Title of Invention

"CUCURBIT[N]URILS AND METHOD FOR PRODUCING SAID CUCURBIT[N]URILS"

Abstract

A method for producing cucurbit[n]urils, where n is from 4 to 12, comprising mixing substituted and/or unsubstituted glycoluril with an acid and a compound that can form methylene bridges between glycoluril units, and heating the mixture to a temperature of from 20° to 120° to thereby form cucurbit[n]. Novel cucurbit[n]urils, where n = 4, 5,7, 8, 9, 10, 11 and 12 and substituted cucurbit[s,u]urils, where s = number of substituted glycoluril units, u = number of unsubstituted units and s + u = 4 - 12 are also described.

Full Text

The present invention relates to cucurbit[n]urils and method for producing said cucurbit[n]urils. The present invention also relates to cucurbit[n]urils, to cucurbit[s, u]urils, and to a method of separating cucurbit[n]urils and/or cucurbit[s, u]urils. The present invention also relates to novel compounds used in the preparation of cucurbit[n]urils and cucurbit[s, u]urils. Cucurbituiji is the name given to a cyclic oligomer formed by 3inl~.ng six (6) glyzoliirii units via methylene bridges. Cacurbituri1 was first described in the literature in 1905 in a paper by R. Behrenel, E. Meyer and F. Rusohe, Leibigs Ami. ~hem• ; 339, 1,2905. The macrocyclic sTh~cture of cucurbituril was first described it 1981 by WA Freeman et. aL, "Cucurbituril" J. Am.. Ohern. Soc., 103 (1981), 7367-7368. Cucurbituril has •a chemical formula of CH36NO12 ~nd is a inacrocyclac compound having a central cavity. An AMI. -mnnm1~e~ .s~wucture of cucu.rbituril is shown in Figure 1. The internal cavity of cucurbituril has ~ diameter of about .550 pm, a depth of 650 pm with portals at either end about 400 ~m across. This rigic~ cavity TZias been shown to have high selectively in binding a variety of medium-small molecules and in this regard reference is made to Cintas, P., 1. Inclusion Phenomena and Molecvi.ar Recognition in Chemisty; I7~ 205, 1994 The preparatioh of cucurbituril has generally followed the procedure first described in the article byR. 3ehrend et, a.L published in .1.905. In German patent no' DE 196 0377, published 7 August 1997~ a process for synthesising cucurbitu.ril is described. This process includes dissolving acetylene diur~a (glycoluril) in an aqueous solution of a strong mineral acid in the presence of excess formaldehyde, with war~ning. The wateZ is evaporated from the mixture to completely eliminate the water from the mixtute. The remaining polymer mixture is then. heated to a temperature. up to 1450C to~ complete the reaction. The applicants for this patent have stated that a yield of up to 824% of the theoretical yield can. be obtained. LEn German patent no. DE 4001139, the use of cucurbituril to remove organic compounds with hydrophobic groups, dyes. decomposition products from dyes and/or heavy metals from aqueous solutions is described. The patent actually states that a cyclic oligomer which is obtained by condensation of urea. thiourea. derivates of urea and/or derivatives of the thiourea with dialdehydes and formaldehyde is used. Although the patent states that the degree of polymerisation. n, of the cyclic oligomer varies between about 3 and about 8. the examples of the patent showing cyclic o1i~omers having a degree of polymerisation. n. only of 6. Example 1 shows the preparation of cucurbituril by heating glycoluril under reflux with formaldehyde. Experiments conducted by the present inventors in fol1owin~ the procedure of Example 1 of DE 4001139 have shown that cucurbituril having 6 g1~coluri1 units joined together is formed. In the words of DE 4001139. n~6 for this product. No evidence was found of any cyclic oligomer having a degree of polvmerisation, n, other than 6. Indeed, a paper by Buschmann et. al.. Inorgica Chiroica Acta, 1992. 193, 93 states that under the synthetic conditions as described in DL 400 1139, only cucurbituril having a degree of polymerisation. n, of 6 is formed. The present inventors have now developed a method for producing cucurbiturils having a degree of polymerisation of 4 to 12. To assist in differentiating such compounds. the present inventors have adopted the terminology "cucurbit[n]uril"' where n is a number from 4 to 12, to: denote the different compounds. For example, a cyclic oligomer having 4 basic glycoluril (substituted or unsubstituted). units joined together would be denoted as "cucurbit [4]uril". In a first aspect. the present invention provides a cucurbit[n]uril having the formula (I) whereinn=~4to 12. and wherein. for each unit of the formula (IL making up the cucurbit[n]uril, R1 and R2 are independently selected from H, an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical or a heterocyclyl radical, or R1 and R2 form a cyclic hydrocarbon radical or heterbcyclyl radical, but excluding unsubstituted cucurbit[6]uril and decamethylcucurbit[5]uril. In another aspect, the present invention provides a method for producing a cucurbit[n]uril, where n is from 4 to 12. but excluding unsubstituted cucurbit [6]uril and decamethyl cucurbitli5]uril which comprises mixing substituted and/or unsubstituted g1~coiuri1 with an acid and a compound that can form methylene bridges between glycoluril units; and optionally a templating compound selected from ammQnium chloride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, caesium chloride. ammonium bromide, lithium bromide, sodium bromide, potassium bromide, rubidium bromide. caesium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide. caesium iodide, potassium sulfate. lithium sulfate. tetrabutviammonium chloride. tetraethylammonium chloride, o-carborane. thioacetamide. N -(1-napthyl) ethyienedianiine. 2,2'-biquinoline, p-bromo aniline. taurine, blue tetrazolium, 2 -amino- 3-methyl benzoic acid, indol-3-aidehvde, cysteine. 4-acetamidoaniline. p-aniinophenol, acetamide. 4-amino acetophenone, 4-dimethvlaminobenzaldehyde, 2-aminobenzimadazole. bis-( 4,4' -bipyridyl)- a,d-p-xylene. red phosphorus and lithium p-toluenesuifonate; and optionally a solvent; and heating the mixture to a temperature of from 20~ to 1200C to thereby form a cucurbit[n]uril. Preferably, n is from 5 to 10. Preferably. the method of the present adding a salt to the mixture. It has a salt to the mixture assists synthesis of a variety of cucurbit[mllurils invention further comprises been ound that adding in achieving the of differing unit sizes, Without wishing to be bound by theory, it is believed, that an ion ternolating effect may be occurring. Thus, 'selection of the particular salt can control the amount of ~. derived cucurbit~n]uril in the product. It has also been found that a number of other compounds can be added to the mixture in place of the salt, or in combination with the salt, to achieve the templating effec: described above. The templating effect causes the relative amount of cucurbit[njurils of differing unit sizes to be altered if the salt or otb.er compound is added to the mixture. For example, the salt or other compound, when added to the reaction m~xnire. may alter the ratio of, say, cucurbitr5~uri1 to cucurbit~6~uxil, when that ratio is compared with the ratio of cuqurbit~5~uri1 to cucurbitF6~u.ril that is produced using reaction mIxtures having no salt or other compound added thereto but otherwise reacted underj i~entica1 conditions. For ease of descriotion.. such salts and other compounds will be described hereinafter throughout this specification as "templating compounds1'. In a ~roferred embodiment the method of the first aspect of the present invention further compnses adding one or more tempiating compounds to the mixture, The emniating zom~ounds can be selected from a large number of compounds and indeed any compounc~ that can alter the ratio of cu.curbit~n.~urils of different unit sizes produced in the method of the present fttventio~t can be used as a tempiating compound. The rempiating compound may be an organic compound, a salt of an organic compound, or an .iuorganic compound. Suitable compounds that may be used as a templating compound include ammoniuz chloride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, caes.iu.tn chloride, amnionium chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, caesium bromide, litbi.um iodide, sodium iodide, potassium iodide, rubidium iodide, caesium iodide, potassium sulfate, lithium sulfate, tetrabutylarnmonium chloride, tetraethylammonium chloride, O-carb orane, thioacetantide, N- (2. -napthyl) ethylenediamine, 2,2 -biquinoyl, p-bromoanal.ine, taurine, blue tetrazolium, 2-antino-3-methyl benzoic acid, indol-3-aldehyde, cystine. p.-acetamidoanitine p-aminophenol, acetamide, 4-acetami doaiutine, p-aminophenol, acetamide, 4- amino acetopben.one, 4-dimethylaininobenzaldehyde, 2- aminobenzimadazol, bis-(4,4'-bi~yridy1~ )-~. o~-p-xylene, red phosphorus, and lithium p-toluenesulfonate. The present inventors believe fhat a large number of other compounds couk be suitable for use as templating compounds and therefore the above list should no: be considered to be exhaustive, The anions of the acid may also be considered to be a template. The tetnplating eomoounds may be added singly to the reaction rnxtu~e or ~wo or more tempiatng compounds may be added to the reaction mixture L~ a salt is used as the templating compound salt that is added to the mixture is preferably a metal balide, ammonium halide, or the corresponding suiphates. or metal tos-Aates, It is preferred that the anion of the salt corresponds to the anion of the acid used. For example, where the acid tised is hy&oohlorie acid, a metal chloride or ammonium chloride is the preferred salt, If sulphuric acid is used, metal sulphate or ammoniun sulphate is the preferred salt, Similarly, iodide-containing salts are ~referabiy used where hvdriodic acid is the acid, and bromide-containing salts are preferably used where hydrobromic acid is used. The acid, is vreferably a strong mineral acid or a strong organic acid. I: principle, any acid can ~e usec~ The acid acts to catalyse the reactions ta~.ng place. Preferred acids for use ~n the ~nethod of the first aspect of the ~resenz invention include sulfuric acid, hydrochloric acid, hydrobrounic acid, hydrojodic acid, deuterated sulfuric acid. phosphoric acid, p-toluenesulfonic acid, and methane sulfonic acid. I: will be appreciated that this list is not exhaustive and that any acid that can catalyse the reaction may be used in the method of the first aspect of the present invention. It is especially preferred that the acid has a concen~atiozt of at least 5 M. In some embodiments of the first aspect of the present invention, a solvent may aIsb be added to the reaction mixture. The solvent is preferably selected from trifluoroacetic acid, methanesuffonic acid, and 1,1, l-~-ifluorethanoi. The compound that can form merhylene bridges between gycoluril units is most preferably formaldehyde, Daraformaldehyde, ~ioxane or one or more precursors for formaldehyde. For convenience, the invention will hereinafter be described with reference to the case where formaldehyde is used. The mixture is preferably heated to temperarure of from 20CC to 11 000, more preferably 600C to I 10~0, most preferably from R0~C to Ii 0CC, It is preferred that boiling of the mixture is avoided, Heating under reflux~ as required in the prior art, is not requfred (but may be use d~. Such temperature conditions are much milder than those u.tiiised in the prior art synthesis process that led to the formation of cucuroitf6Nrii. The prior art processes involved heating the mixmre t.inder reflux follo~'ed by heating to temperatures of up to 145 to 1650C. At room temperatures the present inventors have found that, cucurbit[n]urii was formed only if concentrated sulphuric acid was used as the acid. It has been found that the mixture should, generally be heated to a temperature cf 6000 and above to produce cucarbit~njurils, with increased yields being obtained at temoeratures on the range of 8000 to 1000C. The glycolurils that are used in the ~resen: invention have an unsubstitured structure ~s shown in :or~ula I beiow~The general structure for ~he cucurbitfnlurils synthesised in accordance with the process of the present invention iS shown in formula 2 below wherein n = 4 to 1.2, preferably 4 to 10. (Formula 2) Substituted and unsubstituLed glycolurils, or a n~,i,~ure thereof, zn~y be used to synthesise cucurnitrnjuril in accor~.snce with the present invention, Substituted glycolurils have the general formula as shown in formula below: (Formula 3) wherein k1 and P~ are the same or different and selected front an optionally substituted strai~hr chain, branched or cyclic, saturated or unsaturated hydrocarbon radical or R~, and R2form a cyclic hydrocarbon radical. The hydrocarbon radical for substituents Th and R2 may include alkyl, alkertyl, alkynyl, aryl and heterocyclyl radicals, There are large numbers of substituted glycolurils l~own in the literature, Particular reference is made to a review article by Harm Petersen in Synthesis4 1 923, 243-293, which contains a list of about 30 substituted glycoiurils~ The entire contents of this review article are hereby e~press1y incorporated into this specification by cross reference, The literature since the Petersen article has disclosed several other examples of substituted glycolurils and it is believed that essentially any o.4~-diketone could he used to make a glycoluril. (Formula 7) 10 Invesugarions conducted by present inventors have shown that :ucurbit~n2uri1-1ike systems can be synthesised with marv of the substituted glycolurils, preferably when used, in conjunctior. with unsubstituted glycoiur~1s. The following substituted glycolutil compounds have been prepared and used to synthesise substituted cucurbitrlurils: (Formula 4) (Formula 5) ula 6) The compounds of forinu.lae 5, 6 and 7 above are 'novel and accordingly, in another aspect, the present invention provides a substituted glycoluni compound of formula 5, formula 6 or formula 7. The synthesis of substituted cucurbit[njurils opens the possibility of being able to chemically link the substituted cucurbitlnjuril to a substz'ate or to chemisorb them onto a substrate, The solubility characteristics of the product znay also be manipulated by selection of appropriate substituents. As mentioned earlier, cucurbitE6]uri2. was first cheracterised and synthesised in 1905. ~ioweyer, the present inventors believe that cucurbit[njuril. where n—4, 5, 7, 8, 9, IC, 11 or 12 has never previously been synthesised. Accordingly, in a fu~her aspect, the present invention provides cucurbit[njurL, where n = 4, 5, 7, 8, 9, 10, 2.1 or 12, Preferably, n = 5,7, B, 9 or 10. The presen: also. provides substituted cucurbit~n3uriis, where r. = 4, 5. ~, 7, B, 9, 1.0, IL or 12. lo order to clarify nomenclature when substituted cucurbiturils are forme& t~e presen: inventors have ~roDose.d that substituted cucurbiturlis it. accordance with the present invention be identified, by the scheme "cuctzbliEs,uluril", ~'here s the number or substituted glycoluril units and u = the number of unsubstituted glycoluril units in the cucuroituriL Using this nomenclature, the present invention also provi cucurbit~s,.uThrii, where s and u are as de~ned above and s-~-u=~ to 2.2, preferaciv 5 'tc 10. In all of the experimental work conducted by the present invez~tors •ro date in relation to substituted cucu~oiturils1, the substituted cucurbiturils have incorporated both substituted and unsubstituted glycoluril units into the cucu~bituril structure. Thus, it is prefez~ed that u does not equal zero. If s e~uais zero, cucurbit[s,~Juril is equivalent to cucurbitlnlurils, The substituted cucurbitlinjurils are preferably synthesized from substituted g~yco}uri1. or amixture of substituted and unsubstituted glyc~luril. The substituents may be as described above,n order show the structure of cucurb4n~uri. in cases where n = 4. 