( 12) Patent Application Publication ( 10) Pub. N o. : US 2004/ 0097755 A1
( 19) United States Abbott et al. ( 43 ) Pub. D ate: May 20, 2004 ( 54) ION IC LIQUID S AN D THEIR USE AS SOLVEN TS ( 76 ) Inv entor s : Andr ew P. Abbott, Leices ter ( G B ) ; D av id L. D av ies , Leices ter ( G B ) ; G len Capper , Ex m outh ( G B ) ; Raym ond K . Ras h eed, B r am pton ( G B ) ; Vas uk i Tam byr aj ah , D eh iW ala ( G B ) Cor r es pondence Addr es s : J ones Tullar & Copper Eads Station PO B ox 226 6 Ar ling ton, VA 22202 ( US) ( 21) Appl. N o. : 10/ 3 8 1, 06 0 ( 22) PCT F iled: Sep. 26 , 2001 ( 8 6 ) PCT N o. : PCT/ G B 01/ 043 00 ( 3 0) F or eig n Application Pr ior ity D ata Sep. 27, 2000 ( G B ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0023 706 5 Publication Clas s i? cation 1 m . . . . . . . . . . . . . . . . . . . . . . . 7 55 ; c07c 229/ 06 ; 5 I c17 c0 c 2 / 24 c07c 211/ 6 3 ( 52) US. Cl. . . . . . . . . . . . . . . . . . . . . . . . . . . . 56 2/ 553 ; 56 2/ 6 05; 56 4/ 28 1 ( 57) AB STRACT Ionic com pounds W ith a f r eez ing point of up to 100 C. ar e f or m ed by th e r eaction of an one am ine s alt of f or m ula ( I) R1R2R3 R4N +X_, s uch as ch oline ch lor ide W ith an or g anic com pound ( II) capable of f or m ing a h ydr og en bond W ith X; s uch as ur ea, W h er ein th e m olar r ation of I to II is f r om 111. 5 to 1: 25. R1, R2, R3 and R4 m ay be H, optionally s ubs tituted C1 to C5 alk yl, optionally s ubs tituted C6 to C10 cycloalk yl, optionally s ubs tituted C6 to C12 ar yl, optionally s ubs tituted C7 to C12 alk ar yl, or R1 and R2 tak en tog eth er m ay r epr es ent a C4 to C10 optionally s ubs tituted alk ylene g r oup, th er eby f or m ing W ith th e N atom of f or m ula I a 5 to ll-m em ber ed h eter ocyclic r ing and all of R1, R2, R3 and R4 ar e not identical, X m ay be N 03 , F , Cl, B r ' , I, B 13 4, C104, CN , 503 C13 3 , or COOCF J . Th e ionic com pounds ar e us ef ul as s olv ents , and electr olytes f or ex am ple in electr o plating , electr oW inning , and electr opolis h ing , and as cata lys ts . US 2004/ 0097755 A1 ION IC LIQUID S AN D THEIR USE AS SOLVEN TS [ 0001] Th is inv ention r elates to ionic com pounds and m eth ods f or th eir pr epar ation. In par ticular th e inv ention r elates to ionic com pounds W h ich ar e liq uid at r elativ ely loW tem per atur es , i. e. g ener ally beloW about 100 C. , and pr ef er ably beloW about 6 0 C. and m or e pr ef er ably W h ich ar e liq uid at or near to am bient tem per atur e. [ 0002] Th er e is m uch cur r ent inter es t in th e ? eld of ionic liq uids . Such s ys tem s , W h ich ar e ex am ples of m olten s alts , h av e a num ber of inter es ting and us ef ul ch em ical pr oper ties , and h av e utility, f or ex am ple, as h ig h ly polar s olv ents f or us e in pr epar ativ e ch em is tr y, and as catalys ts . Th ey als o h av e par ticular application in electr och em is tr y, f or ex am ple in batter ies , f uel cells , ph otov oltaic dev ices and electr odepo s ition pr oces s es , f or ex am ple in bath s f or th e electr oplating of m etals . [ 0003 ] G ener ally s peak ing , ionic liq uids h av e v er y loW v apour pr es s ur e and th us , in contr as t to m any conv entional s olv ents , ar e v er y adv antag eous in th at th ey pr oduce v ir tu ally no h aZ ar dous v apour s . Th ey ar e th er ef or e adv antag eous f r om a h ealth , s af ety and env ir onm ental point of v ieW . [ 0004] One s uch s ys tem W h ich h as been k noW n f or m any year s is th at f or m ed f r om 1-eth yl-3 -m eth ylim idaZ olium ch lor ide-alum inium ch lor ide ( EMIC-AlCl3 ) . Th is s ys tem is a th er m ally s table liq uid betW een 100 C. to ca. 200 C. , dependent on th e m olar r atio of EMIC to AICl3 utilis ed. [ 0005] Such EMIC-AlCl3 s ys tem s h av e been us ed ex ten s iv ely as s olv ents f or v ar ious ionic r eactions and as electr o lytes , as des cr ibed, f or ex am ple in US. Pat. N o. 5, 525, 56 7, F R-A-26 11700, F R-A-26 26 572, W O95/ 218 72, and EP-A 8 3 8 447. Th er e ar e a num ber of dif f iculties in utilis ing s uch com pounds . Th es e ar is e pr incipally f r om th eir cos t, and f r om th eir W ater s ens itiv ity. [ 0006 ] In r ecent year s , oth er ionic com pounds h av e been m ade W h ich ar e liq uid at r elativ ely loW tem per atur es . F or ex am ple, US. Pat. N o. 4, 76 4, 440 dis clos es loW tem per atur e m olten com pos itions , f or m ed by r eacting , f or ex am ple, tr im eth ylph enylam m onium ch lor ide W ith alum inium tr ich lor ide. Th e r es ulting ionic com pound h as a loW f r eeZ ing point ( ar ound 75 C. ) , but s uf f er s f r om th e s am e W ater s ens itiv ity as EMIC-AlCl3 , becaus e of th e pr es ence of alum inium tr ich lor ide. [ 0007] Pr opos als h av e been m ade to utilis e oth er m etal h alides , in place of alum inium tr ich lor ide. F or ex am ple, US. Pat. N o. 5, 73 1, 101 dis clos es th e us e of ir on and Z inc h alides as th e anion por tion of an ionic liq uid com pos ition. Th e cation por tion is f or m ed by an am ine h ydr oh alide s alt, of th e f or m ula R3 N . HX ( X= h alide) . Th is r ef er ence indicates h oW ev er th at th e alum inium com pounds ar e pr ef er r ed. [ 0008 ] PCT/ G B 00/ 01090 dis clos es ionic liq uids , f or m ed by th e r eaction of q uater nar y am m onium com pounds s uch as ch oline ch lor ide W ith h alides of Z inc, tin, or ir on. [ 0009] SAITO, SHUJ I ET AL: Com plex es of ur ea and s ym m etr ical tetr aalk ylam m onium h alides J . AM. CHEM. SOC. ( 196 6 ) , 8 8 ( 22) , 5107-12 dis clos es com plex es of ur ea and s ym m etr ical Tetr aalk ylam m onium h alides . Th e com plex es ar e cr ys talline, and th er e is no dis clos ur e of th e us e of as ym m etr ical am m onium com pounds , nor of th e us e of liq uids f or m ed f r om s uch com plex es as s olv ents . May 20, 2004 [ 0010] K OICHI TAN AK A ET AL: Molecular ag g r eg a tion of alk yltr im eth ylam m onium br om ide and alcoh ol in th e s olid s tate MOL. CRYST. LIQ. CRYST. , Vol. 277, 1996 , pag es 13 9-143 is concer ned W ith th e s epar ation of pr im ar y alcoh ols f r om m ix tur es of pr im ar y and s econdar y alcoh ols , by com plex ation W ith q uater nar y am m onium br om ides W ith an alk yl ch ain leng th of at leas t 10. [ 0011] O. K RISTIAN SSON ET AL: Inter action betW een