluorinated alkyl groups such as, for example, 1,1,2,2-tetrafluoroethyl, 1,1,2,3,3,3-hexafluoropropyl, and 1,1,2,2,3,3,4,4- octafluorobutyl, and derivatives of perfluorinated and partially fluorinated alkyl groups such as HCF 2 CF 2 OCF 2 CF 2 -, CF 3 CF 2 OCF 2 CF 2 -, HCF 2 CF 2 CF 2 OCF 2 CF 2 -, CF 3 CF 2 CF 2 OCF 2 -, CF
• Y represents H, F, or an Rf ⁇ CH 2 OCH 2 - group, wherein Rf ⁇ is as described above.
• the fluorinated alcohol and the fluorinated sulfonate ester are combined in approximately the same equivalent amounts (a 1 : 1 equivalent ratio), although other ratios may be used; for example, a molar ratio in a range of from 0.8 to 1.2.
• Useful bases include organic and inorganic bases. Exemplary bases include alkali metal carbonates (optionally in combination with a tetraalkylammonium halide), tertiary amines, sodium hydride, and combinations thereof.
• the combined components are placed in a pressure vessel under conditions that cause reaction of the components and formation of the corresponding fluorinated ether, although in some cases the reactions can be carried out in glass vessels at ambient pressure. Typical conditions include stirring and heating, although in some cases one or neither may be desirable. After sufficient time has elapsed the mixture is typically returned to ambient temperature (if heated), then the fluorinated ether is obtained by workup and purification; for example, as described in the Examples.
• the fluorinated alcohol that is, a partially fluorinated alcohol
• a perfluoroalkanesulfonyl fluoride having from 1 to 4 carbon atoms in a polar aprotic solvent.
• mild heating is applied to facilitate reaction in a timely manner.
• Fluorinated ethers according to the present disclosure and compositions (typically liquid) comprising them, may be used in various applications where chlorofluorocarbons (CFCs) have been used.
• the fluorinated ethers can be used in solvent compositions for precision or metal cleaning of electronic articles such as disks or circuit boards; as cell size regulators in making foam insulation (for example, polyurethane, phenolic, or thermoplastic foams); in chemical fire extinguishing compositions in streaming applications; in carrier fluids or solvents for document preservation materials; as and in lubricants; in inert compositions for carrying out polymerization reactions; in displacement drying compositions for removing water, such as from jewelry or metal parts; in resist developer compositions in conventional circuit manufacturing techniques including chlorine- type developing agents; and in stripper compositions for photoresists when used with, for example, a chlorohydrocarbon such as cis-or trans-dichloroethene or trichloroethylene.
• the fluorinated ethers can be used alone or in admixture with each other or with other commonly-used solvents (for example, alcohols, ethers, alkanes, alkenes, perfluorocarbons, perfluorinated tertiary amines, perfluorinated ethers, cycloalkanes, esters, ketones, aromatics, siloxanes, hydrochlorocarbons, hydro fluorocarbons, and mixtures thereof).
• co-solvents can be typically chosen to modify or enhance the properties of a composition for a particular use and can be utilized in ratios (of co-solvent(s) to fluorinated ether(s)) such that the resulting composition has essentially no flash point.
• the fluorinated ethers can be used in combination with other compounds that are very similar in properties relative to a particular use (for example, other fluorinated ethers).
• fluorinated ethers can comprise conventional additives such as, for example, surfactants, coloring agents, stabilizers, antioxidants, flame retardants, and mixtures thereof.
• Fluorinated ethers according to the present disclosure can typically be used as solvents for cleaning and drying applications such as, for example, those described in U. S. Pat. Nos. 5,125,089 (Flynn et al.), 3,903,012 (Brandreth), 4,169,807 (Zuber), and 5,925,611 (Flynn et al.).
• Both organic and inorganic substrates can be cleaned by contacting them with a composition comprising at least one fluorinated ether according to the present disclosure.
• Most contaminants can be removed, including hydrocarbon contaminants, fluorocarbon contaminants, particulates, and water.