5, 7 or 8, zliaimised chemical structures were Drepared using ?C-Sparan. a rnoiecuiar modelling and visualisation package. The mini~ised structures are shown as formulae S tc K below: orrula B — CucurbitL4luril (C~ ~ N~ O~) ula 9 — Cucurbit~f]uri1. [C30 BI~c N20 Q~~) Formula 11 — Cucurbi:(8NrL (C42 }i45 N~2 Q~~) The inimnsed structures of Pormu~ae S to 11 clea&~ show the inner cavity of the eucurbituril. As the value o: n increases, the stze of the inner cavity increases" w~ch enables different compotuids to fit into the inner cavity. The reaction product of the process of the ~resenr ~nvenho: contains a mix~ure of di~erent cucurbitLn]u.riis or cucurbitFs,u}uriis. There ~e several methods that could be used to seDarate and purify these products and these are described below Successive Recrystalltsation All of the cuoc it~n~ urils that have been obse~red are apparently soluble in acid solutions. Oucur'bitF5 or 7 or ~ or 1 0~uril have been purified by successive recrystallisations from acid solutions. Eecause of the siiniiar nature of the cucurbiturils. this is a ato~w process with more than 10 recrvstaflisations recuired to '~urLfy cu&~rbit7Jurfl, As shown in the German patents zucurbit~6Jur2 can be obtained in a relatively pure state from ~ single recystallisation process. Selective disso1utionIpreci~itation We have been able to demonstrate that different cucurbiturils have mark.ediy different solubilities in various salt solutions. It is possible to separate cucurbit~6j.uril and cucurbitf7jurii from a tixture contaimng cucurbit[5-8~urils by dissolving cucurbitL~ or 7]uril out of the con~plex mixture using a 0.1M Na2 304 solution. We have also demonstrated the use of selective precipitation as a purification method. A solution of cucurbit[6Jurii and cuourbit~7Juril was mixed with bis(4~~,ct-z-xylene with several crystals depositing out of the saxnole. According to another aspect, the present invention comprises separating a mixture of cucurbit[n]urils. where n = 4 to .2, by mixing the mixture of eucurbit~njurils with a salt solution in whic1'~ at least one of the cucurbit~n2uriis, but not all of the cucurbit[n]urils, dissolves, separating solids ir. which at least one of the cucurbit~nJuri1s, but not all of the cucit~n~urils, dissolves, separating solids from the solution recovering the dissolved at least one cucurbitfn3utils from the solution. This method may also be used to sevarate mixtures of different substituted cucurbit[s,ujurlLs. As ar. example, Utbiuit chloride ir. hydrochloric acid solutions selective> assists the crvstaliisa:ion of zucurbi:~6]urii and '-cucurbitfSjuri leaving cucurbizF5]ut'L and cucurbit~T]uri in solution. Potassium chloride in hydrochloric acid solutions seiect~ve1y assists the crystallisanon of cucurbit~5~uri and cucuroit~Sjuri1 ieavit~g cucurbit~6~uril and cucar~it(7]uri1 ui solution, Any of the salt compie~~ed cucurbit[n~uriis can be separated from their salt b~' a process of desalting or ion exchange resins such as Dowel 50. Dissolved in formic 'acid water, the mixtures are loaded onto the resin and the salts eluted with dilute drochioric acid/formic acid solutions until satisfactory salt removal and ther. the final recovery of the cucurbit[njuril is achieved by elution with 5M or higher of aqueous hydrochloric acid. Chrornatographic Separation &tb Thin Layer Ohomatography (The and Kigh Pressure Uquid Chromatography (LC have demonstrated ability to separate out various oligomers of cuuroit~n~nri1. 3och of these systems are under continuing invest~gat1om TLC using -a silica stationary phase and 0. IM Hydrochloric acid as the mobile phase resulted in a mixture of cucu:bit[n~urils se~rating into several bands, HPLC separation has beer. attempted using a C—2.~ stationary phase and C.5M Na2SO4 mobile chase. The retention times of :ecrysta.ilised samples of cucurbit~6~urll arid cucurbit[7~urii were comparable with peaks foi.2nd in mixed samples of crude cucurbit~nJurils. In a further aspect, the present invention provides amethod for separating a mixture of cueurbitLn1uriis~ where = 4 to 10. by dissolving the mixture of cucurbitLn]uril~ ~nd subjecting the thus- ted solution of cucurbit[rijurils to chromatographic separation. This method tu.ay also be used to separate mixtures of cueurbit[sj~urils. In addition, rolymer resins as chromatographic supports, such as, Dowex or Sephadex ion exchange columns or polyanilnes arc effective :n the purification of cucurbit~n~urils. The eluant most commonly used was, 30-50% acucous formic acid or a mixture of fo~nic acid 98% and aqueous hydrochloric acid 0.5M in a. ratio of 1:2 respectively. Samples sizes of to 2 gin were able to be purified on a b~d of 25cm of resin, In order to more fully understand the present invention, the proposed reaction mechanism will be discussed hereunder i: is to be understood that the following reaction mechanism is a proposed mechanism and the present invention should no; be considered to be limited thereto. The proposed reaction me.chanism hereunder should be rca: z conjunction with Figures la. Ib, to and Id, The synthesis of cucurbitfn~uril or substicared cuzurbit>JurL (where r. equals the nuinoer of glycouuli units marking up cuourbirarit is an acid caralysed process. In the mechanism detailed below the first important intermediate 1 has bee: isolated and is the reaction of a glycoluril with four equivalents of formaldehyde. The dehydration of this retro to. the cyclic diether 2 has been demons~ated by the isolation of pure 2 where R = pheny> The intermediates .~ or B are both produced through a series of acid catalysed steos. This mechanism is not prescriptive, as it is nossibie for either A or B to be produced Similarly, it without going througt 1 or 2. - is possible for glycoluril units to begin linking on one side prior to reaction with formaldehyde on the other This is a dynamic process with multiple reversible reaction steps The mechanism shown here is Only to be considered representative of the many possibilities The reaction from glycoluril to cueurbit[n]urii involves a number of intermediates produced through reversible reaction steps. The influences acting on the balance of these reversible steps are many and some can be manipulated a a variety of' points there 'ov effecting the out come of The reacrion~ Examples The following examples illustrate preferred embodiments of the present invention: Example I Synthesis of' eucurbit[nluriis 2., fg — glycoluril 6.9 ml — mineral acid (hydrochloric 36%, hydrobromic 48%, hydriodic 47% or sulphuric acid 98% or 50%) or organic acid (para toluene suiphonic acid) S nintol — of the corresponding alkali metal halide, ammonium halide or the corresponding suiphates in the case of sulphuric acid or alkali metal tosylates 600 rig — red phosphoms (this was added ro reaction mixtures when hydriodic acid was 'N 1s3ea2, Notes A -. Following the addition of formaldehyde there. is an. exotherziic reaction. On larger scale the reaction inixture is cooled in an ice bath. Formaldehyde can be substimted by paraforxnaldehvde or trioxane or any formaldehyde producii~g precursor. 2. ?roceeding to the ne~; stage of the reaction procedure after lhr or 1 month a: room temperature makes little difference to the our come except in the case of concentrated sulphufic acid where the reaction continues to cucurbit~n2urils a: room temperature. 3. A reaction temperature of 6O~C and above is sufficient to give cucurbit~nJurUs but at the lower temperatures with extended reaction times to achieve completion, up to SDhrs. The given yields above for the larger unit oueurbit(>=7L~ril are on average increased a further 50% on the tabled yields. .~n some cases pressure was generated during heating. In the e'vent of a -pressure build u~ the pressure was released 5. The repeated dissolving and evaporation was primarily carried out to remove excess formaldehyde and volatile formaldehyde by products. Example 2 Synthesis Cucur~itjIs,uJuri1s The ~ame te~npianz~ controls are applicd to substin.~ted cucurbi~[~1uriL~ either by rhe above method where g?ycoiuril t~sed is s bsrituted or as descr~be~ below. A mixture of tetracyclic ether B (2.5 nunol) and glycoluril (0.355 gin, 2.5 namol) was dissolved or suspended in the appropriate acid (6~9tnl) (note 1). Then in the cases where a salt was used to maninulate reaction products the alkali metal ion or ammonium salt (Sinmol) with rite corresponding anion appropriate to the acid was added Heat was then applied to the reaction mixture, which was maintained at a temperature of 1 O0~C for 3hrs (Note 2). The reaction mixture was cooled to room temperature and th~ products were isolated by adding methanol (lOmi) and collecting the resultant precipitate by filtration. The solid material was washed with methanol ~nd acetone and air dried, Further purification was effected bx recrystafisatior. from aqueous hydrochloric acid or hvdrobromac acid or dissolving in formic at and precipitating by the addiuor."o-f water. The composition of these mixed substituted cucutit{n3uriis was determined by Electrospray Mass Spectrosconv. Notes B 2. The Tetracyclic ether B refers to B. described in the mechanistic ere the substiruents R are ayI, aryl, phenanthroline anti pyridyl. Pera toluene sulphonic acid was the acid of choice for the tetracvclic ethers where R equals aryl or ~yridy1 and the temperature of the reaction mixture was maintained a: 11000. Exsmnle Analysis of Cucurbituril Mixture The analysts ef the cucurbliuri reaction mixture is routinely carried on: by 1C NIMR. 'The resent inventors have been able to achieve the x-ray crystal structure for cucurbitf5)urii, oucurbitSlurl and cucurbitf 102 nrA. These are shown hereunder, Srructures of zucurbirturil. cucurbit[SJuril and cucurbit{l0]uril as determined by x-ray crystallography, Waters, salts etc. of crvstallisatiun are not shown, (CucurbitE6]urii is wet established in the literature.) Solutions of pure cucurbiti7]uffl, as determined by ~C NMR have been prepared and Blectro-Spray Mass Spectroscopy has confunned the presence of only cucurbitL2]uril. (While pure cucurbiff7]urii is a crystalline rn~ rn et The results of this Table are graphieaflv shown in Figures and 3, Using this info~atior.. the inventors have now identified zuourbit[]uril (methine carbon 73.45 p~rn and methylene carbon ~5.42 ppm) in standard reaction nii~tures. Cucurbit[ Ijuril and cucurbitF 12)uril have only been observed by the methylene carbon when ~C labeLed formaldehyde was used as a reactant. Under these conditions the ouourbitfll2uru methylene carbon was observed at 56.86 p~m and the cucurbitf2~uril metbylene carbon was observed at 5775 ppm. The inventors have routnely used the integration of ~C MAR over the methine region of the spectra to determine the relative amounts of each cucurbit[n]uzfl in the mixture, In... d.oing so it was assumed that the signs]. response for each species is related to the number of methine carbons for that eucurbit~n]uril and that there is little difference in signal response between the different cucurbit[n3urils. The integration-percent is then directly pro'oortional to the mass percent of each, component. Exa~pie 4 Synthesis of cucurbitfujurils in hydrochloric acid. ~1ycoIuril (250 mg) and hydrochloric acid (36 % w/v,2000 rnL) were placed in a reaction flask. Formna]in (40% w!v) '250 p.12 was added in one portion and the reaction mixture heated to 00CC for 15 hours, The reaction mixture was cooled and the products were collected by the removal of solvent on a rota-y evaporator, Yield ~3C % by N1~ Appro~u~ate Yields b~ ~C NMR (% of recovered product. cucurbit~5lurU cucurbit6]uri 42% cuczbitr'7~u:i cucurbitf.~luril cucurbi:~9jurii cucurbit( I O3uril cucurbi: 1 i~urll Synthesis of cucurblt[n]urils tn sulfuric acid~ GiycolurL (500 mg) and sulfuric acid (9 M. 500 mM were placed Li~ a reaction flask. Fortualin (40% w/v) (250 uL, was add.e~ in. one portion and the reaction mixture heated to I 00~2 for 15 hours. The reaction mixture was cooled and the products were precipitated by addition of methanol and Yield —S5 % by NMP.. A~roximate Yields by ~C ~ (% of recovered product) cucurbit~5juri1 21% cucurbitE6~uril 64% cucurbit[T;uril cucurbit~8~uriJ I cucui~uri~ cucurbit~l0~uril cucurbit[l1~uril example 6 Synthesis of cueu~bit[n]uri1s in sulfuric acid. G~ycoluri1 2.5 g) and sulfuric acid (9 M~ 6.9 mL) were placed in a reac~on flask. Formal.j.n (40% w/v) (1.5 n~.L) was added in. one portion and the reaction mixture heated to ~.00~C for 3 hours. The reaction mixture was cooied and the prodt~cts were ~naiysed by ~C NMR. Yield >98 % by NMR Approximate Yields by ~3C NMR (% of recovered product) cucurbit(5]uril 26% cucurbitt6]uril 49% cucurbit{2~uril 19% cucurbicl8~urii 6% cucurb49juril %rZl % cucurbithl0]uril cucurbitrlljuril Synthesis of cucurbitln~1uri1.s in hydrochlork acid. Glycoluril (77 ~ an~ hydrochioris acid (10 M. 0.4 mL) ~vere placed in ~ reaction flask. ? ~aform~dehyd~ (3 mg) was added in one portion and the reaction znixture heated ic 105CC for 2..5 hours. The reactior. mixture was cooled and the products were analysed by 1~CN1v2~ Yield >~ % by NM~ Approximate Yieid~ by ~ C MvIR (% of recovered product) cucurbit(S~uril - 19% cucurbit~6)uriI 54% cucurbitL7~urii cucurbit8lurii 6% cucurbitL9juril cucurbitfi0Ju~i cucurbi2.1]uril Ex~~ie8 Synthesis of cucurbit[n]urils it hydrochloric acid. 0-lycoluril (7? mg) ano hydrochloric acid (9 M. 0.4 nIL) were placed ~n a reaction flask. Para.formaldehyde (23 ~g) was added in one portion and the reaction ~ixmure heated to i05~C for 2.5 hours. The reactior. mixture was cooled and the ;roducrs were analysed by ~C NMR. Yield >98 % by NMR Approximate Yields by :SC NI~ (% of recovered product) cucurbit~5~uril 18% eucrbit~G~uri1 56% cucurbitt7iuril 19% cucureitESiuril 6% cucurbit~9jjuril cucurbit~ I 0~uriI ~ cucurbat{1 1Juril Exampie 9 Synthesis of cucurblt[njurik lit hydrochloric acid. Glycoluril (77 ntg) and hydrochloric acid (~ M, 0.4 mL) were placed in a reaction flask, Paforrualdeityde (33 mg) was added in one portion and the reaction n~ixture heated to 1050C for ~ ~ bours. The. reaction mixture was cooled and the products were analysed by Yield. >~ % by NMR Apri~ximate Yields by ~ C NMP. (% of recovered product) cucuroit~5]urE 15% cucnrbitl6lurL cucurbit7lu:il 23% cucurbic[Siuril 4% cucurbit~9Jurii cucurbit 1 Oluril cucurbixE :Juri! Bxantnle 10 Synthesis o~ oueurbitfnjuirlls ix~ hydrodhioric acid. 2lycoiuril (7? mg) and hydrochloric acid (7 M, 0.4 ruL) were placed in a reaction flask. Paraformaldehyde (33 mg) was added in one portion and the reaction mixture heated to 1 05CC for 2.5 hours. The reaction mixture was cooled and the products were analysed by 1~C NMR. Yield >9~ % bY NIv~ .