m eth anol and Cl, B r , I, N 03 , C104-, SO3 CF 3 and PF 6 Anions s tudied by F TIR s pectr os copy ACTA CHEMICA SCAN D IN AVICA, v ol. 51, 1997, pag es 270 273 dis clos es com pounds f or m ed betW een q uater nar y am m onium cations and m eth anol [ 0012] K EIJ U SAW AD A ET AL: X-Ray analys es of com plex es f or m ed betW een s ur f actants and ar om atic com pounds . I. A com m on s tr uctur al patter n of com plex es B ULLETIN OF THE CHEMICAL SOClETY OF J APAN . , Vol. 71, 1998 , pag es 2109-2118 dis clos es th e pr oduction of v ar ious s olid m ater ials f r om q uater nar y am ines and a v ar iety of ar om atic com pounds [ 0013 ] N EG ITA ET AL: 14N N uclear q uadr opole r es o nance of th e m olecular com plex es of ur ea B ULLETIN OF THE CHEMICAL SOClETY OF J APAN . , Vol. 54, 198 1, pag es 3 91-3 93 dis clos es s olid com plex es of ur ea W ith q ua ter nar y am ines . [ 0014] MASOOD A. K AHN : Hydr og en bonding and cr ys tal pack ing tr ends in tetr aalk ylam m onium h alide-cat ech ol com plex es : Synth es is , s pectr os copic and cr ys tal s tr uc tur e s tudies of Me4N Cl-catech ol, Et4N C1-catech ol, Et4N B r -catech h ol and Pr 4N B r -catech ol com plex es . [ 0015] J OURN AL OF MOLECULAR STRUCTURE, Vol. 145, 198 6 , pag es 203 -218 dis clos es cr ys talline com pounds pr epar ed f r om s ym m etr ical am ines and catech ol [ 0016 ] US. Pat. N o. 5, 73 1, 101 A ( LACROIX CHRIS TIN E P M ET AL) 24 Mar . 1998 ( 1998 -03 -04) and MASOOD A. K AHN ET AL: nov el h ydr og en bonding in cr ys talline tetr a-n-butylam m onium s alts of catech ol h alides CAN AD IAN J OURN AL OF CHEMISTRY, Vol. 6 3 , 198 5, pag es 2119-2122 dis clos e loW tem per atur e ionic liq uid com pos itions pr epar ed f r om alum inium tr ich lor ide and tr ieth y lam ine [ 0017] Q. LI; T. C. W . MAK : N ov el inclus ion com pounds cons olidated by h os t-h os t and by h os t-g ues t h ydr og en bond ing : com plex es of th iour ea W ith ( 2-h ydr ox yeth yl) tr im eth y lam m onium car bonate and ox alate dis clos es s olid inclus ion com pounds pr epar ed f r om th iour ea and q uater nar y am m o nium com pounds . [ 0018 ] W e h av e noW f ound th at it is pos s ible to f or m com pounds W h ich ar e liq uid at tem per atur es of 100 C. or beloW by r eacting an am ine s alt, pr ef er ably a q uater nar y am ine s alt, W ith an or g anic m ater ial, pr ef er ably one W h ich is a s olid at 20 C. , and W h ich is capable of f or m ing a h ydr og en bond W ith th e anion of th e am ine s alt. Com pounds s uitable f or f or m ing s uch h ydr og en bonds include am ides , s uch as ur ea, th iour ea, and acetam ide, car box ylic acids s uch as ox alic acid, benZ oic acid and citr ic acid, alcoh ols , ph enol, and s ubs tituted ph enols , as W ell as s ug ar s s uch as f r uctos e. Alth oug h it is not intended to be bound by any par ticular th eor y of oper ation, it is believ ed th at h ydr og en bonding of th e or g anic com pound W ith th e anion of th e am m onium US 2004/ 0097755 A1 com pound allows ch ar g e delocalis ation, W h ich s tabilis es th e liq uid f or m of th e com pound. [ 0019] Accor ding to th e inv ention, th er e is pr ov ided an ionic com pound, h av ing a f r eez ing point of up to 100 C. pr ef er ably up to 6 0 C. , f or m ed by th e r eaction of at leas t one am ine s alt of th e f or m ula R1R2R3 R4 N *X ( I) [ 0020] W ith at leas t one or g anic com pound ( II) W h ich is pr ef er ably a s olid at 20 C. , and W h ich is capable of f or m ing a h ydr og en bond W ith X, [ 0021] W h er ein R1R2R3 and R4 ar e each independently: [ 0022] H, [ 0023 ] optionally s ubs tituted C1 to C5 alk yl, [ 0024] optionally s ubs tituted C6 to C10 cycloalk yl, [ 0025] optionally s ubs tituted C6 to C12 ar yl [ 0026 ] optionally s ubs tituted C7 to C12 alk ar yl, or W h er ein [ 0027] R1 and R2 tak en tog eth er r epr es ent a C4 to C10 optionally s ubs tituted alk ylene g r oup, th er eby f or m ing W ith th e N atom of f or m ula I a 5 to 11-m em ber ed h eter ocyclic r ing , X is N 03 , F , Cl, B r , I, B F 4_, C104, CN , SO3 CF 3 _, or COOCF 3 _, and W h er ein th e ter m optionally s ub s tituted m eans th at th e g r oup in q ues tion m ay or m ay not be s ubs tituted W ith at one or m or e g r oups ( pr ef er ably f r om 0 to 6 g r oups ) s elected f r om OH, SH, SR5, Cl, B r , F , I, N H2, CN , N O2, COORS, CHO, coR5 and CR5, W h er ein R5 is a c1 to C10 alk yl or cycloalk yl g r oup, and W h er ein th e m olar r atio of I to II is f r om 111. 5 to 112. 5. [ 0028 ] Com pound II is pr ef er ably a com pound of th e f or m ula R COOH, R7R8 N H, RQCZ N HZ , or R1 OH, W h er ein: [ 0029] R6 , R7, R8 , R10 ar e each H, a Cl-C8 alk yl g r oup, an ar yl g r oup, or a C7-C12 alk ar yl g r oup optionally s ubs tituted W ith f r om 0 to 6 g r oups s elected f r om OH, SR5, Cl, B r , F , I, N H2, CN , N O2, COORS, coR5 and CR5, W h er ein R5 is H, a c1 to C alk yl or cycloalk yl g r oup 10 003 0 R9 is a r ou as de? ned f or R , or N HRll, g p W h er ein R11 is H or a Cl-C6 alk yl g r oup, and Z is O or S. [ 003 1] Pr ef er ably, Com pound II is ur ea, aniline, or a s ubs tituted aniline, a Cl-C6 aliph atic acid, a Cl-C6 aliph atic am ine, a Cl-C6 h ydr ox y aliph atic acid, or a dicar box ylic acid of th e f or m ula HOOC( CH2) nCOOH, W h er ein n is 0 or 1 acetam ide, a ph enol or a s ubs tituted ph enol, an alk ylene g lycol, or citr ic acid. Mos t pr ef er ably, com pound II is ur ea, acetam ide, ox alic acid dih ydr ate, ph enol, eth ylene g lycol, or citr ic acid. [ 003 2] Th e Com pounds I and II ar e m ix ed in a m olar r atio of f r om 1: 1. 5 to 112. 