• fluorinated ethers according to the present disclosure for the drying of or displacing water from the surface of articles (such as circuit boards), a process of drying or water displacement generally as described in U. S. Pat. No. 5,125,978 (Flynn et al.) can be used. That process comprises contacting the surface of an article with a liquid composition comprising at least one fluorinated ether according to the present disclosure, typically in admixture with a non-ionic fluoroaliphatic surface active agent.
• the wet article is immersed in the liquid composition and agitated therein, the displaced water is separated from the liquid composition, and the resulting water-free article is removed from the liquid composition.
• fluorinated ethers according to the present disclosure as cell size regulators in making plastic foam (such as foamed polyurethane)
• the process reactants and reaction conditions described in, for example, U. S. Pat. Nos. 5,210,106 (Dams et al.) and 5,539,008 (Dams et al.) can be used.
• One such process comprises vaporizing a blowing agent mixture in the presence of at least one foamable polymer or the precursors of at least one foamable polymer, the blowing agent mixture comprising at least one fluorinated ether according to the present disclosure.
• Such processes for depositing a coating on a substrate comprise applying, to at least a portion of at least one surface of the substrate, a composition comprising (a) a solvent composition comprising at least one fluorinated ether according to the present disclosure; and (b) at least one coating material that is soluble or dispersible in the solvent composition.
• Exemplary coating materials that can be deposited by the process include pigments, lubricants, stabilizers, adhesives, anti-oxidants, dyes, polymers, pharmaceuticals, release agents, inorganic oxides, document preservation materials (for example, alkaline materials used in the deacidification of paper), and combinations thereof.
• fluorinated ethers according to the present disclosure as fire extinguishing and prevention agents, the processes generally described in U. S. Pat. No. 5,718,293 (Flynn et al.) may be used. Such processes for the extinction of fires comprise applying or introducing to a fire a composition comprising at least one fluorinated ether according to the present disclosure. Fluorinated ethers according to the present disclosure may be used alone or in combination with other fire extinguishing or prevention agents. If using the fiuorinated ethers according to the present disclosure in cutting or abrasive working operations, the processes generally described in U. S. Pat. No. 6,759,374 (Milbrath et al.) can be used.
• Such a process for metal, cermet, or composite working comprises applying a working fluid to the metal, cermet, or composite workpiece and tool, the working fluid comprising at least one fluorinated ether according to the present disclosure and at least one lubricious additive.
• the working fluid may further comprise one or more additives (for example, corrosion inhibitors, antioxidants, defoamers, dyes, bactericides, freezing point depressants, metal deactivators, co-solvents, and the like, and mixtures thereof).
• Such processes comprise polymerizing at least one monomer (preferably, at least one fluorine-containing monomer) in the presence of at least one polymerization initiator and at least one fiuorinated ether according to the present disclosure.
• GC gas chromatography using a flame ionization detector (uncorrected for response factors);
• IR infrared spectroscopy,
• GC/MS gas chromatography - mass spectroscopy;
• NMR nuclear magnetic resonance spectroscopy
• mL refers to milliliters
• mol refers to moles
• g refers to grams.
• 1,1,2,2,3,3,4,4,4-nonafluorobutane-l-sulfonyl fluoride (332 g, 1.1 mol, obtained from 3M Company of Saint Paul, Minnesota) and water (300 g) were combined in a 3-L, 3-necked round bottom flask.
• the flask was equipped with a magnetic stirrer, cold water condenser, thermocouple and a 250-mL addition funnel.
• Aqueous potassium hydroxide (149.3 g, 45 weight percent, 1.22 equivalents) was added dropwise via an addition funnel at such a rate that the temperature did not exceed 35 0 C. Once the addition of the base was complete the mixture was stirred for 16 hours at room temperature.
• Aqueous potassium hydroxide (45 percent by weight in water, 154 g, 1.05 mol) was added dropwise via the addition funnel at such a rate that the temperature did not exceed 35 0 C. Once the addition of the potassium hydroxide was complete, the mixture was stirred for 16 hours at room temperature. Precipitated salts were then filtered from the mixture and the lower liquid fluorochemical product phase was separated from the upper aqueous phase and washed once with water to give 350 g crude product. The product was distilled at atmospheric pressure and the distillation cut boiling from 140-150 0 C used without further purification (96.3 percent purity by GC).