~p~roxitnate Yields by ~C NMR (% of recovered product) cucurbit~51uril 18% cucurbi:lEluri 57% cucurbitEluril 23% cucurbi:L8]urll 3% cucurb4~) uril ~.. % cucurbitf 10] uril ~ 1% zucurbitiji .~urfl Synthesis of cucurbit~njw11s in hydrochloric acid. Glycoluril (77 mg) and bydrochloric acid (5 M, 0.4 nIL) were placed in a reaction flask. P~raformaldehyde (33 mg) was added in one portion and the reac~.on inixmre heated to 10502 for 2.5 hours. The reaction mixture was cooled azLd the pro~cts were analysed by 122 NMR. Yield >8 % by Nl~ Approximate Yields by 1~C NMR (% of recovered product) cucurbit[5] uril 10% oucurbit[6urii 60% cucurbit[7}uril 27% cucurbit{~Juri1 3% cucurbitE9iurij cucurbit[10]uril cucurbif 1 l~u:i Synthesis of cllcurbitfn)urHs in bydroch~oric acid Givcoluril (2,L g) and hydrochloric acid (36 % w/v, 2 z~) were placed in a reaction flaSk. ~ormahn (40% w/v) (2,4 rnL) was added in one portion and the reaction mixture heated to 1 100C for 3 hours. The reaction mixture was cooled and the products were analysed by C NMR. Yield >9S % by NMR Approximate Yields by ~C NN~ (% of recovered product) cucurbit~5juril 6% cucurbit[6Ilurii 60% cucurbit7juril 30% cucurbit~8]uril 3% cucurbit~9]uzi cucu~bitf 1 OJuril cucurbit~i i)uri Example Synthesis of cucurbir[n]urils in hydrochloric acid. Glvcoluril (2.4 g~ and hydrochloric acid (36% w/-v. 2 n~) were placed in. a reaction ~1ask. Formalin (40% w/v'; (2,4 mL) was added in one portion and the reaction ~ii~twe heated to 11000 for 18 hours, The reaction -mixture was cooled and'the products -were analysed by ~ NMR. Yield >9S %byNN~ Appro,dmate Yields by C N1v~ (% of recovered product) cucurbit~]uril 6% zucurbit~6IIuril 60% cucurbit~7]uri1 30% cucurbit8]uril 2% cucurbitL9juril cucurbitfl.0]uril cucurbith i]urIl Example 14 Synthesis of eucurbitLn]urils in hydrochloric acid. Glycoluril (2,1 g) and hydrochloric acid (36 % w/v, .3 tt2L) were placed iii. a reaction flask, Paraforntaldehyde (S87 mg) ~was added in one portion and the reaction tu.ixture heated to 11000 for 18 hours, The reaction mixture was cooled and the products were analysed by Yield >98 % by NM?. Approximate Yields by '~C NM?. (% of recovered produt., cucurbit5)urii 9% cucurbit~61uri 52% cucurci:r7]uril 29% cucuroit[~3uril 8% cucurbi:LJuril ctacurbitll0]uri2 cucurbit~2 i]urii Synthesis of cucurbitErijurils in hydrobrorriic acid. GlycolurLi (Z 1 g) and bydrobromic acid (4~ % w/v, 3 inL) were placed in a reaction flask. Paraformaldehyde (887 ntg~ was added in one portion and the reaction mixture heated to l OODC for 18 hours. The reaction mixture 'was cooled and the products were analysed by C NM?.. Yield >98 % by NM?. Ap~ro~zinate Yields by ~C NM~. (% of recovered ~roduc~ cucurbit[5)uril 8% cucurbitE6]urii 50% oucufeit7luril 29% cucurbtrF8}uzil 12% cuzurb:t9lurii cucuKoit: oucurbitl i]uril Exana~le 16 Synthesis of cucurbitfn)urils in hydrochloric acid. Glycoluri~ (1 0~ nag~ and hydrochloric acid (36 % w/v, 0,4 mL) were placed in a rea~ton flask, Formalin (40% w/v) ~105 ~2L) was added in one portion and the reaction mixture heated tc 60CC for 63 hours. The reaction mixture was cooled and the products were analysed by ~C NMR. Yield. >8 %byNN.~. Approximate Yields by ~C NMR (% of recovered product) cucurbitE5]urfl 4% cucurbit~6Juril 64% cucurbitE7]uril 23% cucurbitt8juri 9% cucurbitLuril cucurbitLi03uril cucurbit~2 lIuril S~rnthesis o~ cucurbit[njjurils in hydrochloric acid. Glvcouril .. ~g) and hydrochloric acid (8 M, 0.4 naL) were placed tr~ a reaction flask. Parafortnalae:vde (23 ~g) was added in one portion and the reactior. mixture. heated to I 05CC for 2~ hours. The reaction mixture ~'as cooled and the products were analysed by Apprcx~Inate Yields by ~C NIV~ (% of recovered product) cucurbitL5ThrLi 13% cucurbiz~6~uril 60% curbit~7juri 22% cucufoitE8]uril 10% ct~curbit[9juril ~2 cucurbitfl0)uril cucurbitKl]uril Exampie 18 Synthesis of cucurbitErilurils in phospbnric acid. O¾cciurii ~>5 ~) and ~hos~horic acid ~conc, 6~ n~L) were placed in. a reaction flas..~t, (40% wp~ -: ~orrnaiin - ~L wa~ added in one nortior~ and the :eacnon m~x:ure heated to 00CC for I ~ hours. 'he reaction mixture was cooled and the products were analysed b'v ICNMR, Yield >9~%bv NMiR Ap~roxiInate Yields by - C Nl~ (~ of recovered product) cucurbit~)uri1 10% cucurbitFG~uril 50% cucurbitl7luril 28% cucurbitf8>ril cucurbi:E9]urfl cucurbitf10juril cucurbit[1'JuriI ~le19 Synthesis of cticurbit[n]urlls in hvd~ochIoric acid, C->'cKurii 1.02 g) and hydrochloric acid (36 * wfv, 0,5 tnL) were placed. in a reaction flask, Paraformaldebyde (~.3 0 mg) was added in one portion and the reaction mixture heated to 100CC for 15 hours. The reaction mixture ~as cooled and the products were analysed by "~C NM?.. Yield >9~ % b~ NM?. Ap~rcximate Yields bx C NM?. (% of recovered product) cuzuroltlflluriI 4% cucurbit~6]uriI 53% zucurbi:7)urL cucurbitrs]urii cucurbi:rjuril cucurbitV~0]uri1 Example 20 Synthesis of cucurbitEnlurils in deuterated ~u1f uric acid. GlvcolurL (Th nag) and deuterated sulfuric acid (c.onc, 0,4 naL) were placed in a reaction flask. Formalir. (40% w/v) (72 p.L) was added ir. one portion and the reaction mixture heated to rt~C for 2 months. The reaction mi~tture was cooled and the products were an~ysed by ~C NN~~ Yield >9~ % by NIvIR A~oroximate Yields b\ ~C NMR (% o recovered product) cucurbit5]uril cucuroit~6]uri >95% cuzurbit'T2uril cucufoitf~)uril zucurbit(9lurr <.1> cucurbit~03urfl cucurb Synthesis of cucurbittn)urils in hydrochloric acid. Glycoluril (108 nag) and hydrochloric acid (36 % w/v, 0.4 nJ...) were placed in a reaction flask. Formalin (40% w!vl (108 ~.tL) was added in one portion kept at room temperature for I month. The products were analysed by ~ NMR. Yield -No cucurbiturils present NI'A~ suggests oligomeric product. Exar~nie 22 Synthesis of cucurbit[nlurils in hydrochloric acid. Ulcoluril (1000 g) and hydrochloric acid (36 % w/v 1420 mM were plahed in a reaction flask. Paraforntald.ehvde (422 g ) was added in one portion and the reaction mixture heated to I05~C for 18 hours. The reaction mixture was cooled and the products were collected by :he removal of solvent on a rotary evaporator. Y~eio cua~ltativ~ -nas~ ~coverv and >E % cuci.~rbit .2urilL. Y~ NMF. .4nprox~jnatc Yicid~ b', 'C NM?. ~% of recovered prociuc~ cucu:bit[fjuril zuzbit~6JurLi 47% cucurbitT3urii 27% cucurbttfSjurll 6% cuc..~rbitrjuriI cucurbitl0]u:il ~2 % cucurbit~I jurii Exan~ple 23 S~n thesis of cucurbit[njurils in p-tohaenesulfonic acid. GlycoiurLi (I gj and p-toiuenesulfonic acid (—90 % w/w, 6S g) were placed in a reaction flask. Forni~Iin (40% wK) (1 mL ~g) was added in one portion and the reaction mixture heated to 1 O0~C for 2 hours, The reaction mixture was cooled and the nrod.ucts 'were nrecinitated by additioc of methanol and collected by vacuum filtratior., Yield >9~ % by NM? A~prcumate Yields by 22 NMR (% of recovered product) cucuroi:~. 6% cucurbitF63uril 68% cu curbit [7 uril 20% :ucurb~:ES~uril 5% curoit~9~rLi oucurbit~i0Thrii zucurb±t7>]urii Example> Synthesis of cucurbitEnjurils in methane sulfonic acid, ~1ycoluri '146.5 mg) s~d naethane sulfonic acid (neat, 1.5 niL) were placed in a reaction flask, ?arafomialdehyde C65 .5 nig) was added in one portion and the reaction mixture heated to 90CC for 22 hours, The reaction mixture was cooled and the collected using a ccnu-ifuge.Tbe collected solid was then dried at S0~C overnight. Yield >98 % by NM? A~proxinaate Yields by ~ C NM?. (% of recovered nroduct) cucurbitf 5] urfl 6% cucurbitlE]uril 52% cucurbit[7]uril 33% •cucurb~t[8]uril 9% cucmrbit[9juril cucurbit{l0]uril cucurbijii>ri.l Exarn~'±e 25 Synthesis of cucurbitEn)urils in methane sulfonic acid. Glycoinril 197.6 mg and methane sulfonic acid (neat, 2.5 nU~) were placed in a reaction flash. Paraforznaldehyde (91.1 mg 'was added in one portion and the reaction mixture heated tc 9000 for 23.5 hours, The reaction mixture was cooled and the collected using a centntu2e.The collected solid was then dried at 800C overnight. Yield >98 % by NM?. A~pr9xtmate Yields b~ UC NM?. (% of recovered product) cucurb~m[5iuriI 8% cucurbitl6]urll 54% cucurbli~7]uri1 30% cucurbic~8]uril 8% cucurbit[9]uril cucurbit0Nril cucurbit~ II )uri Example 26 Synthesis of cuourbltEnlurils in methane su~fonk acid, G~vco!ur~~'32Z,t mg> and methane suifonic acid (neat. 15 mL.' were o~aeed In a reaction nias~:. Parafor~aldehyde 1302 mgj was added in one portion and the reaction mixture heated rc 0~C for 23.5 hours. The reaction mixture was cooled and the collected using a centrifu~e.The collected solid was ±en dried at 8002 overnight. Yield >98 %by NM?. NM? (% of recovered product) Apnrox~mate Yie±es cy ~C cucurbit~5~urfl 3% cucur~i:L6]uril 54% cucurbit7]urii 32% cucur~it[8]urii 11% cucur~it[9]urii cucurclt[ 1 OJuril cucurbit(i Ijuril ~.xample 27 Synthesis of cucurbitEnjurils in methane ~uIfonic acid~ G-lycoluril (497.3 nag) artd methane sulfonic acid (neat, 1.5 ~nL) were placed in a reaction flask. Paraformaldehyde (20~.,0 mg) was added in one portion and the reaction mixture heated to 9002 fo: 25 dours. The reaction mixture was cooled and the collected using a cer~rrtfuge.The collected solid was then dried at 800C overnight. Ao~rirnate Yieldsbv C NM? '% of recovered Droduct~ cucurbit5~uriI 0% cucurbitl6iuril 77% cucurWt~7]uriI 23% cucurbit~8]uril cucurbitE9~uri1 cucurbi~liO]uril ~I % cucurba~Ji l)urLi Exani~1~28 SvnthesL~ of cucurbit~n]uri1s in methane sulfonic acid, Glyc.oiuril 1144,6 mg) and methane sulfonic acid (neat, 1.5 mL) were placed. in a reaction flash. ?araforrnaldehyde (61.3 nag) was added in one portion and the reaeti:6n mixture heated to 700C for 22,5 hours. The reaction mixture was cooled and the co~lectcd using a centrifugeThe ~oUected solid wa~ then dried at SOCO overnight. Yield >98 % by NIv~. Approximate Yields by ~C NM? (% of recovered product) cucurbit[Suril 0% zucurbitE6jurll 49~c cucurbitFiuril 34% cucurbltr8iuril 17% cucurhit~9juril cucurbitr 101 uril ~l % cucurbitFi 1)uril Exarn~1e 29 Synthesis of cucurbit[n]uri~s in methane sulfonic acid. Glycoluril (145,2 mg) and methane sulfonic acid (neat, 1.5 mL) were placed ~ a reaction flask. Paraformaldehyde (62.9 nag) was added in one portion a.nd the reaction mixture heated to 3000 for 24 hours. The reaction mixture was cooled and the collected usizg a centrifugeThe collected soi~d was then dried at 800C overitight. Yield >9~ % by NMR Approximate Yields by ~C NM? (% of recovered product) cucurb~t[5~uril 4% cucur'oit[6]urfl 56% cucurbit['7Juril 28% :ucurbit[SJuril 11% cucurbit{9jurii ~l % cucurbit[l0]uril ~z1 % cucurbttL~ juril 30 Exam~> 30 Synthesis of cucurbit~n]uri1~ in methane sulfonio acid, Glycoinril ~l4 5 nag and methane sulfonic acid (neat. 1,5 mL; were placed in a reaction fiasi.2. Paraformaldebvde (60.7 tug) was added in one portion and the reaction mixture heated to 1000C for 25 hours. The reaction mixture was cooled and the collected using a centriuge.The collected solid was then dried a: 30CC overnight. Yield >9~ % by NM?. A~pprqximate Yields b~ ~C NM?. (% of recovered product; cucu~it5]urL 3% cucuroitF6~urLi 59% cucurbitL7luril 32% cucuroit{8]uril 6% cucurbit~9lufll cucurbit~10juril .zi % cucuroit~l ijuril Bxaxn~ie 31 Synthesis of cucurbit[n]urfls in methane sulfonk acid. 2iVcoluril (i~±~ .3 nag) and methane sulfonic acid (neat, 1.5 rnL) were placed in a reaction rIa~h. Paraforutaldehyde (60.2 nag) was addec in one portion .and ~he reaction mixture heated to Ii 00C for 27 hours. The reaction mixture was cooled and te collected using a centrifugeThe collected solid was then. dried at 800C overnight. Yield >9~%by NM?. ~ Nv~. (% of recovered product) Approximate Yields by cucurbitESluril 0% cucurbit[6]uril 93% cucurbit[7]uril 7% cucurbit[S]urii 0% cucurbitf9]uril ~zl% cucurbit[10]urii cucurbitll 1]uril 2xam~le 32 Synthesis of cueurbit[n]urils in methane sulfonic acid using o-carborane as azi added template. Glycoluril (146.9 mg), methane sulfonic acid (neat. 1.5 mL) and o-carborane (—18 nag) were placed in a reaction flask. Paraformaldehyde (64.2 nag) was added lit one. portion and the reaction mixture heated to 90CC for 22.5 hours. The reaction mixture was cooled and 31 the nroducts were pecipitated by addition of ethanol and collected using a :~ntrifuge The collected solid was ther- dried at 80~0 overnight and analysed by ~C Ni~.. Yield >98 % by' NlvrR Approximate Yields by ~ NMR (mass % of recovered product; cucurbit[5]urll 5% cucurbitl6]urd 52% cucuroitijurii 31% cucuroit[Siurii 10% cucurbitd]urii cJ cucurbitfiOluril cucurbitji]uril Synthesis of cucurbitfnjurils In methane sulfonic acid using o-carhorane as an added template. Glvcoluril (200,5 nag). methane sulf'onic acid (neat, 1.5 rnL) and o-carborane (102,7 nag) were placed in a reaction flask. Paraformaldehyde (94.2 nag) was added In one portion and the reaction mixture heated to O~C for 24 hours. The reaction mixture was cooled and the nroducts were pecipitated by addition oS ethanol and collected using a centrifuge.The collected solid was then dried. at SO~C overnight and analysed by' 132 NM?.. Yield >98 % by NM?. A~pro~urnate Yields by 'Q NTh~ (mass % of recovered product) cucurbiz{Sjuril 8% cucurbit[6]uril 53% cucurbir(7]uril 29* cucurbitESluril 10% cucuroit9]uril cucurbi:rl Oluril oueuroit[l l]u.ril 2xample 34 Synthesis of cucnrbit[n]urils In methane sulfonic acid using o-carborane as an added template. Glycoluril (299.0 nag). methane sulfonic acid (neat, 1.5 nat) and o-carboa'ane (152.4 mg) 'were placed in a teaction flask, Paraformaldehyde (126,2 nag) was added in one portion and the reaction mixture heated to 90CC for 24 hours. The reaction mixture was cooled and the products were pecipitated by addition of ethanol and collected using a centrifugeThe collected solid was then dried at 8002 overnight and analysed by '~C NM?.. Yield >98 % liv NM?. Approximate Yields by 22 NM?. (mass % of recovered product) cucurbit5]uril 3% cucurbi: TFuri~ 33% cucurbit~jun. cucur'oiz~91urii K cucurbitFl ?urL Exam~ie 35 Synthesis of cucn~bit~n3urlls in methane sultonic acid using o~ca'rborane a~ ati ad.cled template. Glycoluril (501.9 mg> methane sulfonic acid (neat. 1.5 rnL) an~ o-carborane (166.2 ~g) wem ol aced in a reacnoo flask, Paraformaldehyde (20'~S mg) was added in one portion anc the. reaction rn (turin heated to 9O~C for 25 hours, The reaction mixture was cooled and the products were pecivitated by additior. of ethanol and collected using a centrifuge The