5, pr ef er ably about 1: 2. In g ener al, th e am ine s alts ( I) us ed in th e pr epar ation of th e ionic com pounds accor ding to th e inv ention ar e pr ef er ably as ym m et r ic, i. e. , th e s ubs tituent g r oups ( R1, R2, R3 and R4) ar e pr ef er ably not all identical. May 20, 2004 [ 003 3 ] Th e pr ef er r ed am ine s alts of F or m ula I ar e th e s am e as th os e W h ich ar e pr ef er r ed in PCT/ G B 00/ 01090, nam ely ones W h er e R4 is a C1 to C10 alk yl or a cycloalk yl g r oup, s ubs tituted W ith at leas t one g r oup s elected f r om OH, Cl, B r , F , I, N H3 , CN , N 02, 0R5, COORS, CH0, and CORS. It is par ticular ly pr ef er r ed th at R4 is an eth yl g r oup, s ubs tituted W ith one or m or e of h ydr ox yl, ch lor ine, or an es ter ( i. e. th at th e s ubs tituent R4 is der iv ed f r om ch oline, ch lor och oline, or a ch lor och oline es ter ) . Speci? c ex am ples of R4 g r oups W h ich h av e been f ound to be s uitable ar e 2-h ydr ox yeth yl, 2-br om oeth yl, 2-ch lor oeth yl, 2-acetoeth yl, N -decyl, cyclo h ex yl, 2-h ydr ox y 3 -ch lor opr opyl, and 3 -br om opr opyl. In a f ur th er pr ef er r ed em bodim ent, th e am ine cation is ch ir al. [ 003 4] Th e counter -ion X of com pound ( I) is pr ef er ably h alide, f or ex am ple br om ide or ch lor ide. [ 003 5] Th e ionic com pounds accor ding to th e inv ention m ay be pr epar ed s im ply by m ix ing th e am ine s alt ( I) , W ith th e h ydr og en bond donor ( II) . Th e r eaction is g ener ally endoth er m ic, and is us ually car r ied out by h eating , f or ex am ple to a tem per atur e of 100 C. or m or e. [ 003 6 ] Th e ionic com pounds accor ding to th e inv ention m ay be utilis ed f or a W ide r ang e of pur pos es , f or ex am ple as electr olytes in electr och em ical dev ices s uch as batter ies or f uel cells , in ph otov oltaic or electr och r om ic dev ices , and in electr och em ical depos ition electr opolis h ing , or electr o-r e ? ning . Th e com pounds ? nd par ticular application f or car r ying out applications W h er e a polar but non-aq ueous s ol v ent is r eq uir ed. Th ey m ay als o be em ployed as iner t m edia, f or dis s olv ing ionic s pecies s uch as tr ans ition m etal com plex es , and, eith er alone, or af ter com plex ing W ith oth er m etal ions , as catalys ts , or as ch em ical r eag ents . Th ey m ay als o be us ed f or ex tr acting a s olute f r om an im m is cible s olv ent. [ 003 7] Th e ionic com pounds accor ding to th e inv ention als o m ay be us ed as an alter nativ e to th e tr aditional m ix tur es of s tr ong acids as s olv ents f or th e electr opolis h ing of m etals , f or ex am ple s tainles s s teel and alum inium . At leas t th e pr ef er r ed com pounds accor ding to th e inv ention ar e m or e env ir onm entally f r iendly th an th e tr aditional acid m ix tur es us ed f or electr opolis h ing s tainles s s teel, as W ell as being ch eap and r eus able. In addition th ey can r es ult in loW er poW er cons um ption and r educed local env ir onm ental h aZ ar ds in th e W or k place, f or ex am ple th os e caus ed by g as ev olution s uch as m is ting of conv entional acid m ix tur es . [ 003 8 ] A num ber of pr ef er r ed em bodim ents of th e inv en tion ar e illus tr ated in th e f olloW ing ex am ples . Th e com po s ition of all of th e pr oducts W as ch ar acter is ed us ing 1H N MR s pectr os copy, and th eir ionic ch ar acter W as ch ar acter is ed by conductiv ity m eas ur em ents , us ing a J enW ay 4071 conduc tiv ity m eter and tem per atur e pr obe. All of th e com pounds h ad an electr ical conductiv ity of at leas t 10 #5 cm ' 1 at 10 C. abov e th eir f r eeZ ing point. Th e s tar ting m ater ials us ed in th e Ex am ples W er e all anh ydr ous m ater ials , and W er e dr ied under v acuum f or 2 h our s pr ior to us e. EXAMPLE 1 [ 003 9] Ch oline ch lor ide ( a q uater nar y am m onium com pound of th e g ener al f or m ula I abov e, in W h ich R1, R2, and R3 ar e m eth yl, R4 is C2H4OH, and X is Cl' ) 1. 40 g ( 0. 01 m ol) W as added to 1. 2 g of ur ea ( 0. 02 m ol) in a labor ator y tes t tube. Th e m ix tur e W as h eated to a tem per atur e of 70 C. US 2004/ 0097755 A1 f or a per iod of 20 m in, to pr oduce a clear colour les s liq uid. Th e m elt W as allowed to cool at a r ate of appr ox im ately 1 C. per m inute, and th e tem per atur e r ecor ded at W h ich initial cr ys tal f or m ation W as obs er v ed and r ecor ded as th e f r eez ing point. ( F or all eutectic m ix tur es , com plete f r eez ing of th e com pos ition tak es place at a tem per atur e m uch loW er th an th at of initial cr ys tal f or m ation, but th e s olidi? cation is s loW , and in s om e cas es th e m ater ials can r em ain as g els f or s ev er al days bef or e s olidi? cation) . Th e conductiv ity of th e 2: 1 Ur ea/ ch oline ch lor ide ionic liq uid at 19 C. W as 3 3 8 MS cm _1. Th e f r eeZ ing point of th e m ix tur e W as 12 C. EXAMPLES 2 TO 15 [ 0040] Th e pr ocedur e of Ex am ple 1 W as r epeated, us ing 0. 02 m ols of th e com pounds II identi? ed in Table 1, in place of ur ea. Th e r es ults ar e s h oW n in Table 1. In each cas e, th e h eating W as car r ied out until a clear m elt W as f or m ed, and th e f r eeZ ing point W as th en deter m ined by th e ? r s t appear ance of cr ys tal f or m ation, at a cooling r ate of 1 C. per m inute. TAB LE 1 Ex am ple N o Com pound II F r Pt. of Melt ( C. ) Am ides 1 Ur ea, N HZ CON H2 12 2 Acetam ide, CH3 CON H2 51 3 Th iour ea, N HZ CSN H2 6 9 4 Salicylam ide, oHOC6 H4CON H2 91 5 B enz am ide, CSHSCON H2 92 Car box ylic acids 6 G lyox ylic acid below 0 7 Malonic acid, HOOCCHZ COOH below 0 8 Ox alic acid, HOOCCOOH 48 9 B enz oic acid, C6 H5COOH 95 Alcoh ols 1O B enz yl alcoh ol, C6 H5CH2OH 6 1 11 Ph enol C6 H5OH 3 0 12 p Meth yl ph enol 10 13 o Meth yl ph enol 8 14 m Meth yl ph enol B eloW 3 5 15 p Ch lor o ph enol B eloW 3 5 16 D -F r uctos e 5 17 Vanilin p-HO r n OCH3 C6 H3 CHO 42 18 p Am ino ph enol 93 Am ines 19 Aniline 44 2O Hydr ox ylam ine h ydr och lor ide 8 1 [ 0041] In or der to dem ons tr ate th at th e f or m ation of th e liq uid ionic com pound is th e r es ult of h ydr og en bonding betW een Com pound II and th e ch lor ide anion, attem pts W er e m ade to pr epar e s im ilar m ater ials us ing v ar ious oth er s tar t ing m ater ials , us ing th e s am e pr ocedur e as Ex am ple 1. Th e r es ults ar e s h oW n in Table 2, as Com par ativ e Ex am ples 1 to 8 . [ 0042] In th e s am e m anner as des cr ibed in Ex am ple 1, com pounds W er e pr epar ed f r om ch oline ch lor ide ( 0. 01 m oles ) and each of th e com pounds s h oW n in Table 1A ( 0. 