• reaction mix was then emptied and washed with 2 x 500 mL portions of water and 1 x 250 mL portion of IN HCl.
• GC analysis of the reaction mixture indicated a 97 percent conversion to the product.
• the chloroform solvent was removed by rotary evaporation.
• the product was dried over anhydrous magnesium sulfate which was then filtered from the product.
• 2,2,3,4,4,4-hexafluorobutan-l-ol (61.3 g, 0.337 mol, obtained from Sinochem Corp.), 2,2,3,4,4,4-hexafluorobutyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-l-sulfonate (156.4 g, 0.337 mol), potassium carbonate (46.5 g, 0.337 mol), tri-n-butylamine (0.75 g, 0.004 mol) and 150 mL of acetone were combined in a 600-mL Parr pressure reactor. The mix was heated to 75 0 C with vigorous stirring for 18 hours. The mix was then emptied and the solids were filtered from the product.
• Oldershaw distillation column The main fraction (approximately 98 percent purity as measured by GC, uncorrected for response factors) boiled at a temperature of 170 0 C at atmospheric pressure.
• the structure was consistent with analysis by GC/MS, ⁇ F NMR, and 1 H NMR.
• 2,2,3,3,4,4,5,5-Octafluoropentan-l-ol (22.1 g, 0.097 mol) was added dropwise at 50 0 C to a suspension of sodium hydride (2.5 g of 95 percent purity, 0.097 mol) in anhydrous diethylene glycol dimethyl ether (200 g) over a two hour period. At the end of this time, the solution was homogeneous.
• the reaction mixture was then heated to 95 0 C for 16 hours and 105 0 C for an additional six hours.
• water 100 milliliters was added, and the mixture distilled using a Dean-Stark trap to return the water and organic solvent back to the distillation vessel while allowing separation of the lower fluorochemical phase in the trap.
• HCF 2 CF 2 CF 2 CF 2 CH 2 OCH 2 CF 2 CF 2 CF 2 CF 2 H Purification of the ether was effected by treatment of the nonaflate-contaminated mixture with a solution of lithium chloride (25 g) in dimethylformamide (200 mL) at 50 0 C. Under these specific conditions, the nonaflate was found to react rapidly with the lithium chloride to give HCF 2 CF 2 CF 2 CH 2 CI and lithium nonaflate.
• the reaction mixture was poured into water, the lower fluorochemical phase separated and washed twice more with water and the resulting mixture distilled (boiling point: 205 0 C, 70 °C/2 at mm Hg) to give a purity of 91.5 percent as measured by GC, uncorrected for response factors.
• the assigned structure was consistent with the GC/MS analysis, infrared spectroscopy, 1°F NMR, ⁇ H NMR, and 13 C NMR.
• 2,2,3-Trifluoro-3-(perfluoropropoxy)propanol (71.6 g, 0.24 mol, prepared as described in U. S. Pat. Appln. Publ. No. 2007/0051916 Al (Flynn et al), Example 1), 2,2,3,3- tetrafluoropropyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-l-sulfonate (119.23 g, 0.288 mol), potassium carbonate (39.7 g, 0.288 mol), tri-n-butylamine (0.75 g, 0.004 mol) and 150 mL of acetone were combined in a 600-mL Parr pressure reactor.
• the temperature of the reactor was set to 75 0 C and the mix was stirred for 24 hours. The mix was then emptied and the salts were filtered from the product solution. The product solution was washed twice with 100 mL portions of water to remove additional salts. The lower phase was then dried over anhydrous magnesium sulfate, filtered and then purified by fractional distillation using a concentric tube column. The main fraction (94 percent purity by GC, uncorrected for response factors) boiled at a temperature of 161-162 0 C at atmospheric pressure. The assigned structure was consistent with the GC/MS analysis.
• 2,2,3,4,4,4-Hexafluorobutan-l-ol 50 g, 0.27 mol
• 2,2,3,3,4,4,5,5,5- nonafluorobutanesulfonyl fluoride (41.5 g, 0.14 mol, obtained from S inochem International Corp.)