collected solid was then dried at 80CC overnight and analysed by ~C NMR. Yield >9~ % by NMR Apprc~dmate Yields by ~ C N1AR (mass % of recovered product) cuc~rbit~5]uril 0% cucurbit~6luril 63% ;ucurbi:flTJuril 28% cur:itjjB]uril 9% cucurbi:l~uril cucuroitll0]uri~ cuzurbit[il]urii Examnie 36 Synthesis of cucurbit~njurils in methane sulThnic acid using o-carborane a~ an added template. Glycoluril (145.0 mg), methane sulfonic acid (neat, 1.5 rnL) and o-carborane (53.4 mg> were niaced in a reaction flask. Paraformaidehyde (62.5 mg) was added in one portion ~nd the reaction mixture heated to 70CC for 22.5 bonrs. The reaction mixture was cooled and the products were pecipitated by addition of ethanol an,d ~ollec~ed using a cen~ifuge.The collected solid was then dried at S0~C over.ight ~d analysed by ~C NMR. Yield >98 % by NMR Approximate Yields by ~C NMR (mass % of recovered product) cucurbit~5]uril 0% cucurbim~6juril cucurbi:FJuril 32% cucurbit~8Juril 20% cucurbit~9]uril cucurbim~10luril zucurbi:~ll]uri1 Examole 37 Synthesis of cucurbit[njurils in methane sulfonic acid using o-carborane as an added template. Clycoluni (146.9 nag). metnane sulfonic acid (neat, >5 nI; and o-carborane (53,d nag) were paacec in a reaction flask. Paraformaliehyde (64.0 nag) was added in. one potor. and the reaction mixture heated to SO~C for 24 hours. The reaction mixture was cooled and the produces were pecipitated by addition of ethanol and collected ustn~ a centhfugcThe collected solid was then dried a: S0~0 overnight and analysed by '~C NM?.. 71e16 >98 % by NM?. Approximate Yields by 12Q NMR (mass % of recovered product) cucu:bi:ES]urti 4% cucurbit?Sjurii 48% cucurbitVflurfl 29% cucuti:ESiu 199 cucurbieF9j~rE cucufoi: 1 OJuril 'K cucorbictl i]uril Bxampie 3t Synthesis of cucurbit[n)urils in methane sulfonic acid using o~carborane as an added template. Glycolur? (>2.? rrig~, methane sulfonic acid (neat. >5 mD and o-carborane (48.6 mg) were placed in a reaction flask. Parafoznaldehyde (60.7 nag) was added in one portion and The reactior. mixture heated to i0002 for 25 hours, The reaction mixture was cooled and the products were. pecipitased by addition of ethanol and coliected using a centrifugeThe collected solid was then dried a: 80CC overnight and analysed by '~0 NM?.. Yield >98 % by NM?. Approximate Yields by 150 NI\~ (mass 9 of recovered producr~) cucurbit[5]uri 2% cucurbi:E6] ThI 53% cucurbit[7]uril 31% cucurbic[8>ril 14% cucurbitf)urll cucurbitflOjuril 1% cucurbit2 Ijuril C 9 Examnk 3 Synthesis of eucurbitfn~uri1s in methane sulfonic acid using o-carborane as an added template. &~ycoiurE (145,5 zg> methane sulfonic acid (neat, 15 n~L) and o-carborane (4~ mg) were niaced in a reaction fiask. Parafcrtna~dehyde (60,? mg) was added in one portion and the reaction mixture heated to 11 00C for 2? h~ut& The reaction mixture was cooled and th: products were pecipitatod by addition o~ ~t~anoi and oollected using a centrifuge.Thc colie.cted solid was then dried a: 800C overnight and analysed by ~C NMR. Yield >98 % by ~ '~ c ~ (mass % of recovered ~roduct~ Approximate Yields b~~' - cucurbitf5)uril 0% cueu:bitE6jurU 65% cucurbitE7luril 26% cucurbit[S3urii 9% cueurbit[9~uril cucurbit~l0~uri1 K % zuciirbirjlllurii Exam~ie 40 Sytithesis of cucurbi~[nlurils in hydrochloric acid using thicacetanaide as an added teniplat~. Glycoluril J42. 1 mg> hydrochloric acid (36 % w/v, 0.7 rnL) ~nd thioacetamide (12.8 ~g) were placed in a react~on flask, P formaldehyde (60.0 ing) was added in one portion and the reaction mixture heated to 95CC for 4 hours, The reaction mixture was cooled and the products were coliected b;' the removal of solvent on a rotary evaporator and analysed by NMR. Yield>98%bvNMR Approximate Yields by Th NIv2. (mass % of recovered prodt~ct) cucurbi:E5]uril 0% cucurbitE6)uril 64% cucurbitE7~uril 36% cucurbit[Sjuril 0% cucuzbitEjurii cucurbitEl0]uril cucurbit{1 l~uri Examnie 41 Synthesis of cucurbit~jn]uri1s in hydrochloric acid using N..(1-napthyl)ethy~ened.iazn.ine as an added template. Givcoiurili (11.2.1 nag). hydrochloric acid (36 % w/v, 0.7 ~L) and Minapchl)ethylenedia7nine (44.1 n~g) were placed in a reaction flask. Paraformaldehyde (60.0 mg) was added in one portior and the reaction mixture heated to 9500 for 4 hours. The reactior. mixture was cooled and the products 'were collected by the re~ova1 of solvent on a rotary evaporator and analysed by NM?.. Yield >9E 9 by NM? Approximate Yields by 15C NMR (mass % of recovered product) cucurbit[5Juril 12% cucurbitf6lurii 53% cucurbitf7lurii 22% cucurbitf8]uril 12% cticurbitE9]u.ril cucurbitliOjuril cuc~rbitI l]uni ExamLe 4~2 Synthesis of cucurbitEnjunils in hydrochloric acid using 2.2 -biquinoyl as an added template. Glycoluril (142.1 nag). hydrochloric acid (36 % w/v, 0.7 mL} and 2,2'-biquinoyl (43.6 mg) were placed in a reaction flask. Parafo~aldehyde (6C,0 mg) was added in one portion and the reaction mixture heated to 95~C for 4 hours. The reaction mixture was cooled and the products were collected by the removal o~ solvent on a rotary evaporator and analysed by NMR. Yield >98 % by NMR Approximate Yields by bC NM?. (mass % of recovered product) cucurbirE5juri2 6% cucurbitI6]uri~ 62% cuctarbit['7]urij 26% cucurbftf8]uril 6% cucurbit[9]uril cucurbit~10Juti1 cucurbir~l l]uril Exam~ie. 43 Synthesis of cncurbitEn~rils in hydrochloric acid iasing p-bromoaniline as an added template. Glycoktrii (142,1 nag), hydrochloric acid (36 % wlv, C.~ rnL) and -bromoan3line (29,3 mg) were placed in a reactior. flask. ?~raformaldehyde (60.0 mg) w~s added in one potion and the reaction mixturt heated to 950C for 4 hours, The reaction ~ix~ure was cooled and the products were collected o~ the removal of solvent on a rotary evaporator and analysed by' Yield 9~ 9 bx' NM?. ApproxImate Yield.s b~ '~C NlvrR (nasa % of recovered product) cucur~itE5]uriI 11% cucurbitE6]urll 36% cucuroit7junl 36% cucur~it[8]uril 15% cQcuroit[9]urii cucuroit[l0]uril cucuroitf 1 1]uril Bxamnle 4~ Synthesis of cucurbit~n]urils in hydrochloric acid using tetrabutylammoniu~ chloride as an added template. Glycoluril (142.1 nag), bydrochlotic acid (36 % w/v, 0,7 nI) and tetrabutyla~nmonium chior2de (47.3 nag) wers placed in a reaction flask, Parafornaaldehyde (60.0 rug) was added in one ponion and the reaction mixture heated to 95CC for 4 hours. The reaction mixture was cooled and the products were collected by the removal of solvent on a rotary evaporator and analysed by NMR. Yield >98 % by NM?. Approximate Yields by ::C NN{R (mass % of recovered product) cucurbit[5]u.ril 5% cucurbitE6]urll 55% cucurbitF'7]uril 25% cucuroit[8~uril 5% cucurbit[93ur11 cucurbit[lOjuril oucurbitElliuril hxamule 4~ Synthesis of cucurbit~n]urils in h~drochkoric acid u.sing taurine as an added template. Glycoluril ~I4Z.I mg), hydrochloric acid (36 9 w!v, 0.7 mL) and taurine (21.3 rug) were placed ir. a reactior. flask. Paraformaldebyde (60.0 mg) was added in one. portion and the reaction mixture heated to 95CC for 4 bours. The reaction mixture was cooled and the products were collected b~ The removal & solvent on a rotary evaporator and analysed by NM?. Yield >9~ % by NM?. Approxrnate Yields by 'C N1v~ (mass % of recovered product) cucurbit[Slurii 16% cucurbitf6]u:il 51% cucurbit'7]uril 23% cucurbitL8]uri) 10% cucuxbit[9]urll cucurbitl0]uril cucurbitFl ]uril Examvle 46 Synthesis of cucurbit[n]urlLs in hydrochloric acid using blue retrazoliLtxri as an added template. Glycolurd. '142.1 mg) hydrochloric acid (36 9 wh.', 02 mD and. blue tetrazolium (123.7 rug) were placed in a reaction ~1ask. Paraformaldehyde (60.0 rug) was added in one p~rt~on and the reaction mixture heated to 95CC for 4 hours. The reaction mixture was cooled and the producrs were collected by the removal of sol~ren: on a rotary evaporator and analysed by NM?.. Yield >S. % by NM? Approximate Yields by 3C NM?. (mass % of recovered product) cucurbitE5]urii cucurbitE6}uril 55% cucurb47]uril 23% cucurbit[8]urii cucurbirE9juril cucurbitllOluril cucurbitf 1 i]uril Bxaz~le 47 Synthesis of cucurbit[rijurils in 1~ydrochloric acid using 2-amino..3-methyl benzoic acid as ai~ added teniplata. Glvcoiurfl ~42.1 rng~, hydrochloric acid (36 % w/v 07 rnL) and 2~arnino-$-rnerh.y1 beuzoic acid (25,7 mg) were placed in a reaction ~1ask. Paraformaldehyde (60.0 rug) was adae~ i one po~ior. an~ the reaction mixture heater to ~5'~C for ~ nours. The reaction mitrure was cooled and toe produet~ wem collected b~' the remova of soiven: onaro.tary evao orator and analvse~ b\ NN~. Yie.id >98 9 bvNMR Approx2znatt Yields by '~2 NM?. (mass % of recovered product) cucurbit~5;~ril 59 cuzt~rbitf6juri~ 55% cucur:flurii 25% zuzurbitF8)urli 59 cuzuro~tf9]urii zuzuThitJmuri cucurbit jurL Example 48 Synthesis of cucurbitEn:iu.rils in hydrochloric acid using indoi-3-aldehyde as an added template. Givooluril (i42. nag). hydrochloric acid. (36 ~ w/v. 0,7 rnL ane rndo~-3-aldebyde (24.7 rug: were placed in ~ reaction ±iask. ?araform~ldehyd.e (60.0 mg) was added in one portion end the reactioh mixture heated to 950C for ~ hours. The reaction inixture was cooled and the products were collected by the removal of solvent or~ a rotary evaporator and analysed NMR Yi.eid >98 ~ by NM?. Approximate Yields by ~C NMR (mass % of recovered product) cucurbit(5]urii 39 cucur'~iU6~uril 70% eucurbitf7]uril 25% cucurbitES]uril 29 cucurbitr9]uril ~ti % cucurbitEl0]uril <:1> cucurbit[ lJuril Example 49 Synthesis oT eucurbitfn)urils in hydrochiork acid using cystine as an added template. Glycoluril (142.1 nag), liydrochloric acid ~36 9 w/v, O.~ mL) end cyst~n.e (40. mg~ were placed in a reaction flask. Paraformaldehyde (60.0 nig) was added in one portion and the reaction mixture heated to 95CC for 4 hours. The reaction ntixttue was cooled and The products were collected by the removal of solvent on a rotary evaporator and analysed by NMR. Yield >98 9 by NM?. Approximate Yields by '~C NM~ (mass 9 of recoverd product) cucurbitE5juril 5% cucurO~t f6j ur2 ci~curoit r7j uri cucurbir[8]uriT cucurbiz[9] aril cucuroitV 0]uril cucurbi:l ]urii 55% 25% 5% <:9> Bxam~le 50 Synthes1~ of cucurbitinThrils in hydrochloric acid using p.acetamidoani.line as an added template. Glycoluril (:42.: mg), hydrochloric acid (36 % w/v, 0.7 ~) a~ p-acetamidoaniline (25.5 mg, were placed in a reaction flask. Paraformaldehyde (60.0 nag) was added in one portior. and the reacmiou mixture heated to 9500 for 4 hours. The reaction mi,tture was cooled and the products were collected by the removal of solvent on a rotary evaporator and analysed by MAR. Yield >9S % by NM?. Annroximate Yields by ~C NM?. cucurbit5]uril 5% cucurcitE6juril 55% cucuroit[7]uril 25% cucuroitE8]uril 5% cucu.rbir[;]uril cucuroitri iluril (mass % of recovered product) ~xa~ple SI Synthesis of cucurblt[n]urils in hydrochloric acid using p-azninophenol as an added template. Glycoluril (142.1 nag), hydrochloric acid (36 % w/v, 0.7 inL) and p-axninophenol (TS.6, rug) were placed in a reaction flask. Paraforinaldehyde (60.0 rug) was added in one portion and The react~on mixture heated to 9$C0 for 4 hours. The reaction mixture was cooled and the products were collected by the removal of solvern on a rotary evaporator and analysed. bYNMR Yield >98 %by NM?. Ap~rox.imnate Yields by '~C cucurbir[5]uril 13% cucurhitf6]uril 39% cucurbitE7li.nil 36% cucurbitE8]uril 12% cucurbit[9]uriJ cucurbitLlo]uril cucurbitf 1 1 luril NMR (mass % of recovered product) Exant~le 52 Synthesis of cucurbitinjurils In hydrochloric acid using acetamide as an added template. Glvcoluri (142.: nag). hydrochloric acid (3~ % w/v. 0.7 mL) ~d acetamide (10.0 rug) were placed in a reaction. flask. Paraformaldehyde (60.0 nag) was added in one portion and the reaction mixture heated to 95CC for 4 hours. The reactio.u mixture was cooled and tbe products were collected by the removal of solvent on a rotary evaporator and analysed by NM?.. Yield >9~ 9 by NM?. Anproximate Yields by ~ C NM?. (mass % of recovered product) cuourbit~5~urll 9% cucurbitEG3urii 31% cucurbit~7Juri 39% cucurbitE23uril 17% cucurbitE9~uril cucurbit 1 0~uril cucurbitEi liuril ExrnaDle ~3 Synthesis of cucurbitlln]urih in hydrochloric acid using 4-aminoacetophenone as an added tenipiate. Glycolufli (142,1 rug), hydrochloric acid (36 % w/v~ 0.7 mL) and 4-aminoacetophenone (3 .0 rug) were placed in a reaction flask. Paraformaldehyde (60.0 nag) was added in one portion and the reaction mixture heated to 950C for 4 hours. The reaction mixture was cooled and the products were collected by the removal of solvent ot~ a rotary evapora.tor and analysed by NM?.. Yield >9~ % by NM? Approximate Yields by '~C NTh~ (mass ~ of re~overed product) cucur~itf5uri1 9% cucurbit~63urU 44,5% cucuroitE7]uril 35% cucurbitE8juri). 12% cuctrrbitE9~urll cucurbit~10Juril cucurbit[i.1)uril Exarrrrle 5~ Synthesis of cucurbitEnlurils in hydrochloric acid using 4.. dimethylamlnobenzaldehyde as art added template. Glycoluril (142.1 nag). hydrochloric acid (36 % w/v, 0.7 znL) and 4-damethylarzilnobenzaidehyde (25~4 mg) were placed ic a reaction ~ Pataformaldehyde (60.0 mg) was added in one portion and the reaction mixture heated to 95~O for 4 hours. The reaction mixture was cooled and the products were collected by the re~ov.ai o~ solvent on a r~Lary evaporator and analysed by NMR. Yield >9S %bvNMR Approximate Yields by ~C NMR (mass % of recovered product) cucurbit[5]uril 5% cucur5it[6~urL 55% cucurbitE7]uril 25% cucurbi t~8luril 5% cucurbirE]utii cucurbit~ 1 Ojuril cucurbit(i ijuriJ Example 55 Synthesis of oncurbitlnjurih in hydrochloric acid usin,g 2-aminobeuzimaclazol as an added template. GlycoJuril (14Z1 rag), hydrochloric acid (36 % w/v, 0.7 rnL) and 2-axninobenzimadazol (22.6 tug) were placed in a reaction flask. Paraformaldebyde (60.0 mg) was ad.cled in one oortion and the reaction mixture heated to 950C for 2 hours. The reaction mixture was cooled and the products were collected by the removal of solvent on a ro~axy evaporator and analysed by NMR. Yield>98 %byNMR Approximate Yields by ~C NM?. (mass 9~ of recovered product) cucurbitf5]uril 9% cucurbitE6luril 40% cucurbit[7~uril 30% cucurbitJ~8juril 11% cucurbitE9~uri1 cucurbi:[lOJuril cucurbitEl juril Example 56 Synthesis of cueurblr[njurits in hydrochloric acid using bls-(4~4 .bipyridyl>ct, ct-pxylene as an added template. Glycciuri) (142,1 nag). hydrochloric acid (36 % w/v, 0.7 ruL) and bis-(4A-blpyrsdyl)-ot o~f-p-xv1ene (IC.8 nag) were placed in a reaction task. Paraforrnaldehyde (60,0 tug) was added in one portion and the reaction mixture heated to 95CC for hours. The reaction niixture was cooled and the products were collected by the removal of solvent on a rotary evaporator an6 analysed by NI\4R. Yield >95 9 by NM?. Approximate Yields by '~C NM?. (mass % of recovered product) cucurbitE5~uril 8% cucurbitf6jurii 42% cucurbit~7Juril 46% cucurbitF8]uril 5% cucurbitE9]uril cucurbit[l0~urii cucurbitll ijurE Example 5? Synthesis of cticurbitfn~urils in hydrochloric acid using tetraethylarrunoniunt chloride as an added template. Glvcoluril (142.1 rug), hydrochloric acid (36 % w/v, 0.7 mL) and tetraethylammon~urn chloride (2.8.2 rug) were olaced in a reaction flask. Paraforrualdehyde (60.0 mg) was added in one port on and the reaction mixture heated to 95~C for 2 hours, The reaction mixture was cooled and the products were collected by the removal of solvent on a rotary evaporator and analysed by NMR. Yield >98 % by MAR Approximate Yields by ~C NMR (mass 9 of recovered product) cucurbitr52uril 0% cucurbit[ 6)uril 10% cucurbit[73u~1 70% cucurbit[SJuril 18% cucurbitE3uril cucurbit[ 1 0)urfl Examole 58 Synthesis of cucurhit(n3urils in hyclroc.hioric acid using an~monium chloride as a~t added template. Q~ycoiuri (>49 g) hydrochloric acid (36 % wA, 6~ mL) and ammonium chloyide (280 mg~ were placed in a reaction flask. Formaliri (40% w/v) (1.5 naL) was added in one ponion and the reaction mixture heated to 1000C for 3 hours. The reaction rnb~ture was cooled and the products were collected by the removal of solvent on s rotary evaporator and analysed by NM?.. Yield >98 9 by NM?. Approximate Yields by ~ NIJ. (mass % of recovered product) cucurbitE5juril 15% cucurbit[6Juril 62% cucurbizV7 Juril 20% cucurbitf8)urii 3~c cucurbitE9)uril cucurbitEl0)uril cucurbit~I1]uri1 Examole 59 Synthesis of cucurbit[njurlls in hydrochloric acid using lithium chloride as an added template. Glycoluril (1.49 g), hydrochloric acid (36 % w/v 6.9 mL~ and litb chloride (211 mg) were placed in a reaction flask. Formalin (40% w/v) (1.5 ntL) was added in one portion and the reaction mixture heated to l0O~C for 3 hours, The reaction mixture was cooled and the oroducts were collected by the removal of solvent on a rotary evaporator and analysed b'v N~. Yield >98 %by NM? Approximate Yields by ~C NM?. (mass % of recovered product) cucurbit[5)uril 7% cucurbit{6~ uril c~curbitE7]uri1 22% cucu.rbit[8]uril 3% cucurbitE]uril cucurbitEl0]uril cucurbit[l ijuril Examoic 60 Synthesis of cucurbit(njurils in itydrochioric acid usi~,g ~odiun~ ebJoride as an added templaLe. Glycoluril (1.49 g., hydrochloric acid (36 % w/v, 6.9 mL) and sodium chloride (292 n~g) were placed in a reaction flask. Bormalin (40% w/v) (1.5 inL) was added in. one portion and the reaction mixture heated to 1000C for 3 hours, The reaction mixture was cooled and the products were collected by the removal of solvent on a rotary evaporator and analysed by NI~'TP~. Yield >9~ 9 by NM?. Approximate Yields by ~C NMR (mass % of recovered product) oucurbit5jurE 3% cucurbitE6~uril 73% cucurbirf7lurii 22% cucurbi48luril 3% cucurbit[]urii cucarbitflOjuril cucurbitEl Ijuril Example 61 Synthesh of' cucurbitfn)urils in hydrochloric acid using potassiims chloride as an added Lemplate. 2~ycoiurL (1.49 g). hydrochloric acid (36 % w/v, 6.9' mL) and potassium chloride (372 mg) were placed in a reaction flask. Formalir (40% w/v) (1.5 nL) was added in one portion and the reaction mixture heated to 100CC for 3 hours, The reaction mixture was cooled and the products were collected b~ the removal of solvent on a rotary evaporator and analysed by NMR. Yield >9~ %byNMR Approximate Yields by ~C NMR (mass % of recovered product) cucurbitL5iuril 2.4% cucurbir[6]uri2 61% cucurbitE7]uril 14% cucurbitESluril 2% cucurbitEjuril cucurbitflOjuril cucurbitElijuril Exarnole 62 Synthesis of cucurbitEnlurils in hydrochloric acid. using rubidium chloride as an added template. Glycoluril (1.49 g), hydrochloric acid (36 % w/'~, 6.9 mL) and rubidium c~oride (604 rug) were placed in a reaction flask. Formalin (40% w/v) (1.5 mL) was added in one po~ion and the reaction mixture heated to l00~C for 3 hours, The reaction mixture was cooled and the products were collected by the removal of solvent on a rotary evaporator and analysed by NMR, Yield >9~ % b~' NN'~. Approxima~ Yields by ~c N~N~R (mass % of recovered product) cucurbir[SJuril 14% cucurbi:[6JuriI 70% cucurbitE7juril 15% cucurbitL8juril cucurbitf9~uril .~ cucurbitElojuril cucurbitfl l3urii 'K Synthesis of ueurbit[ii]urils ha hydrochlDric acid using oaesiuin chloride as an added template. Glycoluril (1.49 g), hydrochloric acid (36 9 wA', 6.9 inZ) and caesium chloride (S42 nig) were placed in a reaction flask. Fornialin (40% w/y) (1.5 niL) was added in one portion and the reaction mixture heated to 100DC for 3 hours, The reaction mixture was cooled and The products were collected by the removal of solvent on a rotary evaporator and analysed by NMR. Yield >9S % by NMR Approximate Yields by ~C NMR (mass % of recovered product) cucurbitL5]uril 4% cucurbit~6)uril 79% cucurbltE7luril 16% cucurbitEBluril 1% cucurbitE9~uri1 cucurbitElOluril :cucurbit{1 l]uril Exatnole 5L Synthesis of cucurbitEnjurils in hydrobroinic acid using ammonium bromide 25 an added template. Glycoiuri K. 49 g> hvdrobromic acid (48 % w/v, 6S tuL) and a~soniurn bromide (490 mg; were placed ii-. a reaction flask, Formalln (40% wlv) (1.5 n2L) was added in one portion and the reactior. mixture heated to 1000C for 3 hours. The reaction mixture was cooled and the products were collected by the removal of solvent o~ s rotary evaporator and analysed by NMR Yield >98 % by NMR Approximate Yields by ~ C N1~ (mass % of recovered product) cucurbitL5~urll 8% cucurbitL6>ril 66% cucurbitE7lurii 23% cucurbitE8lu.rL 3% cucurbitfjuril 'K cucurbitEl0~uri1 cucurbit~i liLaril E~xaz~le 65 Synthesis of cucurbit[n~uriIs in hydrobromic acid. Glycoluril (I .49 g) and hydrobroinic acid (48 % w/v, 69 niL) were placed in a reaction thsk. Formalin (40% w/'4 (1.5 mL) was added in one portion and the reaction mixture heated to l0O~C for 3 hours. The reaction mixture was cooled ~nd the products were collected by the removal of solvent on a rotary evaporator and analysed by Nl~. Yiei]d>98 %byNM~. Approximate Yields by '~ C NM?. (mass % of recovered product) cucurbitf53urll 5% cucurbit[6Juril 59% cucurbitf7luril 30% cucurbit[8Juril 5% cucurbitL9I~uril cucurbitf lOjuril cucuroitE1l~uri1 E~iample 66 Synthesis of cucurbitEnjurils in hydrobrorn~ic acid using litb.ium bromide as an added t~inpIate. Oivcoiu:r Ki 49 g). hydrobrornic acid (48 9 wA'. ES mL; and lithium bromide (425 mg) were placed ir. a reactioL flask. Formalln (40% w~v). (1,5 mL was added in one portion and the reaction mixture heated to 000C for 2 hours. The reaction mixture was cooled and the products were collected by the removal of solvent on a rotary evaporator and analysed by NM?.. Yield >98 % by NMR Approximate Yields by ~C N.~'2. (mass 9 of recovered product)' cucurbatE5juril '7% cucurbit~6]urii 499 cucurbitfT)uril 36% cucufoith8luril 2% cucurbitE9~uril cucurbitrl0~uril cucurbitEl l]uril Example 67 Synthesis of cueurbit[nlhxrils in hydrobronile acid using sodium bromide as an added template. Glycoluril (>49 g), hydrobronaic acid (4~ % W/v. 6.9 mL) and sod.tum bromide (515 nig) were placed in a reaction flask. Formalin (40% w/v) (1.5 mL) was added in one portion and the reaction mixture heated to 10002 for 3 hours. The reaction mixture was cooled and the products were collected h~ the removal of solvent on a rotary evaporator and analysed by NM?.. Yield ~98 % by N1~ Approximate Yields by ~C NMR (naass % of recovered product) cucurbitESiuril 16% cucurbitE6]uril 44% cucurbitE7l Urli 35% cucurbit~8]uril 5% cucurbitL9]uril cucurbitLlo]uril cucurbitEl lIuril Examole 68 Synthesis of cucurbitfujurils in hydrobromic acid using sodium bromide as an. added template. Glycoluril (1.49 g), hydrobromic acid (48 9 w/v, 6.9 inL) and sodium bromide (5000 ing) were placed in a reaction flask. Formalmn (40% w/v) (1.5 mL) was added in one portion and the reaction mixture heated to 10000 ~or 3 hours. The reaction mixture was cooled and the products were collected by the removal of solvent on a rotary evaporator and analysed by NM?., Y2eld >9~ % by NMR Approximate Yields &' C cucurDitF5)uril 409 cucurbitE6]urii 51% cucuroit7]uril cucurbit[8]uril cucurbit[9luril cucurbit[ Ojuril 'K cucurbitfl Iluril NMR (mass 9 of recovered produci Examole 69 Synthesis of c~icurbitfn~urlls in hydrobromic acid using potassium bromide as an added template. Glvooluril (1.49 g), hydrobromic acid (48 % w/v, 69 mL) and potassium bromide (595 mg) were placed In a reaction flask, Formalin (40% w/v) (1.5 ~L) w as added in one portion. and the reaction mixti~e heated to I 0O~C for 3 hours, The reaction mixture was cooled and the products were collected by the removal o~ solvent on a rotary evaporator and analysed by N1vER Yield >98 % by NMR Approximate Yields by ~C NM~. (mass % of recovered product) cucurbit[fjuril 369 cucurbitE6)uril cucurbitE7)uril 18% cucurbitF8juril 2% cucurbitEluril cucurbitllOluril cucurbit[lijuril Exaxnole 70 Synthesis of eucurbit[nJuril~ in hydrobroniic acid using rubidium bromide as an added template. Glycoluril (1.49 g), hydrobrotnic acid (48 % w/v, 6.9 znL) and rubidium bromide (827 mg) were placed in a reaction flask, Forznalin (40% w/v) (1.5 mL) was added in otie portion and tbe reaction mixture heated to 1000C for 3 hours. The reaction mixture was cooled and the products were collected by the removal of solvent on a rotary evaporator ~nd analysed byNMR. Yield >98 % by NMR Approximate Yields cucurbit fSuril cucurbitf6)uril cucurbitE7juril cucurbit[SJurll by ~22 NM?. (mass % of recovered product) 25% 43% 24% 8% cuc.uri: zucumeit[lO3urL cucurbitJi1 luril Exathie 71 Synthesis of cucurbitfnjurils in hydrobromic acid using caesiun2 bromide as an add.ed template. Olycoluril (149 g). hydrobromic acid (48 % w/v, 6 9 mL) and caesiurn bromide (1070 mg) were placed in a ~eactJon fiask. Forrualin (40% wAr) (1.5 ~) was added in one pOrtion and the reaction mixture heated to 10000 for 3 hours. The reaction mixture was cooled and the products were coll~cted by the removal of solvern on a rotary evaporator and analysed bx' MAR. Yield >9~ %byNMR Approximate Yields by ~C NMR (mass % of recovered product) cucurbitE5juril 15% cucurbit~6~uril 59% cucurb~:t7)urii 23% cucurbit[8]uril 3% cucuroit[Juri cucurbitEl0~uril .& % cucurhitEl 1~uril Exarnole 72 Syiithesi~ of cucurbit~n]uriIs in hydrochloric acid. using ammoniurn chloride as an 2dded teznplat~. Glycoluril (1.49 g), hydrochloric acid (36 % w/v, 6.9 tL) and ammonium chloride (2~0 nag) were placed in a reaction flask. Formalin (40% wA') (1.5 mL) was added in one portion and the reaction mixture heated to 6000 for GO houxs. The reaction mixture was cooled and the products were collected by the removal of solvent on a rotary evaporator' and analysed by N1~. Yield >98 % by NMR Approximate Yields by ~5C N1V~ (mass % of recovered product) cucurbitE5luril 11% cucurbitf6juril 60% cucurbitE7juril 21% cucurbitf33uril 3% cucurbitE9luril cucurbit~lO3uril cucurbit[ I iJuril Example 7? Synthesis of cucui-bitEnjurUs in hydrobromic acid using rubidium bromide as an added teitiplate. Glycoluril (1.49 g), hydrobromic acid (48 % w/v, 6.9 znL) and rubidium bromide (827 nag) were placed in a reaction flask. Fonrialin (409 wlv) (1,5 mL) was added in one portion and the reaction mixture heated to 60CC for 84 hours. The reaction n23.xture was cooled and tbL products were collected by the removal of solvent or2 a rotary evaporator and analysed by N~AR. Yield 98 % by Nlv~. Approximate Yields by '~C NM?. (mass % of recovered product) cucurbit~5luril 34% cucurbitE6luril 39% cucurbit~7Juril 19% cucurbittSluril 9% cucurbi:E9luril 1% cucurbitElOluril cucurbirl:l 1~uril ~zl% Exarn.ple 7~ Synthesis of ~ncurbitJjnjurik in hydrochloric acid using potassium chloride as an added ternpiate~ Glycoluril (250 g) hydrochloric acid (36 % w!v, 1200 mL) and potassium chloride (62 g) were placed in a reaction flask, Paraformaidehyde (210 g) was added in one portion and the reaction mixture heated to 95CC for 4 hours. The reaction ~i,tture was cooled and the products were collected i~y the removal of solvent on a rotary evaporator and analysed by NMR. Yield >98' % by NM? Approximate Yields by '~C NMR (mass % & recovered product) cucurbit~5~uril 39% cucurbi:EG~uril 36% cucurbitE72uril 20% cucurbitES)uril 5% cucurbit[juril cucurbitElOjuril cucurbit[11)uril Examole '75 Synthesis of cucurbitfnjurils in hydrochloric acid using potassium chloride as an added template. Glvooluril (8 g), hydrochloric acid (36 % w!v, 70 mL) and potassium chloride (2,1 g) were olaced in a reaction flask. Paraformaldehyde (3.5 g) was added in. one portion and the reaction mixture heated tc 100CC for 35 hours. The reaction mixture was cooled and the products were collected b\' the removal of solvent or, a rotary evaporator and analysed by NMR Yaeld >98 % by NMR Approximate Yields by ~C NMR (mass % of recovered product) cucurbitE5]uril 26% cucurbit[6]uril 56% cucurbitE7]uril 15% cucurbitE8juril 3% cucurbit[9]uril cueurbitl0juril cucurbitfl1~uri2 Exarnole 76 Synthesis of cucurbitEn~urils in hydrobromic acid using lithium brQmide as an added template. ~1vcoluril (1.49 g), hydzobroinic acid (48 % w/v, 6.9 rnL) and li~.um bromide (4.3 g) were placed in a reaction flask. Formalin (40% w/v) (1.5 mL) was added in one portaon~ and the reaction mixture heated to 100CC for 3 hours. The reacdon mixture was coo~od and the products were precipitated by addition of methanol and collected by vacuum fll'tation. Yield>98 %byNMR Approximate Yields by '~C NMR (mass % of recovered product) cucurbit(5)uril 13% cucurbit~6Juril 63% cucurbitf7]uril 22% cucurbit~8]uril 3% cucurbitf9]uri.l cucurbit[lOJuril cucurbitflljuril Example '77 Synthesis of cucurbit[nlurils in hydroiodic acid. G~vzolurii (1.4 g,~ and hydrolodic. acid (~'7 % wA', 6.9 naL) were placed in a reaction flask. Formalin (40% w~v) (1.5 tnt) was added fr. one portion and the reaction rnixt~re heated to 1000C for 2 hours. The reaction tiuixture was cooled and the ~roduct~ w~re precipitated by addition of methano and collected by vacuum filtration. Yield 2.2 g Approximate Yields bx NMR (mass % of recovered product) cucurbitE5iuril 2% cucurbitl6)uril '72% cucur'oit[7)uril 22% cucurbitl8]uril 2% cucurbitl9]uril cucurbitElo]uril ~J cucurbit[llJurii Example 78 Synthesis of cucurbitEnjurUs in hydroiod.ic acid using litbium iodide as an added template. Glycoluril (i.4 g), hydrolodic acid (57 % w/v. 6.9 rnL) and lithium iodide (665 mg) were placed in a reaction flask. Formalin (40% w/v) (1.5 mL) was added in one portion and the reaction rnbcture heated to 1000C for 2 hours. The reaction mixture was cooled and the products were vrecipitated by addition of methanol and collected by vacuum filtration. Yield 0.9 g Approximate Yields by t2C Ni~v~ (mass % of recovered product) cucurbitE5)uril 16% cucurbit~6] uril 28% cucurbit[7)uril 56% cucurbit~8)uril cucurbitEjuril cucurbit[ 10) uril cucurbitf I l)iiril Exa.r~~le 79 Synthesis of cucurbit~n)urils in hyd.roiodic acid using sodium iodide as an added template. Glycoluril (1.49 g). hydroiodic acid (57 % w/v, 6.9 niL) and sodium iodide (745 zng) were placed in a reaction flask. Bormalin (40% w/v) (1.5 niL) was added in one portion and the reaction mixture heated to l00~C for 2 hours. The reaction n~ture was cooled and the products were precipitated by addition of methanol and collected by vacuum filtration. Yield >98 % by NMR Approximate Yields by '~C NMR (mass % of recovered product) cucurbit~5)uril 19% zuzuroitlS)uril 559 cuc.urbitF'7~uriI 129 cucurbit[8juri~ cucurbitr9)uril cucurhitriciuril c~curoit~ 1)uril ~leSO S~ynthesis of cucurb~t[jnJuri1s in hydroiodic acid using potassium iodide a~ an added templat~ C]ycoiurL (149 g), hydrojodic acid (57 % w/v± ~ rnL) and potassium iodide (S2~ i~g) were placed ir. a reaction flask. Forrnali (40~ wA') (..5 naL) wa.