02 m oles ) . Th e f r eeZ ing point of th e r es ulting com pound is s h oW n in Table 1A [ 0043 ] B y contr as t, th e s ubs tances indicated in Table 2A, W h en s ubs tituted in th e s am e m olar q uantity f or th e ur ea of May 20, 2004 Ex am ple 1 did not g iv e an ionic liq uid W ith a f r eeZ ing point of 100 C. or les s . TAB LE 2 Com p Ex . N o Com pound II F r Pt. of Melt ( C. ) Am ides 1 D im eth ylur ea, N HCH3 CON HCH3 149 Es ter s and Eth er s 2 Anis ole C6 H5OCH3 no m elt f or m ed. 3 4-Iodoanis ole no m elt f or m ed. 4 D ieth ylox alate ( CZ HSOOC) 2 no m elt f or m ed. 5 D ieth ylm alonate no m elt f or m ed. Aldeh ydes and K etones 6 B enz yl m eth yl k etone no m elt f or m ed Oth er 7 Hex ach lor oeth ane no m elt f or m ed. 8 Cycloh ex ane no m elt f or m ed [ 0044] TAB LE 1A Com pound II F r Pt. of Melt ( C. ) Am ides Allyl ur ea 9 Ur ea/ H2O2 com plex 19 Car box ylic acids Tr i? uor oacetic acid B eloW 40 Tr ich lor oacetic acid 24 Citr ic acid 26 Mandelic acid 3 3 Valer ic acid 22 Tar tar ic acid 74 Ph enyl acetic acid 5 m -nitr obenz oic acid 8 5 p-h ydr ox ybenz oic acid 97 G lutam ic acid 13 m -am inobenz oic acid 3 9 Alcoh ols Eth anediol 20 Tr ieth anolam ine 24 2-ch lor oeth anol 6 Vanillin 17 p-h ydr ox ybenz aldeh yde 29 Sug ar s D ( ) F r uctos e 5 D -g lucos e 14 Am ines D iam inoeth ane 29 1, 2-diam inopr opane 6 3 Mis c. W ater 11 p-toluenes ulph onic acid m onoh ydr ate 27 D ibenz enes ulf onam ide 3 9 US 2004/ 0097755 A1 [ 0045] TAB LE 2A Com pound II F r Pt. of Melt ( C. ) Car box ylic acids s alicylic acid 103 tr ans -cinnam ic acid 101 3 , 5-dinitr obenz oic acid 104 nicotinic acid 126 s tear ic acid no m elt f or m ed h ippur ic acid no m elt f or m ed oleic acid no m elt f or m ed ter eph th alic acid no m elt f or m ed Alcoh ols 9-Anth r acenem eth anol no m elt f or m ed. Eth anol no m elt f or m ed. Pr opan-2-ol no m elt f or m ed. Mannitol 108 8 -h ydr ox yq uinoline no m elt f or m ed 2-m eth yl s alicylate no m elt f or m ed 2-ph enyl s alicylate no m elt f or m ed Sug ar s Lactos e no m elt f or m ed Sacch ar in no m elt f or m ed Am ines Pyr idine no m elt f or m ed. B enz yl am ine no m elt f or m ed. tr ieth ylam ine no m elt f or m ed Es ter s and eth er s Eth yl cinnam ate no m elt f or m ed Aldeh ydes and k etones B enz aldeh yde no m elt f or m ed. Am ino acids G lycine no m elt f or m ed. Alanine no m elt f or m ed. Lys ine no m elt f or m ed Ph enylalanine no m elt f or m ed Mis c. F er r ocene no m elt f or m ed. Sar cos ine N o m elt f or m ed. Tetr abutylam m onium h ydr og en s ulph ate 159 1, 2-dich lor oeth ane N o m elt f or m ed. Ur ic acid N o m elt f or m ed N itr oeth ane N o m elt f or m ed. G lycer ol tr iacetate N o m elt f or m ed [ 0046 ] Th e r es ults in Tables 1, 2, 1A and 2A dem ons tr ate th at m any but not all com pounds wh ich ar e in pr inciple capable of donating a h ydr og en atom to a h ydr og en bond ar e capable of f or m ing ionic liq uids with ch oline ch lor ide, by th e m eth od of Ex am ple 1. In g ener al, th e com pounds wh ich ar e f or m th e m os t us ef ul ionic com pounds ( i. e. , th os e with th e lowes t f r eez ing points ) ar e ones in wh ich th e Com pound II em ployed h as a r elativ ely low f r eez ing point, f or ex am ple, les s th an 150 C. , pr ef er ably les s th an 100 C. , m or e pr ef er ably les s th an 50 C. , and yet m or e wh ich h av e a f r eez ing point of 20 C. , or les s ( i. e. , wh ich ar e s olid at am bient tem per atur e) . [ 0047] An additional f actor wh ich h as an im por tant bear ing upon wh eth er a par ticular h ydr og en bond donor com pound ( II) is capable of f or m ing an ionic liq uid h av ing a f r eez ing point of 100 C. or les s is th e dif f er ence between th e deg r ee of s tr uctur e of th e com pound in th e s olid and liq uid s tates . Com pounds capable in pr inciple of f or m ing a h ydr o May 20, 2004 g en bond, but in wh ich dif f er ence between th e deg r ee of s tr uctur e in th e s olid and liq uid s tates is low ar e g ener ally not pr ef er r ed. F or ex am ple long ch ain aliph atic acids wh ich h av e a low f r eez ing point but a low deg r ee of s tr uctur e in th e s olid s tate ar e g ener ally uns atis f actor y. Lik ewis e, com pounds wh ich ar e h ig h ly or der ed in th e liq uid s tate ( s uch as tr i? uor oaceticacid) ar e g ener ally f av our ed. [ 0048 ] Yet a f ur th er f actor with im por tant bear ing upon wh eth er a par ticular h ydr og en bond donor com pound ( II) is capable of f or m ing an ionic liq uid h av ing a f r eez ing point of 100 C. or les s is th e pr es ence of dif f er ent types of f unctional g r oups capable of acting as h ydr og en bond donor s . It is s tr ong ly pr ef er r ed th at only one type of f unctional g r oup capable of acting as h ydr og en bond donor is pr es ent in th e com pounds II. F or Ex am ple, alth oug h two car box ylic acid g r oups m ay be pr es ent, com pounds containing both a COOH g r oup and an N H2 g r oup, ( am ino acids ) ar e g ener ally not pr ef er r ed. [ 0049] One of s k ill in th e ar t will g ener ally be capable of s electing a s uitable h ydr og en bond donor f or th e pur pos es of th e inv ention, bas ed on th e f or eg oing cr iter ia, and th e s peci? c Ex am ples h er ein. EXAMPLE 16 [ 0050] Th e ef f ect of ch ang ing th e natur e of th e anion X was inv es tig ated, by r epeating th e pr ocedur e of Ex am ple 1, us ing ch oline nitr ate, and ch oline tetr a? uor obor ate ( 0. 01 m ol) ins tead of ch oline ch lor ide, in th e pr ocedur e of Ex am ple 1. Th e f r eez ing points of th e r es ulting com pounds ar e s h own in Table 3 . TAB LE 3 Ex am ple N o X' F r Pt. / C. 21 B R, 6 7 22 N 03 4 EXAMPLES 23 TO 41 [ 0051] Th e ef f ect was inv es tig ated of s ubs tituting v ar ious oth er am ine s alts of F or m ula I, f or th e ch oline ch lor ide of Ex am ple 1. In each cas e, 0. 01 m ol of th e am ine s alt, as s h own in Table 4, was h eated with 0. 