Chapter-29---Surfactants

501NextGenerationofInternationalChemicalAdditives.DOI:©2013ElsevierB.V.Allrightsreserved.Chapter29SurfactantsA.  ANTIMICROBIAL SURFACE MODIFICATIONPerfluorosorbitol EstersTitle:FluorosurfactantsUSPatent:8,067,625(November29,2011)Author:WolfgangHierseetal.Assignee:MerckPatentGesellschaftMitBeschrankterHaftung(Darmstadt,DE)Significance:Fattyacidsfunctionalizedwithfluorinatedamines,ethers,orsulfanylgroupswerepreparedandthenusedtoformmono-esterswithsorbitolandsucrose.Fluorinatedsugarsurfactantscouldbeoxidativelyorreductivelydegradedintonontoxicandnonpersistentresidues.Despitehavingafluorinecontentof≤3.8wt%,fluorinatedsorbitolandsucroseestersdisplayedhighsurfaceactivities.AdditiveNamesSorbitol-(E)-10-pentafluorosulfanyldec-9-enecarboxylicacidester(I)Sucrose-(E)-10-pentafluorosulfanyldec-9-enecarboxylicacidester(II)Sorbitol-7-(3,3,3-trifluoropropoxy)heptanoicacidester(III)Sucrose-7-(3,3,3-trifluoropropoxy)heptanoicacidester(IV)Sorbitol-10-N-di-trifluromethyldecanoicacidester(V)Sucrose-10-N-di-trifluromethyldecanoicacidester(VI)SafetyTherearenotoxicitydataavailableonthecurrentfluorine-containingfattyacidestersurfactants.502NextGenerationofInternationalChemicalAdditivesAdditivesHOOOHOHOHOHOSF5HOOOHOHOHOHOO57CF3OHOOOHOOHOOHOHHOOF5S7HO(I)(II)(III)OHOOOHOOHOOHOHHOOO5F3CHO(IV)HOOOHOHOHOHON9CF3CF3OHOOOHOOHOOHOHHOON9CF3F3CHO(V)(VI)Additive PreparationOHHOOOHOHOHOHO66OH6F5SClOH6F5SOH6F5SOCl6F5SO23OC2Hours23OC8HoursSF5Cl(C2H5)3BCH2Cl2C2H5OHKOHCH3CNCCl4Ru(II)Cl2NaIO470OC1Hour23OC3HoursSOCl2C6H5CH3THFSorbitol(C2H5)3N50OC1Hour503Chapter | 29 SurfactantsAdditive Synthesis1.  Preparation of 10-pentafluorosulfanyl-9-chloro-decanolA250-mlsingle-neckround-bottomcontainerwaschargedwith15gof9-decenoldissolvedin250mlofmethylenechlorideandthencooledto−40°Candtreatedwith27gofsulfurchloridepentafluorideand2mlof1Mtriethylborane.Additionaltriethylboranewasaddeduntiltheevolutionalofgasstoppedandthereactionmix-turewasnolongerwarm.Themixturewasthenstirredatanambienttemperatureforanadditional2handthenreactedwithamixtureofsaturatedsodiumbicarbonatecontainingice.ThesolutionpHwasthenadjustedto10usingsodiumhydroxide,andtheaqueousphasewasseparatedandwashedtwicewithmethylt-butylether.Thecollectedorganicphaseswerethenextractedoncewithbrine,driedwithsodiumsulfate,filtered,andtheproductwasisolatedafterthesolventwasremovedusingarotaryevaporator.2.  Preparation of (E)-10-pentafluorosulfanyldecenolA250-mlsingle-neckedflaskcontainingarefluxcondenserwaschargedwith9goftheStep1productdissolvedin120mlofethanoland4.75gofpotassiumhydroxideandthenstirredovernightandconcentrated.Theconcentratewasthentreatedwithwaterandmethylt-butylether,andthephaseswereseparated.Theaqueousphasewasthenextractedthricewithmethylt-butyletherandthenwashedwithbrine.Afterdryingwithsodiumsulfateandfiltering,8.3gofayellowishliquidwasisolatedafterdistillation.3.  Preparation of (E)-10-pentafluorosulfanyldec-9-enecarboxylic acidA250-mlround-=bottomflaskwaschargedwith11.3mmoloftheStep2productdissolvedinasolventmixturecomprising40mlofcarbontetrachloride,40mlofacetonitrile,and50mlofwater.Themixturewasthentreatedwith5.44gofsodiummetaperiodateand234mgofruthenium(III)chlorideandthenstirredat23°Cfor3h.Themixturewasthentreatedwith50mlofmethylenechloride,andthephaseswereseparated.Theaqueousphasewasfurtherextractedtwicewith50mlofmethylenechloride,andextractswerecombined.Afterdryingwithsodiumsulfate,thesolutionwasfilteredandthendistilled,andtheproductwasisolatedasanoilyresidue.4.  Preparation of (E)-10-pentafluorosulfanyldec-9-enecarboxylic acid chlorideAreactorwaschargedwith30goftheStep3productand100goftolueneandthentreatedwith24gofthionylchloride.Themixturewasthenheatedto70°Cfor1handexcessthionylchloride,andthesolventwasremovedbydistillation.Theresultantproductwasusedinthenextstepwithoutfurtherpurification.5.  Preparation of sorbitol (E)-10-pentafluorosulfanyldec-9-enecarboxylic acid esterAround-bottomflaskcontaining18gofsorbitolsuspendedin150goftetrahydro-furanwastreatedwith32goftheStep4productand10goftriethylamineandthenheatedfor1hat50°C.Afterfiltrationandpurification,theproductwasisolated.504NextGenerationofInternationalChemicalAdditivesTestingTestingdataarenotprovidedbyauthor.Advantages over Prior ArtFluorinatedsurfactantsdescribedinthisinventionhavethreeadvantagesabsentinexist-ingsurfaceactivefluorinatedagents.First,allmaterialsproducedusingthismethodaresurfaceactivedespitehavingverylowfluorinecontents.Second,sorbitolandsucrosefluorinatedmonoestersaresolubleinpolarmedia,particularlywaterandalcohol.Finally,oxidativeorreductivedegradationoftheseagentsdoesnotgeneratepersistentorganofluorinedegradationproducts,particularlyfluorinatedcarboxylicacids.Notes1.Phenyl(VII)andnaphthyl(VIII)analogsofthecurrentinventionwerepreparedbyHierse1andusedasantimicrobialsurfaceagents.SF5NaO3SOOCF3NaO3S73(VIII)(VII)2.Hierse2preparedfluorinatedaminoalcohols(IX)andsulfanylalcohols(X),whichhadsurfaceactivitiessimilartothatofclassicalfluorosurfactantsbutuponoxi