~ added in one portion and the reactior. mixture heated ~c 10000 for 2 hours. The reaction mixture was cooled and the oroducts were precipitated b~ addition of methannil and collected by vacuum filtration. Yield >9~. 9 b~ NM? .koproximate Yields by ~C NM?. (mass 9 of recovered product) cucufoitE5juri E,29c cucur~it~6Juril 229 cucurbitE7~uri~ , 10% cucurbitESjuril 1% cucurbitEjurf cucuroittlOluril cucuroltEl juri~ Synthesis of eneurblt[n]urils in hydrojodic acid using rubidium iodide as an added template. Glycoluril (1.49 g), hydrojodic acid (57 % w/v. 6.9 niL) and rubidiuni iodide (1060 mg) were placed in a reaction task. Formalin (40% w/v) (1.5 niL) was added in one portion and the reaction mixture heated to 1000C for 2 hours, The reaction mixture was cooled arrd the products were precipitated by addition of m~.thanol and collected by vacu'~n~ filtration, Yield ~S % by NMR Approximate Yields by ~C NM?. (mass % of recovered product) cucurbit~5]uril 34% cucurbitt6)uril 1 ~% cucurbit~71uril 48% cucurbit~8]uril ~l 9 cucurbit~9)uril cucurbit~l0Juri1 cucurbitEl l]uril Bxamole 82 Synthesis of cucurbit~n}ariLs in hydrolodic acid using caesiu~i iodide as an added template. Giycoluril ( .4 g), hydrolodic acid (57 9? w/v; 6.9 rnL) and caesiuin iodide (1300 mg) were placed in a reaction flask. Formalin (40% w/v) (1.5 mL) was added in one portion and the reaction mixture heated to l0C~C for 2 hours. The reaction tnixture was cooled arid the oroducts were prcci~itated b~' addition of methanol and collected b~' vacuum fil~ation. Yield >98 % by NMR Approximate Yields by '3C NM?. (niass % of recovered product) cucurbitESlurli 8% cucurbttE6juril 36% cucurbitE7)urii 53% cucurbitESluril 3% cucurbitL9juril cucurbitfiOjuril cucurbitElijuril Example 82 Synthesis of cucurbitEn]urils in hydroiodic acid using red phosphorous as an added template. Glycoluril (1.49 g), hydrojodic acid (57 % w/v, 6.9 mL) and red phosphorous (1 g) were placed in a reaction flask. Formalin (40% w/v) (1.5 niL) was added in one portion and the reacuon mixture heated to 100CC for 2 bours. The reaction mixture was cooled and the producr~ were precipitated by addition of methanol and collected by ~acuuinn filtration, Yield >9~ % by NM?. A.p~roximate Yields by ~C N~v1R (mass 9? of recovered product) cucurbit[Sluril 2% cucurbitE6]uril 70% cucurbit~7]uri1 23% cucurbitLEluril 4% cucurbitL9juril cucurbitElOluril Example 84 Synthesis of cucurbitfn]urils in hydrolodic acid using lithium iodide and red phosphorous as an added template. &ycoluri (49 g). hydroiodic acad) ano UtxaauTi ~oQxoe ano rae phosphorous (665 rug and 650 rug respectively) were placed in a reaction flask. Formalin (40% w!v~; (1.5 niL) was added in one portion and the reaction mixture heated to 1000C f 2 hours. The reaction mixture was cooled and the products were precipitated by addition of methanol and collected by vacuun~ filtration. Yield >9~ 9? by NMR Approximate Yields by LC NMR (mass % of recovered product) cucurbit~5)uril 23% cucurbitE6~uril 6% cucurbitETluril 65% cucurbitE8luril 69? cucurbitE92uril cucurbitfl0jurL cucurbitEl ljurii Examole 85 Synthesis of cucurbittnjurils in hydroiodic acid using sodium iodide and red phosphorous as an added template. Glycoluril (1.49 g), hydroiodic acid (57 Tv w/v, 6.9 niL) and sodium iodide and red phosphorous (745 rug and 650 rug respectively) were placed in a reaction flask. Formalin (40% wh) (1.5 mL) was added in one portion and the reaction n2ixture heated to 1 000C for 2 hours, The reaction mixture was cooled and the products were precipitaLed by addition of methanol and collected by vaccurn fil~ation. Yield >98 % by NM?. Approximate Yields by laC NMR (rna.~s % of recovered product) cucurbitL5~uril 57% cucurbitE6juril 9% cucurbitL7)uril 29% cucurbit~Sjurll 5% cucurbitf9juril cucurbitE I OJuril cucurbitElliuril <:1> Example 86 Synthesis of' cucurb~tEnJtiri~s In hydrojodic acid using potassium iodide and red phosphorous as an added template. GIvooluril (1,49 g), hydrolodic acid (57 % w/v, 6.9 niL) and potassium iodide and red phosphorous (825 rag and 650 rag respectively) were placed in a reaction flask, Forrualin (40% w/v) (1.5 niL) was added in one portion and the reaction mixture heated to 100CC for 2 hours. The reaction mixture was cooled and the products were precipitated by addition of methanol and collected by vacuum fii~ation. Yieid >9E 9 b~' NM?. Approximate Yields 'ox' C NM?. Kmass 9 of recovered product) cucurbitL5]uril ?59 cucurbit[dluril 11% cucurbit[7juri~ 10% cucurbit[8]uril 3% cucurbitE9luril cucurbitEl 0]uri~ ~le8'7 Synthesis of cucurbit{njurils in hydrolodic acid using rubidiuni iod.ide and red phosphorous as an added template. Glycoluril (1.49 g). hyd.roiodic acid (52 % wlv, 6,9 mL) and rubidium iodide and red phosphorous (1060 nag and 650 mg respectively) were placed in a reaction flask, Formalin (40% w/v (1.5 rnL) was added in one portion and the reaction mixture heaied to 1000C for 2 hours. The reaction mixture was cooled and the products were precipitated by addition of methanol and collected by vacuum filtration. Yield >8 9 by NM? Approximate Yields by 1C NM?. (mass 9 of recovered product) cucurbitE5luril 58% cucurbitt6Juril 20% cucurbit~7]uril 20% cucurbitEBjuril 2% cucurbit~Juril cuctarbit~10~uril cucurbitEl ljuril Ex~ole88 Synthesis of eucurbit[n~urils in hydrojodic acid using caesiu.ni iodide and red phosphorous as an added template. Glycoluril (1.49 g), hydroiodic acid (57 9 w/v, 6.9 mL~ and eaesium iodide and red phosphorous (1300 nag and 650 mg respectively) were placed in a reaction flask, Formalin (40% w/v~ (L5 inL) was added in one portion and the reaction mixture heated to 1000C for 2 hours. the reaction mixture was cooled and the products were precipitated by addition of methanol and collected by vacuum filtation. Yield >98 % by MAR Approximate Yields by '~C NM?. (mass 9 of recovered product) cucurbitE5juril 21% cucurbitlSiuril 28% cucurbitf7~uril 46% cucurbit[SJuril 5% cucur'oitf]uril cucurbit[! Ojuril cu.curbitfl Ijuril Exa.nt~le 8 Synthesis of cucurbit~n~uriis in suift~ric acid using potassium sulfate as an added template. Glycoluri. (1.49 g). sulfuric acid (9 M, 69 mL) and potassium sulfate (436 mg) were placed in a reactor. flask. Forznalin (40% w/v) (1.5 niL) was added in one portion and the reaction mixture heated to 1 000C for 3 hours. The reaction ~xrure was cooled and the products were precipitated bN' addition of methanol and collected by vacuum filtrati~n. Yield >98 %byNMR Approximate Yields bx' ~C NM? (rn-ass % of recovered product) cucurbitL5]uril 159 cucurbit[6juril 66% cucurbitE7luril 18% cucurbitf82uri 1% cucurbitE92urii cucurbitE lOjuril cucurbitEl ijuril Bxamole 90 Synthesis of cucurbitEn]urilz in sulfuric acid using potassium sulfate as an added template. Glycoluril (1.49 g), sulfuric acid (9 M, 6.9 niL) and potassium sulfate (Sql rn.g) were placed in a reaction flask. Formalin (40% w/v) (1.5 niL) was added in one portion and the reaction mixture heated to 1 000C for 3 hours, The reaction mixture was cooled and the products were precipitated by addition of methanol and collected by vacuum filtration. Yield >98 % by NlvrR Approximate Yields by '~C NM?. (mass % of recovered product) cucurbit[Sjuril 11% cucurbit[6]uril 75% cucurbitF7]urii 15% cucurbitL8]uril 9 cucurbit[9Juril cucurbit[ lOjuril cucurbit[li]urll Example 91 Synthesis of cucurbit[n~uriis in sulfuric acid using potassiun2 sulfate as an added template. Glycoiuri~ (149 g), sulfuric acid ( V 6.9 mL) and potassiuzi sulfate (1307 nag) were placed in a reaction fiask. Forrualin (40% wfv) (1.5 rnLi was added ir. one portion and the reaction mxrure heated to 1 000C for .3 hours, The reaction mixture was cooled and the products were precipitated by addition of methanol and collected by vacuum filtration. Yield >98 % by NMR Approximate Yi5lds by ~C NMR (mass % of recovered product) cuzu~bitE5JurL 33% cucurbit[6]uril 49% cucurbitf7)uril 16% cucurbitE8juril 2% cucurbitE9juril cucurbitElOluril cuzurbitEl lJurii Exanmie 92 Synthesis of caeurbitEn)urils in sulfuric acid using potassium sulfate as an added template. Glvcolurii (149 g). sulfuric acid (9 M, 6~ ~L) aud potassium sulfate (4350 rug) were placed ir. a reaction flask. Forrnab (40% w!v) (1.5 inL) was added in one portion ~nd tbe reaction mixture heated to 1000C for 3 hours. The reaction mixture was cooled and the products were precipitated by addition of methanol and collected by vacuum fiL~ation, Yield >8 % by NM?. Approximate Yields by ~C NVIR (mass % of recovered product) cucurbitL5]uril 23% cucurbit[6juril 64% cucurbit[7]uril 13% cucurbit[8luril cucurbitfjuril cucurbirElOjuril cucurbitEl .lluril Exa~nole 93 Synthesis of cueurb~tLnJuriIs in sulfuric acid using lithium sulfate as an added template. Glvcoiuril (1.4; g), sulfuric acid (9 M, 6~ mL) and lithium sulfate (275 rug) were placed ir. ~ reaction flask. Forrnalir. (40% w/v) (1.5 zL) was added i.n one portion and the reaction n~ixture heated tc'l00~C for 3 hours. The reaction mixture was cooled and the products were precipitated b;' addition of methanol and collected by vacuum filtration. Yield >98 % by NM?. Approximate Yields by 1~C NIv~ (mass 9? of recovered product) cucurbitE5iuril 4% cucurbit[6)uril 71 9 cucurbitV7~uri1 24% cucurbit[8]uril 1% cucurbit[9luril cucurbit~ 1 0~uril cucurbitfl ijuril Synthesis of cu.curbitEn3urils in sulfuric acid using lithiuni sulfate as an added template. GlycoluriQ (1,49 g), sulfuric acid (9 M, 6.9 ~nL) and lithium sulfate (2750 nag) were placed in a reaction ±lask.. Formalin (40% w/v) (1.5 ntL.) was added in one portion and the reaction mixture heated to l00~C for 3 hours, The reaction mixture was cooled and the products were precipitated by addition of methanol and collected by '~acuurn filtration. Yield >8 9? by NIvR Approximate Yields by ~C N1V~. (mass % of recovered product) cucurbitE5)uril 25% cucurbit~6)uril 51 % cucurbit[73uril 23% cucurbit[8]uril 1% cucurbitLluril cucurbitlOluril Synthesis of cueurbit[n]urils in hydrochloric acid using lithium chloride as an added template. Glycoluril (5 g), hydrochloric acid (36 % w/v, 20 mM and lithium chloride (746 nag) were placed in a reaction flask. Paraformaldehyde (2.2 g) was added in one portion and the reaction mixture heated to 10000 for 4 hours. The reaction mixture was cooled and the products were precipitated by addition of methanol and collected by vacuum filtration. Yield >98 9? by NM?. Approximate Yields by ~C N~vIP.. (mass % of recovered. product) cucurbitf5jurii 22% cucuretti6iurii cucurbitEThuril 29% cucurbitEE~urii 12% cucurbitEluri cucurbitflOjuril cuzurbitLl Jurii Example 9C Synthesis of cucurbitEnlurils in p-toluenesulfonic acid using lithiurn p. toluenesulfonate as an added template. Clycoluril (400 rag), p-toluenesQlfonic arid H95 %, 3.5 g) and lithium p-tolUenesulfonate (l5'7 nag) were placed in a reaction flask. Forrnalin (40% W/v) (0.5 mL) was added in one portion and the reaction mixture. heated to l0O~C for 2 hours, The reaction mixture was cooled and the produces were precipitated by addition of methanol and collected by vacuum filuation. Yield 240 nag Approximate Yields by C Nlv2 (mass 9? of recovered product) cucurbit[5J uril 18% cucurbit~6]uril 45% cucurbitr7)urfl 26% cucurbitESjurii 9% cucur~itf91uril cucurbit~l0~uril Bxam'~le 97 Synthesis of cuctirbit[njurils with hydrochloric acid using trifluoroacetie acid as a solveilL Glycoluril (144 nag), hydrochloric acid (36 % w/v, 1 drop) and t.rifluoroacetic acid (1 mL) were placed in a reaction flask, Paraformaldehyde (63 mg) was added i~ one portion and the reaction mixture heated to 900C for 3 hours, The reaction mixture was cooled and the products were precipitated by addition of methanol and the collected solid was then dried at 800C overnight and analysed by ~C NMR. Yield>98%byNMR Approximate Yields by ~C NMR (mass % of recovered product) cucurbie~5]uril 46% cucurbicE6~urii 54% cucurbitETluril cucurbitE8luril cucurbic[9~uril cucurbitfiOjuril .'K % cucurbitEl iJuril Exam~i~ 9E~ Synthesis of cucurbitEnjurils with sulfuric acid usin.g trifluoroacetic acid as a solvent. O¾colurii (44 nag), sulfuric acid (98 % w/v, 2 drops) and trifluoroacetic acid (1 ~) were placed in a reactioD flask. Paraformaldehyde (63 ntg) was added in one portion and the reaction In±xture heated to 90CC for 4 hours. The reaction mixture. was cooled and the products were precipitated by addition of methanol and the collected solid was then dried at 800C overnight and analysed by "'0 NMR. Yield >8 % b~' NM? Approximate Yields by ~ ~C NM?. (mass % of recovered product) cucurbitE5]uril cucurbit[6~uili 100% cucurbitE7luril cucurbitES]uril cuzurbitf9]uril eucurbit[l0]uril cucurbitL 1 iluril Exarnnl~ 99 Synthesis of cucurbit[nlurils with hydrochloric acid usii~g trit'luoroacetic acid as a solvent, C-lycoluril (144 nag), hydrochloric acid (36 % w/v, 5 drops) and trifluoroacetic acid (1 naL) were placed in a reaction flask. Para±'ormaldehyde (63 nag) was added in one portion and the reaction mixture heated to 90CC for 5 hours, The reaction mixture was cocied and the products were precipitated by addition of methanol and the collected solid was then dried at 800C oventight and analysed by ~C NMR, Yield >98 % by NM?. Approximate Yields by '~C NM?. (mass % of recovered product) cu.curbitf5juril cucurbit~6Juril 100% cucurbitE7~uril cucurhit[8~uril cucurbitf)uril cucurbitElOjuril cucurbitEl I luril Exarcple 100 Synthesis of cucurbit~n]urils with hydrochloric acid using trifluoroacetic acid as a solvent, Givcoluril K44 mg) and trifluoroacetic acid (1 mL) were placed in: a reaction tiask. Dry' hvdrocbloric acid gas was then bubbled into the solution for 15 minutes. Praforrualdehyde (63 nag) ~vas added in one portion and the. reaction. mixture heated to 900C for 20.5 hours. The reaction mixture was cooled and the products were precipitated by addition of methanol and the collected solid was then dried at 8000 overnight and analysed by ~C NMR. Y~e]d >9~ 9 by NM?. Approximate Yields by ~ NM?. (mass % of recovered product) cucurbit[5]urfl cucurbit[6]uril 100% cucurbitf'7jurli cucurbitESjuril cucurbitE9juril cucurbitl lOjuril cucurbit~i hurl Exmaple 101 Synthesis of cueurbit(n)urils with hydrochloric acid using trifluoroacetic acid as a ~oivent, Glycoluril (144 nag) trifluoroacetic acid (2 raL) were placed in a reaction flask. Dry hydrochloric acid gas was then bubbled into the solution for iS minutes. Paraformnaldehyde (63 rag) was added in one portion and the reaction mixture heated to 90CC for 25 hours. The reaction mixture was cooled and the products were precipitated by addition of methanci