02 m ol of ur ea, until a clear m elt was f or m ed. F r eez ing points wer e m eas ur ed by cooling , as bef or e. Th e f r eez ing points ar e s h own in Table 4. TAB LE 4 F r . Ex . R1 R2 R3 R4 X Pt. / C. 1 Me Me Me C2H4OH Cl 12 23 Me Me B enz yl C2H4OH Cl 3 3 24 Me Me Et C2H4OH Cl 3 8 25 Me Me Me B enz yl Cl 26 26 Me Me Me C2H4OCOMe Cl 14 27 Me Me Me C2H4Cl Cl 15 28 Me Me Me ClCH2CHOHCH2 ( R) Cl 6 5 29 Me Me Me ClCH2CHOHCH2 ( S) Cl 8 3 3 0 Me H H H Cl 3 3 3 1 Me Me H H Cl 29 3 2 Et Et Et H Cl 95 3 3 Et Et Et B enz yl Cl 3 6 3 4 Me B enz yl C2H4OH C2H4OH Cl 6 3 5 Me H H CH2COOH Cl 3 US 2004/ 0097755 A1 TAB LE 4-continued F r . Ex . R1 R2 R3 R4 X Pt. / C. 3 6 Me Me Me B r C2H4 B r 8 4 3 7 Me Me Me C2H4F B r 55 3 8 Me Me Me Me( CH2) 11 B r 92 3 9 Et Et Et Me B r 9 4O Et Et Et B enz yl B F 4 59 41 Me Me C2H4OH C2H4OH I 46 COMPARATIVE EXAMPLES 9 TO 15 [ 0052] In th e s am e W ay, s alts of a s ym m etr ical am ine, as W ell as oth er am ines of r elativ ely h ig h m olecular W eig h t W er e inv es tig ated, th e r es ults ar e s h oW n in Table 5, as com par ativ e ex am ples 9 to 12. Th es e r es ults dem ons tr ate th at uns ym m etr ical am ine s alts ( R1R2R3 R4 ar e not all iden tical) of r elativ ely loW m olecular W eig h t, ar e pr ef er r ed. TAB LE 5 Com p R1 R2 R3 R4 x - c. 9 B u4N B u B u B u B u Cl 112 10 Me( CH2) 13 ( Me) 3 N Me Me Me Me( CH2) 13 B r no m elt f or m ed 11 Me( CH2) 17( Me) 3 N Me Me Me Me( CH2) 17 B r no m elt f or m ed 12 Hex ( Et) 3 N Et Et Et n-h ex yl B r 108 EXAMPLES 42 TO 44 [ 0053 ] Th e ef f ect of v ar ying th e anion X- W as inv es ti g ated, us ing tetr aeth ylam m onium s alts of v ar ious anions , in com bination W ith ur ea, in th e m eth od of Ex am ple 1. Th e r es ults ar e s h oW n in Table 6 . TAB LE 6 Ex am ple Com pound I cation X' F Pt. / C. 42 ( Et) 4N C104 99 43 ( Et) 4N O3 SCF 3 59 44 ( Et) 4N CN 72 Com p. 25 ( Et) 4N B R, 13 0 Com p 26 ( Et) 4N MeC6 H4SO3 107 Com p 27 ( Et) 4N B r 113 [ 0054] Com par is on of Ex am ple 21 W ith Com par ativ e Ex am ple 25 illus tr ates br oadly th at as ym m etr ical am ines ar e pr ef er r ed. [ 0055] Mis cibility Tes ts [ 0056 ] Th e m is cibility of th e m ater ial pr epar ed in Ex am ple 1 W ith a num ber of com m on s olv ents W as inv es tig ated. It W as f ound to be m is cible W ith m eth anol, D MSO, and W ater , and to f or m tW o layer s W ith acetone, acetonitr ile, acetoph enone, br om obenZ ene, dich lor oeth ane, dieth yleth er , eth ylacetate, h ex ane, pr opylene car bonate, and toluene. W ith THE, a W h ite pr ecipitate W as f or m ed. EXAMPLE 45 [ 0057] Us e of Ionic Liq uids as B atter y Electr olytes [ 0058 ] LoW f r eez ing point ionic liq uids pr epar ed f r om com pound II and am ine s alts can be us ed as electr olytes in May 20, 2004 batter ies . TW o s uch ex am ples ar e des cr ibed beloW . In th e ? r s t, 7 m l of th e m ater ial of Ex am ple 1 ( 2: 1 ur ea-ch oline ch lor ide) W as pr epar ed and pour ed into s epar ated com par t m ents of a s m all g las s cell. Th e com par tm ents W er e s epa r ated by g las s f r it and each contained 3 . 5 m l of ionic liq uid. Th e cell W as s us pended in an oil bath s o th at th e liq uid tem per atur e W as m aintained at 45 C. In one com par tm ent 0. 06 g of F eCl3 W as dis s olv ed and a car bon electr ode ins er ted. A Z inc electr ode W as im m er s ed in th e liq uid con tained in th e oth er com par tm ent. An Ecoch em ie PG s tat 10 potentios tat W as us ed to m eas ur e th e potential dif f er ence betW een th e electr odes th e m ax im um r ecor ded v alue W as 1. 45V. Th e h alf cell r eactions f or th is batter y ar e; Z n> Z n2*+2e ( neg ativ e electr ode) [ 0059] In th e s econd ex am ple 7 m l of 2: 1 ur ea-ch oline ch lor ide W as pr epar ed and div ided betW een th e tW o com par tm ents of a g las s cell as bef or e. To one com par tm ent 0. 05 m l of B r 2 W as added and a car bon electr ode W as ins er ted. A Z inc electr ode W as im m er s ed in th e liq uid contained in th e oth er com par tm ent. Th e m ax im um v alue W as 2. 14V at 22 C. Th e h alf r eactions f or th is batter y ar e; ( pos itiv e electr ode) Z n> Z n2++2e ( neg ativ e electr ode) and, 1/ 2B r 2+e> B r ( pos itiv e electr ode) EXAMPLE 46 D is s olution of Metal Ox ides [ 006 0] An ionic liq uid W as pr epar ed by h eating tW o m olar eq uiv alents of ur ea W ith one m olar eq uiv alent of ch oline ch lor ide in a s uitable r eaction v es s el at appr ox im ately 70 C. Ruth enium ox ide, copper ( II) ox ide, ch r om ium ( VI) ox ide, v anadium pentox ide, lead ( IV) ox ide, m ang anes e ( IV) ox ide and Z inc ox ide W er e all f ound to be s oluble in th e ionic liq uid, in th e tem per atur e r ang e 6 0 C. to 120 C. N one of th e ox ides of ir on or alum inium h av e s h oW n s ig ni? cant s olubility in th e ionic liq uids and h ence th es e ionic liq uids can be us ed to pr ef er entially ex tr act m etal ox ides f r om th eir or es . Th e m etals can be ex tr acted f r om th e ionic liq uids us ing electr oW inning . [ 006 1] Th e 2: 1 ur ea-ch oline ch lor ide ionic liq uid can als o be us ed to pr oces s com plex m ix tur es of m etal ox ides and alloW electr oW inning to be us ed to r ecov er th e m etals . Th is pr oper ty of th e ionic liq uid and its r elativ ely loW bulk cos t g iv es it th e potential to be us ed to tr eat ar c f ur nace dus t on an indus tr ial s cale. Electr ic ar c f ur nace dus t containing ir on ( III) ox ide ( > 3 0% ) , Z inc ox ide ( > 3 0% ) , alum inium ox ide ( ~ 10% ) , s ilica ( ~ 5% ) , calcium ox ide ( ~ 5% ) and lead com pounds ( ~ 5% ) W as us ed in th is ex per im ent. N or m ally it is tr eated as a W as te pr oduct and bur ied in land ? ll s ites . HoW ev er th is is an ex pens iv e pr oces s and th e lead content caus es com plications due to its h ig h tox icity. [ 006 2] Z inc ox ide and lead com pounds can be dis s olv ed in 2: 1 ur ea-ch oline ch lor ide and th e r es pectiv e m etals s ubs e q uently electr odepos ited onto a s uitable cath ode. Ox ides of F e, Al, Si and Ca W er e f ound to be alm os t totally ins oluble in th e abov e ionic liq uid. Ur ea-ch oline ch lor ide ionic liq uid W as pr epar ed by com bining ur ea ( 0. 02 m oles ) W ith ch oline ch lor ide ( 0. 01 m oles ) in a beak er and h eating at 8 0 C. Ar c f ur nace dus t ( 0. 5 g ) W as added to th e r es ulting clear colour les s liq uid and th e m ix tur e W as h eated at 8 0 C. f or 1 h our . Af ter 1 h our a br oW n s us pens ion W as obtained W h ich W as tr ans f er r ed to an electr och em ical cell. Metal electr odepos i tion W as ach iev ed us ing a nick el cath ode and a titanium US 2004/ 0097755 A1 anode ( both electr odes W er e 50 m m by 10 m m and 1 m m th ick ) and applying a potential dif f er ence of 3 . 