• potassium carbonate 38.2 g, 0.27 mol
• tetrabutylammonium bromide 1.2 g, 0.004 mol
• 153 g of acetone (solvent) were combined in a 600-mL Parr pressure reactor. The mixture was heated to 75 0 C with vigorous stirring for 16 hours.
• 2,2,3,3-Tetrafluoropropan-l-ol 50 g, 0.38 mol
• 2,2,3,3-tetrafluoropropyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-l-sulfonate 157 g, 0.38 mol
• potassium carbonate 52.3 g, 0.38 mol and 197 g of acetone (solvent) were combined in a 600-mL Parr pressure reactor. After degassing, the reactor was sealed and the mixture was heated to 75 0 C with vigorous stirring for 18 hours. After cooling, the reactor was opened and the contents filtered to remove the insoluble salts. The acetone was removed by rotary evaporation.
• the product was distilled at atmospheric pressure and the distillation cut from 112 - 152 0 C subsequently treated with LiCl (20 g) in N,N-dimethylformamide (150 mL) at 50 0 C as described in Example 4 to remove the residual 2,2,3,3-tetrafluoropropyl 1 ,1 ,2,2,3,3,4,4,4-nonafluorobutane-l-sulfonate.
• the structure was consistent with the GC/MS, IR, 19 F NMR, 1 H NMR, and 13 C NMR.
• EXAMPLE 8 Preparation of 5 -(2, 2, 2-trifluoroethoxy)- 1 , 1,2,2, 3, 3, 4, 4-octafluoropentane; H(CF 2 CF 2 ) 2CH 2 OCH 2 CF 3 .
• 2,2,3,3,4,4,5,5-Octafiuoropentan-l-ol 50 g, 0.215 mol
• 2,2,2-trifiuoroethyl trifluoromethanesulfonate 50 g, 0.215 mol, obtained from Synquest Labs, Inc., Alachua, Florida
• potassium carbonate 29.7 g, 0.215 mol
• 175 g of acetone solvent
• 2,2,3,3,4,4,4-Heptafluorobutan-l-ol 50 g, 0.25 mol, obtained from 3M Company
• 2,2,3,3,4,4,4-heptafluorobutyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-l-sulfonate (120.5 g, 0.25 mol, prepared as described above)
• potassium carbonate 34.5 g, 0.25 mol
• 175 g of acetone (solvent) were combined in a 600-mL Parr pressure reactor. After degassing, the reactor was sealed and the mixture was heated to 75 0 C with vigorous stirring for 112 hours. After cooling, the reactor was opened and the contents filtered to remove the insoluble salts.
• the acetone was removed by rotary evaporation. Some of the product ether distilled with the solvent during the rotary evaporation so the distillate was poured into water and the lower fluorochemical phase separated and added to the rotary evaporation residue. To this residue was then added approximately 250 mL water and the product azeotropically distilled using a Dean-Stark trap to give after phase separation and water washing 62 g crude product. The yield at this stage by GC analysis was 11 percent. The product was treated with LiCl (15 g) in N,7V-dimethylformamide (250 mL) at 50 0 C as described in Example 4 to remove the residual nonafluorobutane- 1 -sulfonate. The product was then distilled to a purity of 78 percent.
• 2,2,3,3-Tetrafluorobutane-l,4-diol (HOCH 2 C 2 F 4 CH 2 OH, 20 g, 0.123 mol, obtained from 3M Company), 2,2,3,3,4,4,4-heptafluorobutyl-l,l,2,2,3,3,4,4,4-nonafluorobutane-l- sulfonate (03FyCH 2 OSO 2 C 4 Fc), 119 g, 0.247 mol, prepared as described above), potassium carbonate (34.1 g, 0.247 mol) and 245 g of acetone (solvent) were combined in a 600-mL Parr pressure reactor.
• the reactor was sealed and the mixture was heated to 75 0 C with vigorous stirring for 112 hours. After cooling, the reactor was opened and the contents filtered to remove the insoluble salts. The acetone was removed by rotary evaporation. To this residue was then added an excess of water, and the product azeotropically distilled using a Dean-Stark trap to give after phase separation and water washing 57.2 g crude product.

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