and the collected solid was then dried at S0~C overnight and analysed by ~"C NMR• Yield >98 % by N~ Approximate Yields by '~0 NMR (mass 9 of recovered product) cucurbitf5]uril cucurbit[Gluri2 100% cucurbitf7juril c~1 % cucu:bitf8)uril ~l % cucurbitL9luril cucurbit[lQJuril cucurbitEl ~juril Example 102 Synthesis of cucurbitFn]uri.ls with sulfuric acid using trifluoroacetic acid as a solvent, Glycoluril (144 rag), sulfuric acid (98 % wA', 1 drop) and trifluoroacetic acid (1.5 raL) were placed in a reaction flask. Paraformaldehyde (63 rag) was added in one portion and the reaction mixture heated to 900C for 23 hours, The reaction mixture was cooled and the products were precipitated by addition of methanol and the collected solid was then dried at SO0C overnight and analysed by 1~C NMR. Yield >8 % b~ NM?. ~pproxanate Yields b\' ~C NMP~ (mass 9 of recovered product? cucurbi!!5lurii cucurbitf6]urfl 37% cucurbitf7)uri 399 cucurbit(SJuril 24% cucurbitEluril cucurbitF l03urii cucurbitf. l)urii Exarnole 103 Synthesis of cucurbitEnlurils with sulfuric acid using trifluoroacetic acid as a solvent. Glycoluril (144 nag), sulfuric acid (98 % w/v, 2 drops) and trifluoroacetic acid (1,5 mL) were placed in a reaction flask. Paraformaldehyde (63 mg) was added in one portion and the reaction mixture heated to 900C for 23 hours. The reaction mixture was cooled arid the products were precipitated by addition of methanol and he collected solid was then dried at 800C overnight and analysed by ~"C NM?.. Yieid >98 9 by Nl\~ A~proxirnate Yields by '~C NM?. (mass 9 of recovered product) cucurbitEs]uril cucurbitE6)uril 100% cu:urbitE7Thirii cucurbttE8jurii cucurbitEluril cucurbitElOluril cucurbitEl :~urii Examole 104 Synthesis of cucurbitEn~uri1s with sulfuric acid using trifluoroacetic acid as a solvent. Glycoluril (144 nag), sulfuric acid (98 % wlv, 5 drops) and trifluoroacetic acid (1.5 in~) were placed in a reaction flask. Paraforinaldehyde (63 nag) was added in one portion and the reaction mixture heated to 90CC for 23 hours. The reaction mixture was cooled and the products were precipitated by addition of methanol and th~ collected solid was then dried at 800C overnight and analysed by ~C NM?.... Yield >98 9 by NMR Approximate Yields by ~C NMR (mass % of recovered product) cucorbitESluril cucurbitL6~uril 48% cucurbit["7~uril 32% cucurbit~8Juril 20% cucurbit[Juril cucurbizElQluril cucuro~t~ JUni Example lQS Synthesis of cucurbitinlurils with sulfuric acid using trifluoroacetic acid as a solvent, Glycoiurii (144 mg), sulfuric acid (~E % w/v, 5 drops) arid trifluoroacetic acid (1,5 triL.) were olaced in a reaction flask. ?araformaldehyde (63 nag) was added in one portion and the reaction mixture heated to 900C for 3 hours. The reaction mixture was cooled and the products were precipitated by addition of methanol and the collected solid was then dried a: 80CC overnight and analysed by C NM?. Yield >92 % by NM?. Approximate Yields by ~C NM?. (mass % of recovered product) cucureit[5]uril cucurbitE6~urii 57% cucurbit[7jurii 28% cucurbitESjuril 15% cucurbitE)urii cucurbitElOjuril cucurbit[ll]uril Example 106 Synthesis of cucurbitEnlurils with sulfuric acid using trifluoroacetic acid as a solvent, Glycoluri) (l~ rug), suifun: acid (fuming, 3 drops) and tri.fluoroacetic acid (1.5 mL) were placed in a reaction flask. Paraformaldehyde (63 rug) was added in one portion and the reaction rn.ixture heated to 90CC for 25.5 hours. Tbe reaction mixture 'was cooled and the products were precipitated by addition of methanol and the collected solid was then dried at 800C overnight and analysed by t3C NM?.. Yield>98%byNMR Approximate Yield.s by C NMR (mass % of recovered product) cucurbit[5]uril cucurtit(6jurfl 47% cucurbit[7Juril 34% cucurbitESluril 20% cucurbit[9]uril cucurbit[l0]uril cUcurbitEllitinI 1% Exana~le 102 Synthesis of cucurbitlnjurils with sulfuric acid using methanesulfonic acid as a solvent. Glvcoluril (44 rag). sulfurac. acid (98 % w/v, dro~ and methanesulfonic acid (>5 ruL.) were placed in. a reaction flask. Parafortnaldehyde (63 nag) was added in one portior. anc the reaction. mixture heated to 900C for 26 hours. The reaction mixture was cooled and the products were pecipitaced by addition o~ ethanol and the collected solid was then dried at 8O~C overnight and anaiyse~ by ~C NM?., Y~eid >98 9 b~' NM?. Approximate Yields b~' ~~C NM?. (ruass 9 of recovered product) cucurbie~5]uril cucurbit(63uril 62% cucurbitr7luril 33% cucurbit~8]uril cucurbitf]uril cucurbirlloluril Example 108 Synthesis of cucu.rbit~nJurlls with suffiaric acid using methanesuffonic acid. as a solvent. Glycoluril (144 nag). sulfuric acid (98 % wAy, 5 drops) and methanesulfonic acid (1.5 mL) were placed in a reaction flask. Paraformaldehyde (62 rag) was added in one portion and t.he reaction mixture heated to 900C for 26 hours. The reaction mixture was cooled and the products were pecipitated b~' addition. of ethanol and the collected soLd was then d.ried at SC~C overnight and analysed b~' '~C NM?.. Yield >98 % by NM?. Approximate Yields b~' '~ C NM?. (mass % of recovered product) cucurbitE5juril 7% cucurb~r[6]uri1 61% cucurbir[7~urii 32% cucurbitESiuril cucurnitE9luril cucurnitLloluril cuourbitEl 1~uril Example 109 Synthesis of cucurbitfnijurils with sulfuric acid using tri'~iuoroacetic acid as a so]v~nt~ Glycoluril (l44 rag), sulfuric acid (fuzningh 3 drops) and trifluoroacetic acid (1,5 rnL) were placed in a reaction flask. Para.formaldehyde (63 mg) was added in one portion and the reactior~ mixture heated to 900C for 26 hours. The reaction mixture was cooled and the products were pecipitated by addition of ethanol and the collected solid was then dried at 80CC overnight and analysed by C NM?.. Yield >98 9 by NM?.. Approximate Yields b~' ~C NMR (mass % of recovered product) cucurbir~5~urii cucurbit[6)uril 47% cucurbit~7]uril 35% cucurbitf8juril 17% cucurbit[juriJ cucurbittl0jurii cucuroitflljuril Example 110 Synthesis of cucurbitEn]urils with sulfuric acid using triftuoroacetic acid a~ a solvent. Glycoluril (144 mg), sulfuric acid (fuming, $ drops; and trifluoroacetic acid (1.5 mL) were placed in s reaction fiask~ Paraforrualdehyde (63 nag) was added in one portion and the reaction mixture heated to 900C for 26 hours. The reaction mixture. was cooled and the products were pecipitated by addition of ethanol and the collected solid was then dried at 800C overnight and analysed by C NMI?.... Yield >98 % by NMR Approximate Yields by bC Nlv~ (mass % of recovered product) cucurbir~5~uril cucuroitE6JuriJ cucurbitf7)uril 32% cucurbitESluril 21% cucurbirE]uril cucurbitE 10~urii cucurbitEl ijuril Synthesis of eQcurbitEn]urils with sulfuric acid using 124-trifluoroethanol as a solvetit. Glycoluril (144 nag), sulfuric acid (98 % w/v. 1 drop) and 1,1,1-trifluoroethanol (1.5 mL') were placed in ~ reaction. flask, Paraformaldehyde (63 nag) was added in one portion and the reaction mixture heated to 9000 for 25 hours. The reaction mixture was cooled and the products were pecipitated by addition of ethanol arid the collected solid was then dried at 20CC overnight and analysed by '3C NMR. Yield >98 % by NMR Approximate Yields by '~C NMR (mass % of recovered product) cucurbit[5]uril 17% cucurbitE6luril 729 cucurbitE7]uril 11% cucurbitESluril cucurbit[)uril cucurbit[l0]uril cucurb~:i Ijuri. Examule 112 Synthesis of cucurbit~nJurils with su]fur~e acid using 1,14.trit~uoroethanol as a solvent. Glycoluril (l4~ mg), sulfuric acid (98 9? w/v. 5 drops) and .1,l-rrifluoroethanol (1.5 mL'~ were placed ~'. a reaction. flask. ?arafonnald&nyde (63 rag) was added in one portion and the reaction n~ixture heated to 9O~C for 25 hours. The reaction utixture was cooled and the prodt~cts were pecipitated by addition of ethanol and the collected solid was then dried at 80CC overaight and analysed by 'Th NMR. Yield >98 9 by NIv~. Approxintate Yields by C Nlv~ (mass % of recovered product) cucurbitEsluril cucurbitf6juril 11% cucurbitE7luril cucurbitfSjuril cucurbitE93uril cucurbit[l0]urll cucurbitllljuril ~e1l~ Synthesis of' cucurbit~n)urlls with sulfuric acid using 1g14-trifluoroethanol as a so!vent. Glycoluril (144 rug), sulfuric acid (98 9 wAy, 1 drop) and 1,l..1.-tz~fiuoroethanol (1.5 raL) were placed in a reaction flask. Paraformaldehyde (63 rug) was added ~ one portion and the reaction rnLxture heated to 900C for 170 hours, The reaction mixture was Qooled and the products were pecipitated by addition of ethanol and the collected solid was thei~ dried a: 200C overnight and analysed by 13C NMR. Yield>98%byNMR Approximate Yields by C NMR (mass 9 of recovered product) cucurbitE5juril cucurbitLdjuril 100% cucurbit[7]uril cucurbit[SJuril cucurbit[9]uril cucurbit[ 1 Qiuril cucurbit~llluril 1% Exarnole lit:. Synthesis of cucurbitfnjurils with sulfuric acid using 2,14-trifluoroethanol as a solvent. Glycoluril >4 rag). sulfuric acid (98 % wAy, 5 drops) and 11,1-trifluoroethanol (1.5 n~) were placed in a reaction. fiask, Paraformaldehyde (63 mg) was added in one. portiot~ and the reactior. mixture heated to 900C for 170 hours, The reaction nti~ture was cooled ~nd the products were pecipitated b'~' addition. of ethanol and the collected solid was then dried at 8000 overnight and analysedbv ~C NMR. Yield>98%bvNMR Approximate Yields by ~C NMR (mass 9 of recovered product?) cucurbitESluril cucurbitE6]uri.i 100% cucurbitET) uril cucurbitESluril cucurbit[9)uril cucurbitE 101 uril cucurbitEl Iluril ~eil5 Synthesis of cucurbitEn1uri'is with sulfuric acid using trifluoro acetic acid as a solvent and o.carborane as a template. G~ycolurii (l4A~ rag), sulfuric acid (98 % wAy, 1 drop), o-carboraue (IS mg) and ~ifluoro acetic acid (1.5 raL) were ~iaced in a reaction flask. Paraformaldehyde (6$ mg) was added in one portion and the reaction mixture heated te 9Q~C for 25,5 hours. The reaction mixture was cooled and the products were precipitated by addition of methanol and the collected solid was then dried at 300C overnight and analysed by '~C INMR, Yield >98 % by NI'vfR. Approximate Yields by "'C NMR (mass % of recovered product) cucurbit[5]uril cucurbit[6luril 57% cucurbitE7luril 32% cucutbitL8]uril l l% cueurbith9]uril cucurbitE 1 OJuril cucurbitElliuril Exanmle lid Synthesis of cucurbitEn3urils with sul.furic acid using trifluoro acetic acid as a solvent and o.-carboran~ as a template. Glycoluri] (144 nag), sulfuric acid (98 % wAy, 5 drops), 0-carborane (l~ rug) and trifluoro acetic acid (>5 niL) were placed in a reaction flask. Paraformaldehyde (62. mg) was added in one vortion and the reaction mixture heated to 9000 ~or 25.5 hours. The reaction mixture was cooled and the products were precipitated by addition of methanol and the collected solid was then dried at 800C overnight and analysed by ~C NMR. Yield >98 9 by NMR Approximate Yields by 130 NMR (mass 9 of recovered product) cucurbitE5juril cucurbit~6~uril 50% cucur'oitr7~uril 32% cucurbit[S]uril 179 cucurbitE]uril cucurbitEl Q)uril cucurbitf 1 ijuril Exampleii? Synthesis of cucurbitEn~urili with sulfuric acid using trifluoro acetic acid a~ a solvent and o-carborane as a template. Glycoluril (144 nag). sulfuric acid (8 % wlv, I drop). o-ca.rborane (18 mg) and thfluoro acetic acid (1.5 naL) were placed in a reaction flask. Para±'orrnaldehyd.e (63 mg) was added in one oortion and the reaction. mixture heated to 900C for 20 hours. The reaction mi~ture was cooled and the products were precipitated by addition of methanol and the collected solid was then dried at 80CC overnight and analysed by '~C Yield >98 % by NMR Approximate Yields by ~C ~ (tn.ass % of recovered product) cucurbitE5~unil cucurbit[GJuril 51% cucurbitL7juril 399 cucurbit~SJuriV 109 cucurbitf9)uril cucurbitElOJuril cucurbit~l iJunil Examo~e 118 Snthe of cucurbit~n)urils with sulfuric acid using trifluoro acetic acid as a solvent and o.carborane as a template. Glycoluril (144 mg). sulfuric acid (9g 9 wAx, 5 drops), o-carborane (18 rug) and ~rifluoro acetic acid (1,5 znL) were placed in a reaction flask. Paraforrnaldehyde (63 rag) was added ir. onc portion end the i'oection niixrur&~ hxar~d to ~00C for 20 ~ourc. The ~t.ion n~ixturm was cooled and the products were precipitated by addition of znethanoi. and the collected solid was then. dried at 800C overnight and analysed by ~C NMR. Yield >98 % by NMR Approximate Yields by 1~C NMR (mass % of recovered product) cucurbit[6]uril 47% cucurbftE7luril 38% ouourbitE~luril 1 5Q~ cucurbit~93uril cucurbit[10)uril cucurbitEl I Juril E~cample 119 Synthesis of cmicurbitEn~uri1s with sulfuric acid using tritluoro acetic acid ~s a solvent and o.carborane as a template. 'Glvcolurii (710 nag), sulfuric acid (98 % w/v, 7.5 mL), o-carborane (18 mg) and trifluoro ~etn- acid (1.5 moL) were placed in a reaction flask. Pa fornaa2.dehyde (63 rug) was added in one portion and the reaction nuxture heated to 900C for 24.5 hours. The reaction mixture was cooled and the products were precipitated by addition of methanol and the collected solid was then dried at 80CC overn4ht and analysed by ~C MAR. Yield >98 %byNMR Approfim~te Y.ieldi by ~C NTMP (na~is~ 9 of recovered product) cucurbit[5]uril 3% cucurbit~6Juril 53% cucurbit~7Juti.l 33% cucurbitt8]uril 11% cucurbit[9]uril cucurbittlOluril cucurbitElliuril Exarnole 120 Synthesis of cucurbitfnjurils with sulfuric acid using merhanesulfonic acid as a solvent and o-carborane as a template. Glycoluril (144 rog). sulfuric acid (98 9 wiv I drop), o-carborane (iS mg) and metnanesuitonic acm (7.! naL) were placed in a reaction flask. Pdmfu:zI±alU~1iyde (63 L4J was added in one. portion and the reaction mixture heated to 90CC for 22.5 hours. The reaction mixture was cooled and the products were necipitated by addition of ethanol and collected using a centrifugeThe collected solid was then dried at 80CC overnight and analysedbv 13CNMR. Yield >98 9? by Nlv~ ApproximaLe Yields by 13C NM?.. (macs Cib of reeofled prtdi4 cucurbit[SJuril 7% cucurbit[6]uril 53% cucurbitE7]uril 30% cucurbi4Sjurfl 10% cucurbit[jurii cucurbi(IC3urii cucurbit[11]uril Exarnole 121 Synthesis of cneurbit[njuriis with sulfuric acid using inethanesulfonic acid as a So! ~'ent and o-ear'borane as a template. Glycoluril (144 nag), sulfuric acid (98 9? w/v, 5 drops), o-car'borane (18 fig) and rnerhanesulfonic acid (1.5 rnL) were placed in a. reaction flask, Parafbnnaldehyde (63 nag) was added in one portion and the reaction mixture heated to 90~O for 22.5 hours, The reaction mixture was cooled and the products were pecipitated by addition of ethanol and coUecled using a centnrugefl2he collected solid was then dried at .