5 V f or 1 h our . Pr ior to electr odepos ition th e electr odes W er e g ently abr aded W ith g las s paper and cleaned W ith acetone. Af ter 1 h our of electr odepos ition th e nick el cath ode W as r em ov ed f r om th e br oW n s us pens ion, W as h ed W ith acetone and dr ied. A th ick ch ar coal colour ed depos it W as obtained. Th e electr odepos ited m ater ial W as analys ed us ing Ener g y D is per s iv e Analys is by X-r ays . Th e r es ults of th e analys is r ev ealed th e pr es ence of lead ( 77% ) , Z inc ( 16 % ) and copper ( 7% ) . Th er e W as no tr ace of ir on in th e depos it th us s h oW ing th at Z inc ox ide and ir on ( III) ox ide can be s epar ated and h ar m f ul lead com pounds r em ov ed f r om ar c f ur nace dus t. [ 006 3 ] D is s olution of Pr ecious Metal Ox ides [ 006 4] Oth er com m er cially im por tant ox ides f or r epr o ces s ing include pr oces s es f or th e r ecov er y of pr ecious m etals , in par ticular platinum and palladium , f r om m ater ials in W h ich th ey ar e pr es ent as ox ides . Such m ix tur es occur , f or ex am ple, in s pent catalys t r ecov er ed f r om autom obile cata lytic conv er ter s . It W ould be h ig h ly des ir able to be able to r ecov er s uch m ater ials in a pr oces s W h ich is econom ically v iable. G ener ally th e r ecov er y of s uch m etals f r om ox ide m ix tur es inv olv es dis s olution of th e ox ide in s tr ong acids , s uch as aq ua r eg ia. [ 006 5] W e h av e dis cov er ed th at th e ionic liq uids accor ding to th e inv ention, and in par ticular th os e W h er e com pound II is a car box ylic acid ( pr ef er ably ox alic acid) ar e ef f ectiv e s olv ents f or th e dis s olution of platinum and palladium ox ides . Th e dis s olv ed m etals m ay be r ecov er ed f r om s uch s olutions by electr oW inning . F or ex am ple, palladium ox ide ( in th e f or m of s pent catalys t s uppor ted on v ar ious s ub s tr ates ) can be dis s olv ed in th e 2: 1 ox alic acid-ch oline ch lor ide ionic liq uid. In or der to ef f ect th e dis s olution, th e tem per atur e is pr ef er ably m aintained beloW 6 0 C. Palla dium m etal can s ubs eq uently be r ecov er ed by depos ition onto a v ar iety of s ubs tr ates . EXAMPLE 47 [ 006 6 ] An ionic liq uid W as f or m ed by m ix ing ox alic acid ( 17. 7 g ) and ch oline ch lor ide ( 9. 8 g ) at 6 0 C. To th is a s am ple of autom obile catalys t W as added ( 3 . 16 g ) W h ich W as pr incipally PdO on an alum ina s uppor t. A g r ey s us pens ion W as initially f or m ed W h ich tur ned into a g r een s olution W h en th e Pd dis s olv ed and th e s olid pr ecipitated to th e bas e of th e cell. Th e s olution W as electr olys ed us ing a N i cath ode and a titanium anode and an applied v oltag e of 5V f or 3 0 m in W ith an appr ox im ate cur r ent dens ity of 1 m A cm _2. At th e end of th is tim e a black depos it W as obtained on th e cath ode. Th is W as analys ed us ing ener g y dis per s iv e analys is by x -r ays and f ound to be pr im ar ily Pd m etal. EXAMPLE 48 Metal Electr odepos ition [ 006 7] Th e ionic liq uids als o ? nd application in m etal electr odepos ition. Us ing , f or ex am ple a 2: 1 ur ea-ch oline ch lor ide m ix tur e copper , nick el, lead and Z inc can be elec tr odepos ited f r om th eir ch lor ide s alts and th is ? nds appli cation in r epr oces s ing th e s aid m etals f r om indus tr ial W as te pr oducts . [ 006 8 ] F our por tions of 2: 1 ur ea-ch oline ch lor ide m ix tur e ( 0. 2 m ol ur ea and 0. 1 m ol ch oline ch lor ide) W er e pr epar ed and h eated at 8 0 C. Th e pr epar ations W er e per f or m ed in s am ple tubes . A s m all q uantity ( 0. 001 m ol) of a m etal containing com pound ( eith er CuSO4. 5H2O, N iSO4. 6 H2O, PbCl2 and Z nO) W as added to one s am ple of ionic liq uid and May 20, 2004 lef t to dis s olv e. Electr odepos ition W as th en per f or m ed in each ionic liq uid in tur n us ing Pt electr odes 3 m m in diam eter polis h ed W ith 1 pm A1203 pas te. In each ex per i m ent a potential dif f er ence of 3 V W as applied f or 10 m in and th e tem per atur e W as m aintained at 8 0 C. F or each of th e m etals , ch ar acter is tic depos its W er e obtained on th e neg ativ e Pt electr ode. [ 006 9] 2: 1 ur ea-ch oline ch lor ide ionic liq uid ( 16 m l) W as pr epar ed by com bining th e r eactants in a beak er and h eating at 8 0 C. Cobalt ( II) ch lor ide h ex ah ydr ate ( 1. 5% W t) W as added to th e clear colour les s ionic liq uid and dis s olv ed to g iv e a blue liq uid. Th e blue liq uid W as th en pour ed into a PTF E electr och em ical cell of inter nal dim ens ions 41 m m long , 16 m m W ide and 3 2 m m deep. A m ild s teel plate and a s tainles s s teel plate, both 55 m m by 40 m m and 1 m m th ick , W er e g ently abr aded W ith g las s paper , cleaned W ith acetone and ? am e annealed. Th e s teel plates W er e th en placed par allel to each oth er along th e inner leng th s of th e PTF E electr och em ical cell. Cobalt depos ition W as ach iev ed by connecting th e m ild s teel and s tainles s s teel plates to th e neg ativ e and pos itiv e ter m inals r es pectiv ely of a Th ur lby Th ander poW er pack . A potential W as applied and adj us ted s o as to m aintain a cur r ent dens ity of 2 m Acm ' 2 f or 3 0 m inutes . An ISO-TECH ID M 6 6 D ig ital Voltm eter con nected in s er ies W as us ed to m onitor th e cur r ent. Th e ex per im ent W as car r ied out at 6 0 C. Af ter 3 0 m inutes th e m ild s teel plate W as r em ov ed f r om th e cell, r ins ed W ith acetone and dr ied. W ith a cur r ent dens ity of 2 m Acm ' 2 a s em i-br ig h t pale g r ey/ br oW n h om og enous depos it W as obtained. [ 0070] A s epar ate por tion of 2: 1 ur ea-ch oline ch lor ide ionic liq uid ( ~ 5 m l) containing cobalt ( II) ch lor ide h ex ah y dr ate ( 1. 5% W t) W as pr epar ed and pour ed into an electr o ch em ical cell at 6 0 C. Voltam m etr y W as per f or m ed us ing a platinum m icr oelectr ode ( 10 pm diam eter ) , a platinum counter electr ode and a cobalt r ef er ence electr ode. An Auto lab PG STAT12 Potentios tat contr olled by G PES s of tW ar e W as us ed to car r y out th e cyclic v oltam m etr y. [ 0071] Reactions in Ionic Liq uids [ 0072] Heck Reaction 1. 4 eq X 5 m ol % Pd( OAc) 2, 1. 1 eq N aOAc Ur ea: Ch oline M6 0 ch lor 1de( 2: 1) 1 eq OMe x = 1, B r , c1 [ 0073 ] Th e r eaction betW een s tyr ene and 4-iodoanis ole in th e pr es ence of Pd( OAc) 2 and N aOAc at 13 0 C. f or 2 days US 2004/ 0097755 A1 g av e 4-Iodoanis ole W ith a 6 0% conv er s ion to th e pr oduct. Us ing 4-B r om oanis ole g av e 50% conv er s ion to th e pr oduct af ter 2 days under th e s am e r eaction conditions . 4-Ch lor o anis ole did not r eact W ith s tyr ene under s im ilar conditions . [ 0074] Us ing PdCl2 as th e catalys t th e r eaction is f as ter g iv ing a 90% yield of th e s am e pr oduct in 1. 5 days . [ 0075] W h en N aZ CO3 is us ed as th e bas e ins tead of N aOAc W ith PdCl2 as th e catalys t, th e r eaction tim e decr eas ed and yield im pr ov ed W ith 4-iodoanis ole g iv ing pr oduct W ith 96 % yield in 16 h . Af ter r em ov al of th e pr oduct by dis tillation, th e s am e m elt and PdCl2 catalys t ( W ith th e addition of m or e N a2CO3 ) W as r eus ed f or th e s am e r eaction, g iv ing pr oduct in 90% yield. [ 0076 ] Polym er is ation Reactions in Ionic Liq uids Ur ea: Ch oline ch lor ide( 2: 1)
110 c. , 16 h ( AIB N ) 1 r nol % polym er [ 0077] Th is r eaction yielded a polym er W ith a num ber av er ag e m olecular W eig h t of 12, 000 W ith a polydis per s ity indeX of 3 . 2 AIB N Ur ea: Ch oline ch lor ide( 2: 1) > 1m 01% 110 c. , 16 h COOMe polym er [ 0078 ] Th is r eaction yielded a polym er W ith a num ber av er ag e m olecular W eig h t of 12, 8 00 W ith a polydis per s ity indeX of 3 . 2 [ 0079] Stainles s Steel Electr opolis h ing Us ing 2: 1 Ur ea Ch oline Ch lor ide Ionic Liq uid [ 008 0] Ur ea and ch oline ch lor ide in a m olar r atio of 2: 1 ( 16 0 m l in total) W er e com bined in a beak er and h eated at 8 0 C. until a clear colour les s liq uid W as obtained. Th e ionic liq uid W as th en pour ed into a cylindr ical electr och em ical cell ( inter nal diam eter of 8 0 m m ) s us pended in an oil bath at 6 0 C. A Z inc s h eet W as g ently abr aded us ing g las s paper , deg r eas ed W ith acetone, s h aped into a cylinder W ith a diam eter of about 78 m m and s lid into th e electr och em ical cell. Th e Z inc electr ode W as th en connected to th e neg ativ e ter m inal of a Th ur lby Th ander poW er pack . A s tainles s s teel collar , appr ox im ately 40 m m in diam eter , W as s us pended in th e centr e of th e 2: 1 ur ea-ch oline ch lor ide ionic liq uid W ith th e aid of a lead connected to th e pos itiv e ter m inal of th e Th ur lby Th ander poW er pack . Apotential dif f er ence of 12 V W as applied f or 6 m inutes af ter W h ich tim e th e s tainles s s teel collar W as r em ov ed f r om th e ionic liq uid, r ins ed W ith acetone and dr ied. Th e s tainles s s teel collar W as f ound to be May 20, 2004 br ig h t and r e? ectiv e all ov er its s ur f ace. Th e pr ocedur e W as r epeated us ing oth er s tainles s s teel collar s and s tainles s s teel f as tener s of s im ilar dim ens ion and each tim e br ig h t r e? ec tiv e ? nis h es W er e obtained. [ 008 1] Stainles s Steel Electr opolis h ing Us ing 2: 1 Eth anediol-Ch oline Ch lor ide [ 008 2] Eth anediol and ch oline ch lor ide in a m olar r atio of 2: 1 ( 20 m l) W er e com bined in a beak er and h eated at 8 0 C. until a clear colour les s liq uid W as obtained. Th e ionic liq uid W as th en pour ed into an alum inium electr och em ical cell ( inter nal leng th of 6 0 m m , inter nal W idth of 10 m m and inter nal depth of 40 m m ) s us pended in an oil bath at 25 C. Th e outer W all of th e alum inium cell W as connected to th e neg ativ e ter m inal of a Th ur lby Th ander poW er pack . A s tainles s s teel plate, 50 m m by 10 m m and 1 m m th ick , W as deg r eas ed and s us pended in th e centr e of th e alum inium cell W ith th e aid of a lead connected to th e pos itiv e ter m inal of th e Th ur lby Th ander poW er pack . Apotential dif f er ence W as applied and adj us ted s o as to m aintain a cur r ent dens ity betW een 6 0 and 70 m Acm ' 2 at th e s tainles s s teel plate f or 6 m inutes . Af ter 6 m inutes th e s tainles s s teel plate W as r em ov ed f r om th e 2: 1 eth anediol-ch oline ch lor ide ionic liq uid, r ins ed W ith acetone and dr ied. Th e s tainles s s teel plate W as f ound to be br ig h t and r e? ectiv e all ov er its s ur f ace. Th e 2: 1 eth anediol-ch oline ch lor ide ionic liq uid can be m odi? ed by th e addition of lith ium ch lor ide ( 5% W t) . Th e incr eas ed ch lor ide content of th e ionic liq uid incr eas es th e conductiv ity and th us loW er s th e poW er cons um ption dur ing electr opolis h ing . Stainles s s teel polis h ed in 2: 1 eth anediol ch oline ch lor ide containing lith ium ch lor ide is als o v er y br ig h t and r e? ectiv e. 1. An ionic com pound, h av ing a f r eeZ ing point of up to 100 C. f or m ed by th e r eaction of at leas t one am ine s alt of th e f or m ula R1R2R3 R4 N *X ( I) W ith at leas t one or g anic com pound ( II) W h ich is capable of f or m ing a h ydr og en bond W ith X, W h er ein R1, R2, R3 and R4 ar e each independently: H, optionally s ubs tituted C1 to C5 alk yl, optionally s ubs tituted C6 to C10 cycloalk yl, optionally s ubs tituted C6 to C12 ar yl optionally s ubs tituted C7 to C12 alk ar yl, or W h er ein R1 and R2 tak en tog eth er r epr es ent a C4 to C10 option ally s ubs tituted alk ylene g r oup, th er eby f or m ing W ith th e N atom of f or m ula I a 5 to 11-m em ber ed h et er ocyclic r ing , X is N 03 , F , Cl, B r , I, B 13 4, C104, CN , SO3 CF 3 _, or COOCF J , and W h er ein th e ter m optionally s ubs tituted m eans th at th e g r oup in q ues tion m ay or m ay not be s ubs tituted W ith at one or m or e g r oups s elected f r om OH, SH, SR5, Cl, B r , F , I, N H2, CN , N 02, COORS, CHO, coR5 and ORS, W h er ein R5 is a C1 to C10 alk yl or cycloalk yl g r oup, W h er ein th e m olar r atio of I to II is f r om 1: 1. 5 to 1: 2. 5. 2. An ionic com pound as claim ed in claim 1, W h er ein all of R1, R2, R3 and R4 ar e not identical. US 2004/ 0097755 A1 3 . An ionic com pound as claim ed in claim 1 or claim 2, wh er ein com pound II is an or g anic com pound W h ich is s olid at 20 C. 4. An ionic com pound as claim ed in any one of th e pr eceding claim s , W h er ein com pound II is a com pound of th e f or m ula R COOH, R7R8 N H, RQCZ N HZ , or R1 OH, W h er ein: R , R7, R8 , R10 ar e each H, a Cl-C8 alk yl g r oup, an ar yl g r oup, or a C7-C12 alk ar yl g r oup optionally s ubs tituted W ith f r om 0 to 6 g r oups s elected f r om OH, SR5, Cl, B r , F , I, N H2, CN , N 02, COORS, coR5 and CR5, W h er ein R5 is H, a C1 to C10 alk yl or cycloalk yl g r oup R9 is a Cl-C8 alk yl g r oup, Cl-C12 an ar yl g r oup, or a C7-C12 alk ar yl g r oup optionally s ubs tituted W ith f r om 0 to 6 g r oups s elected f r om OH, SR5, Cl, B r , F , I, N H2, CN , N 02, COORS, coR5 and CR5, W h er ein R5 is H, a C1 to C10 alk yl or cycloalk yl g r oup, or N HRll, W h er ein R11 is H or a Cl-C6 alk yl g r oup, and Z is O or S. 5. An ionic com pound as claim ed in claim 4, W h er ein com pound II is ur ea, acetam ide, th iour ea, g lyoXylic acid, m alonic acid, ox alic acid dih ydr ate, tr i? uor oacetic acid, benz oic acid, benz yl alcoh ol, ph enol p-m eth yl ph enol, o-m e th yl ph enol, m -m eth yl ph enol, p-ch lor o ph enol, D -f r uctos e, or v anillin. 