&Y~C overnight arid analysed by '3C NMR. Yield >8 9 by NMR Approximate Yields by '3C NIv~ (mass % of recovered product) cucurbitL5]uril 6% cucurbitl6juril 56% cucurbit7)uril 30% cucurbicfS]uril 8% cucurbit[9~uril cucurbit[ 1 0]uril. bxampse~ 122 Preparation of Substituted Cucurhiturits Substituted givoolurils of the following formulae were used in this synthesis: Examples of xed cucurt it[s,u] urils F teracydic diether~ R=R '=0Th, dilnethyl; RR'06h5, diphenyl; ~ dlbydrophenathroline. C~) A mixure of the d.iinethyl tetracyclic diether (107mg) and caesium chloride (7 1mg) in concentrated hydrochloric acid (0.Smi) was heated at 100k for lbr 4Omins. to give a >85% yield of the decame!hylcucurbitf5juffl and (2) A ndxnre of the dimerhyl tetracyclic t±iether 29~ rn~) and glycoluril (54mg) in concentrated hydrochloric acad (O.Sinl) was shaken at room temperaure for 1hz then heated at 100CC for ilir 40 mins., at. which time reaction was complete. The yield was determined by lao NMR to be >95% for a mixture of The methyl substituted cucurbirfa,u)urils, where s.u equalsl4; 2,3: 3,2; 4,1; 1,5: 2,4; 2,3; 4,2; 5,1; 1,5; 2,5: 3,4; /~ 3; 5,2; 6,1; and s represet ;he unit zarryin~ the substitution The composition of s to u was determined by ES-MS. (2) A mixture of the dimethyl retracyclic dieter (119mg), glycoluril (66mg) and caesium chloride (78mg) in concentrated hydrochloric acid (0.5m1) was shaken at room temperature for 2 hr then heated at 100CC until the reaction was complete at 1hz 20rnins. The yield by 1½ NN2. was near qbantiradve. The composition of s to u was observed to. be different but not accurately determined. (4) The diphenyl tetracyclic dieter (1.9gm), gylcoluril (0.71gm) and para toluene suiphonic acid (104gm) were combined and heated to 12000 for 3hz. While still hot the mixture was poured into methanol (150m1) and precipitate collected by filtradon, The solid iimbij tu1W~Lod w&S ctisscdved in e ±imimum valume of Set formic acid rind this solution was poured into hot water and the precipitate collected to gave 132gm or the pnenyi substituted cucurbit[s,u]urils, where s,u equals 1,4, 2,4; 2,4; 3,3 and s represents the unit carrying the substitution. (6) To a suspension of the dihydrcphenathrohne glycoluril (530mg) in aqueous 40% formaldehyde was added SM hydrochloric acid (iSnil) and the niixture stirred at room temper~t.ua-e !or 5hr hen glvccluril (25%,~) was added and Lhe ffalxtwr heated it 100CC for 31r. ~C NMF. of the mbrture indicated a 2Q-3C)% ±ormazior. of the dihvd.ronhenanthroiine substituted cucurbit( s ,u jurils Variations of these methods could conceivably be applied to any substituted glycolurL where the side chair is s:~bie to the reaztion conditions. Template function The conrroliin~ factors for achieving the sy~thesis of a variey of cucurbiturils of differing uni sizes are pos:ulate~ tc be primatily derived from a templating effect. For example, a: anion is apparently held in position by a rnetaJ cation or the azninonium ion. The metal cations coordinate to the carbonyls of the forming cucur'oituri: intermediates (such as F, GI. and G2j or in the case of the ainmonium cation is held through hydrogen •oondin~ to the carbonyls of these intermediates. The iege: iodide anion and its tight pairing witi-. th~ lithium cation favours cucurbit~7juril bu~ for the more diffuse. ion2 pairs of Sodium. potasSium. or rubidium, iodide does not control the size by templating around the anion but rather templating is predominantly controlled by the cation although this effect diminishes as the anion decreases in size. There has been found a common tend where the eouilibriuin shifts by varying combinations of anion and cations. The proton from the acid not only serves as a catalyst but also acts as a cation capable of hydrogen bonding to the carbonyls of the forming cucurbirfnjurL and also ~ontrol1ing the placement of anions, The degree of the competing influence between these protons and any added cations affects the equilibrium and hence the product distribution. Cucurbitfri]unils where n>7 appears to be controlled by a temnoladug around a cation/anion cluster rather than a single ion pair. Electrospray mass spectroscopy of larger cucurbituuils snpports this showing muTh charged cationic complexes. Further influences upon the equilibrium and hence the product out come is the precipitation of product complexes. For example increasing the concentration by 10 times of a cation such as lithium in sulphuric acid changes the relative proportion of cucuibitL5luril from 5% to 25% as a consequence of the precipitation of the eucurbit[5Juff lithium complexes. In addition to equilibrium shifts caused by changes to the cation zoncentration the equilibrium is also affected by the formation of the cucurbitt6juril iodine complex which occurs under the reaction conditions where hydriodic acid is used and hydriodic acid decomposes to fort. xod±ine. The ad&rior. of red vhbsnhorus eliminates this effect b~ the in s:w reduction of the iodine generated. It. addition, we have found tha: a wide range of other inorganic and organic compounds car. be used as templates These affect the equilibriua through a variet of subtle effects including ion-dipole, diople-diopie and hydrogen bonding. hydrophobic and weal: Van der Waals interactions. lr~ essence any material or compound stable to the reecuor conditions could ac: as s. potential template. Industrial app hoabii ry The potential uses for cucurbitEnjurils axe large with academic. industrial, analytical and pharmaceutical applications As a class these molecules can be favourable compared to the cvziodexn-ins because both molecular systems posses a hydrophobic cavity with polar end caps. Cyclodextrins have been used in a wide range of applications includinz slow release drugs odour entrapment agents in plastic films, and enzinilrnies for synthesis. I: is believed that cucurbit[r3urils will be of use in similar areas where benefit can he taker. of the ability of the cuzurbit~nJurils to take up molecules or compounds into there central cavity. Such potential uses may include: Environmental (water and soTh Remediation, by the binding of polluting products and their removal: - Preventative, eg, by binding of .potential pollutants before wastes are released to the environment; - Uses in biodegradable polymers Domestic and Public - Incorporation into polymers as odourisers, releasing fragrances slowly over time; - Or incorporated into polymers to trap unpleasant odours or toxic vapors ~ncapriilation of bieaching and whitening agents - F1avot~r enhancers, - Flavour optnnisers, hence h~di~g unpleasant flavours. • Po~ypheno.1 removal to reduce discolouration of juices. Pharmaceutical • Slov release drugs, hinitin~ side effects and reducing t7tie frequency of doses; - lncrea~ing drug stability in vivo or on the shelf: ~etoxification, for e~temp~e, decreasing stomach irritations, or th~ ttea:ment of chemical allergens by encaprulation. A~ricu1tural/horticuJ,tural - Slow release of herbicides and pesticides; - Stabii~a±io~ of agricultural chemicals against light and heat. Msnufacturin~ - Enzyme/catalyst mimics; - Regioselective control over reaction products~ • - Manipulation of paint and polymer products; - Chromatographic columns for chemical purification; - Ana~yr~cal tools and dev2ces: - Printing and photogra~hy Miscellaneous - Volatility reduction, for storage, safety, or use; -Uses for insensitive munitions manufacture; • Borensic science~ Cucurbitfn]urils are thermally more robust than cyciodextrins and are stable to strong acid solutions unlike cyciodexuins. The present inventors have also found that cucurbit[6~uril and cucurbitFflu.ril can both bind dioxane aqueous solutions, This dioxane binding property can form the basis of processes for the removal of dioxane. According to a fur~her aspect of the present invention, the present invention provides a process for removing dioxane from a fluid comprising contacting the fluid with cucurbitf63urii andlor cucurbit['7]uril, The physical removal of dioxane could take place using one of the following techniques: • Cucurbitl6 or 7]uril bound to a non-reactive solid support (silica or alum.ina) where the dioxane would bind to the cucurbit[6 or 7Juril and then be removed from solution by simple filtratio~ to collect the solid support • A solution of cucurbitt6 or 7]uril placed in dialysis tubing which would allow the passage of dioxane into the solution where it would be bound by the cucurbit[6 or 7] uril. • Incorporation of the cucurbitL6 or 7Juril into a solid clay support and use filtration techniques to remove bound dioxane. • lnco~oratior. intc a polymer film. lr. this case the dioxane would be entra~ned bY the cucurbit~E or Tluril inside the polmer film When the. capacity of the film has been reached it is simply removed from contact with the product stream, • In all cases the material itself could be regenerated for repeated use, If the dJoxane is contained in the solid, for example in diaxane/contatninared soil, th~ process of this aspec: of the invention may comprise the further sten of wasbin~ the soil wttn a fluid tc thereby cause the dioxane to go into the fluid and subsecuently creating the fluid in accordance with this aspect of the invention. Cucurbit(5A-L has shown uptake of carbon monoxide, Accordingly, the invention further provides a method for removing carbon monoxide from a liquid or vapour containing carbon monoxide. by contacting the li~ui6 or vapour with cucurbit~]urTh The presenz invention provides a method for producing a range of cucurbitfnjurils and cucurbitLs~ujuriis. The synthesis method results in the production of a number of cucurbit~n]uriJs and cucurbitfs~u]urils that have never before been produced or isoia.ted.. S e~aration is possible via chromatography andlor selective. preci~itation~ The vroduet cucurbizfnlurils and cucurbitfs.u]urils are stable to vigorous reaction conditions over a wide range of p~ values. They are soluble in aqueous acid or aqueous salt solutions. The method gives cucurbitarils in much larger yields than previously possible, The use of templatirig compound.s allows a degree of control over the relative amounts of the different cucurbitrn]urils being produced. * Those skilled in the art will appreciate that the invention described herein may be susceptible to variation and modifications other than those specifically described. It is to be understood that the present invention encompasses all such variations and modifications that fall within its spirit and scope We claim: 1. A cucurbit [n]uril having the formula (I) (Formula Removed) wherein n = 4 to 12, and wherein, for each unit of the formula (II) (Formula Removed) making up the cucurbit[n]uril, R1 and R2 are independently selected from H, an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical or a heterocyclyl radical, or R1 and R2 form a cyclic hydrocarbon radical or heterocyclyl radical, but excluding unsubstituted cucurbit[6]uril and decamethylcucurbit[5]uril. 2. A cucurbit[n]uril as claimed in claim 1, wherein for each unit of the formula (II) making up the cucurbit[n]uril, R1 and R2 are both H, and n is 4, 5, 7, 8, 9, 10, 11 or 12. 3. A cucurbit [n]uril as claimed in claim 1, wherein for each unit of the formula (II) making up the cucurbituril, R1 and R2 are both H, or R1 and R2 are independently selected from an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical or a heterocyclyl radical, or R1 and R2 form a cyclic hydrocarbon radical. 4. A method for producing a cucurbit[n]uril as claimed in any one of claims 1 to 3, comprising mixing substituted and/or unsubstituted glycoluril with an acid such as herein described and a compound that can form methylene bridges between glycoluril units; and optionally a templating compound selected from ammonium chloride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, caesium chloride, ammonium bromide, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, caesium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, caesium iodide, potassium sulfate, lithium sulfate, tetrabutylammonium chloride, tetraethylammonium chloride, o-carborane, thioacetamide, N -(1-napthyl) ethylenediamine, 2,2'-biquinoline, p-bromoaniline, taurine, blue tetrazolium, 2-amino-3-methyl benzole acid, indol-3-aldehyde, cysteine, 4-acetamidoaniline, p-aminophenol, acetamide, 4-aminoacetophenone, 4-dimethylaminobenzaldehyde, 2-aminobenzimadazole, bis-( 4,4' -bipyridyl)-α,α-p-xylene, red phosphorus and lithium p-toluenesulfonate; and optionally a solvent; and heating the mixture to a temperature of from 20° to 120°C to thereby form a cucurbit[n]uril. 5. A method as claimed in claim 4, comprising mixing a substituted glycoluril and an unsubstituted glycoluril. 6. A method as claimed in claim 5, wherein the substituted glycoluril has the formula: (Formula Removed) wherein R1 and R2 are the same or different and selected from an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical or a heterocyclyl radical or R1 and R2 form a cyclic hydrocarbon radical or heterocyclyl radical. 7. A method as claimed in claim 6 wherein the hydrocarbon radical for substituents R1and R2 is the same or different and selected from alkyl, alkenyl, alkynyl and aryl. 8. A method as claimed in claim 5, wherein the substituted glycoluril has the formula: (Formula Removed) 9. A method as claimed in claim 5, wherein the substituted glycouril has the formula: (Formula Removed) 10. A method as claimed in claim 5, wherein the substituted glycouril has the formula: (Formula Removed) 11. A method as claimed in any one of claims 4 to 10, wherein n is 4 to 10. 12. A method as claimed in any one of claims 4 to 11, wherein the mixture comprises a templating compound, wherein the templating compound is a salt and wherein the anion of the salt corresponds to the anion of the acid in the mixture. 13. A method as claimed in any one of claims 4 to 12, wherein the mixture comprises two or more templating compounds. 14. A method as claimed in any one of claims 4 to 13, wherein the acid comprises a strong mineral acid or a strong organic acid. 15. A method as claimed in any one of claims 4 to 14, wherein the acid is selected from sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, deuterated sulfuric acid, phosphoric acid, sulfonic acid, p-toluenesulfonic acid, and methane sulfonic acid. 16. A method as claimed in any one of claims 4 to 15, wherein the solvent is selected from trifluoroacetic acid, methanesulfonic acid and 1,1,1 - trifluoroethanol. 17. A method as claimed in any one of claims 4 to 16, wherein the compound that can form methylene bridges between glycoluril units comprises formaldehyde, paraformaldehyde, trioxane or one or more precursors for formaldehyde. 18. A method as claimed in any one of claims 4 to 17, wherein the mixture is heated to a temperature of from 20° to 110°C. 19. A method as claimed in claim 18, wherein the mixture is heated to a temperature of from 60° to 110°C. 20. A method as claimed in claim 18, wherein the mixture is heated to a temperature of from 80° to 110° C. 21. A method as claimed in any one of claims 4 to 20, wherein the mixture is heated for between 1 hour and 24 hours. 22. A cucurbit[n]uril substantially as herein described with reference to the accompanying drawings. 23. A method for producing a cucurbit[n]uril substantially as herein described with reference to the accompanying drawings.

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