6 . An ionic com pound as claim ed in claim 4, W h er ein com pound II is ur ea, aniline or a s ubs tituted aniline, a Cl-C6 aliph atic acid, a Cl-C6 h ydr oXyaliph atic acid or a dicar boXy lic acid of th e f or m ula HOOC( CH2) nCOOH, W h er ein n is 0 or 1, acetam ide, a ph enol or a s ubs tituted ph enol, an alk ylene g lycol, or citr ic acid. 7. An ionic com pound as claim ed in claim 4, W h er ein com pound II is ur ea, acetam ide, oXalic acid dih ydr ate, ph enol, eth ylene g lycol, or citr ic acid. 8 . An ionic com pound as claim ed in claim 1, W h er ein Com pound II h as f r eez ing point of les s th an 16 0 C. 9. An ionic com pound as claim ed in claim 7, W h er ein Com pound II h as a f r eez ing point of 20 C. or les s . 10. An ionic com pound as claim ed in claim 1, W h er ein Com pound II contains only one type of f unctional g r oup capable of acting as h ydr og en bond donor . 11. An ionic com pound as claim ed in claim 1, W h er ein th e m olar r atio of I to II is about 1: 2. 12. An ionic com pound as claim ed in any one of th e pr eceding claim s , W h er ein R4 is a C1 to C10 alk yl or a cycloalk yl g r oup, s ubs tituted W ith at leas t one g r oup s elected f r om OH, Cl, B r , F , I, N H2, CN , N O2, COORS, CORS, CH0 and ORS, W h er ein R5 is as de? ned in claim 1. 13 . An ionic com pound as claim ed in any one of th e pr eceding claim s , W h er ein each of R1, R2, R3 , independently is a C1 to C5 alk yl or a cycloalk yl g r oup, and R4 is h ydr oXy alk yl. 14. An ionic com pound as claim ed in claim 9, W h er ein each of R1, R2, R3 , is m eth yl, and R4 is h ydr oXyeth yl. 15. An ionic com pound as claim ed in any one of th e pr eceding claim s , W h er ein X is ch lor ide. 16 . An ionic com pound as claim ed in any one of th e pr eceding claim s , W h er ein R1, R2, R3 , and R4 h av e th e f olloW ing m eaning May 20, 2004 Me Me Me C2H4OH Me Me B enz C2H4OH Me Me Et C2H4OH Me Me Me B enz Me Me Me C2H4OCOMe Me Me Me C2H4Cl Me Me Me CICHZ CHOHCH2 ( R) Me Me Me CICHZ CHOHCH2 ( S) Me H H H Me Me H H Et Et Et H Et Et Et B enz Me H H CH2COOH Me Me Me Et Me Me Me C2H4F Me Me Me Me( CH2) 11 Et Et Et Me Et Et Et B enz 17. An ionic com pound accor ding to any one of th e pr ev ious claim s in W h ich th e am ine cation is ch ir al. 18 . A m eth od of pr epar ing an ionic com pound, h av ing a f r eez ing point of up to 100 C. , W h ich m eth od com pr is es r eacting at leas t one am ine s alt of th e f or m ula R1R2R3 R4N *X ( I) W ith at leas t one or g anic com pound ( II) W h ich is capable of f or m ing a h ydr og en bond W ith X, W h er ein R1, R2, R3 and R4 ar e each independently: H, optionally s ubs tituted C1 to C5 alk yl, optionally s ubs tituted C6 to C10 cycloalk yl, optionally s ubs tituted C6 to C12 ar yl optionally s ubs tituted C7 to C12 alk ar yl, or W h er ein R1 and R2 tak en tog eth er r epr es ent a C4 to C10 option ally s ubs tituted alk ylene g r oup, th er eby f or m ing W ith th e N atom of f or m ula I a 5 to 11-m em ber ed h et er ocyclic r ing , X- is N 03 , F , Cl, B r , I, B F 4_, C104, CN , SO3 CF 3 _, or COOCF 3 _, and W h er ein th e ter m optionally s ubs tituted m eans th at th e g r oup in q ues tion m ay or m ay not be s ubs tituted W ith at one or m or e g r oups s elected f r om OH, SH, SR5, Cl, B r , F , I, N H2, CN , N O2, COORS, CHO, COR5 and ORS, W h er ein R5 is a C1 to C10 alk yl or cycloalk yl g r oup, W h er ein th e m olar r atio of I to II is f r om 111. 5 to 112. 5 . 19. A m eth od as claim ed in claim 18 , W h er ein th e r eaction is car r ied out by h eating th e com pound of f or m ula I W ith th e com pound of f or m ula II 20. Th e us e of an ionic com pound accor ding to any of claim s 1 to 17 as a s olv ent, as an electr olyte or as a catalys t. 21. A m eth od of r ecov er ing a m etal f r om a m etal oXide, W h ich m eth od com pr is es f or m ing a s olution of th e m etal oXide in an ionic liq uid as claim ed in any one of claim s 1 to 17, and electr olys ing th e s olution to r ecov er th e m etal. 22. A m eth od as claim ed in claim 17, W h er ein th e m etal is platinum or palladium . US 2004/ 0097755 A1 May 20, 2004 23 . A m eth od of electr opolis h ing a m etal ar ticle, W h ich optionally s ubs tituted C6 to C12 ar yl m eth od com pr is es im m er s ing th e m etal ar ticle in an ionic liq uid as claim ed in any one of claim s 1 to 17, and applying opnonany Subs m uted C7 to C12 alk ar yl or W h er em a v oltag e to th e ar ticle to electr opolis h th e m etal. R1 and R2 tak en t0g eth er r epr es ent a C4 to C10 Option 24. A m eth od of f or m ing a s olution of a s olute, W h ich ally Subs tituted alk ylene g r oup, th er eby f or m ing W ith m eth od com pr is es dis s olv ing th e s olute in an ionic com - th e N atOIIl 0f f Or IIlllla I a 5 t0 ll-m em ber ed h et pound, h av ing a f r eeZ ing point of up to 100 C. f or m ed by er ocyclic r ing , X_ iS N 03 1 F , Cl_, B F , I_, B F 4T, th e r eaction of at leas t one am ine s alt of th e f or m ula C1O4_, CN _, SO3 CF 3 _, 0r COOCF J , and W h ef eln 1 2 3 4 i th e ter m optionally s ubs tituted m eans th at th e R R R R N *X ( I) . . . . g r oup in q ues tion m ay or m ay not be s ubs tituted W ith W ith at leas t one or g anic com pound ( II) W h ich is capable at one or m or e g r oups Selected f r om OH, SH, SR5, of f or m ing a h ydr og en bond W ith X, W h er ein R1, R2, Cl, B r , 1: , I, N HZ , CN , N 02, COORS, CH0, COR5 R3 and R4 ar e each independent1y3 and 0R5, W h er ein R5 is a C1 to C10 alk yl or H, cycloalk yl g r oup, Optionally Subs tituted C1 to C5 alk yl, W h er ein th e m olar r atio of I to II is f r om 1: 15 to 112. 5 . optionally s ubs tituted C6 to C10 cycloalk yl, * * * * *