ZA200306735B - Metal bis-triflimide compounds, their synthesis and their uses - Google Patents

Description

1 METAL BIS-TRIFLIMIDE COMPOUNDS AND ME THODS FOR 2 SYNTHESIS OF METAL BIS-TRIFLIMIDE COMPOUNDS 3 4 The present invention relates to meta 1 bis- triflimide compounds and methods for the synthesis 6 of metal bis—triflimide compounds. 7 8 A few metal bistriflimide compounds a re known. WO 9 99/40124 discloses titanium and zirco nium bistriflimidees and the production of these by 11 reacting AgN (SO,CF3), with R'R°MCl, where M is Ti or 12 zr; R! is indenyl, cyclopentadienyl ox 13 pentamethylcy/lcopentadienyl and R? is independently 14 indenyl, cyclopentadienyl, d 15 pentamethylcyclopentadienyl, methyl, methoxy, 16 hydroxy, 2,4, 6-trimethylphenoxy, trif luroethoxy, 17 hexafluroisopropoxy or chloro. Alumi nium

CONFIRMATION COPY

1 pistriflimide and Yttberium bistriflimide are know-n

2 (Syrmlett, February 1996, pl7 1). Scandium . 3 bistriflimide is also known (Synlett, September

4 1996, page 839). Magnesium and lithium bistriflimide are known (Tetrahedron letters 1997,

6 p26-45). :

7

8 The catalysis of chemical reactions is of major

9 importance in chemistry.

The compounds of certairm metals are known to act as L.ewis acids (electron

11 paix acceptors), which interact with the reactantss

12 (and products) of a reaction, producing a reactiorm

13 rate enhancement and/or selectivity enhancement.

14 Also salts of metals which can exist in variable oxidation states (such as transition metals) are

16 known to catalyse chemical reactions.

Examples of

17 the se reactions are Friedel—Crafts, oxidation,

18 red uction, Diels-Alder, isomerisation, coupling,

19 add ition and elimination reactions.

Catalysts come in two general categories; homogeneous where the

21 cat alyst is in the same phasse as the reactants and / . 22 or products, and heterogeneous, where the catalyst=

23 is in a separate phase from the reactants and/or

24 pro ducts.

Homogeneous catalwsts are characterised by

1 properties such as high resactivity and turnov er, but . 2 difficult separation from the products of a 3 recaction. Heterogeneous catalysts are charac terised 4 by properties such as lower reactivity and lower turarnover, but relatively straightforward sepa ration 6 from the products of a reaction. There is a "meed 7 for new catalysts having high reactivity and high 8 tuarnover, that can easily be separated from r eaction 9 pr-oducts. 11 The present invention prowides a metal bistri flimide 12 compound having the formula: 13 [M11 [ (N(SO2CF3) 2) (mx-yzy] ¥H7 [Ly] ™ 14 where M is a metal selected from the metals i:n 16 groups 5 to 10, 12 and 14 to 16 of the period ic 17 table and Cu, Au, Ca, Sr, Ba, Ra, Y, La, Ac, Hf, Rf, 18 Ga, In, Tl, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D vy, Ho, 19 Err, Tm, Lu and the actinides;

IL is a negative or neutral ligand; . 21 n is 2,3,4,5,6,7 or 8 ; 22 X 1s greater than or equal to 1 23 y is 0,1,2,3,4,5,6,70or 8; and 24 z is 0, 1,2,3 or 4.

1 By metal bistri flimide is also meant meatal bis- 2 trifluorometharaesulfonimide. M may reporesent more 3 than one type of metal ion. M is preferably 4 selected from groups 7, 8, 9, 10, 12 ard 14 of the periodic table. By group 8 is meant tke group 6 containing Fe, Ru, Os, Hs; by group 9 Dis meant the 7 group containimag Co, Rh, Ir, Mt,; etc. The cation is 8 preferably in a +2, +3 or +4 oxidation state but may 1°) also be in a +1., +5, +6, +7 or +8 oxid=tion state.

Preferably M is selected from Mn, Fe, Co, Ni, In, Zn 11 and Pb. More preferably M is selected from Mn(II), 1 2 Fe (III), Co(II) , Ni(II), In(III). Exarmples of 13 compounds accor-ding to the present inveantion are 1 4 calcium bis-tri flimide, strontium bis-&riflimide, barium bis-trifflimide, gallium bis-tri—Aflimide, 1 6 indium bis-triflimide, scandium bis-triflimide, 1 7 yttrium bis-tri flimide, lanthanum bis—triflimide, 1 8 cerium bis-triflimide, chromium bis-trIiflimide, 19 manganese bis-t—riflimide, iron bis-triflimide, cobalt bis-triflimide, nickel bis-trif limide, copper 21 bis-triflimide, zinc bis-triflimide, cadmium bis- . 2 2 triflimide, tira bis-triflimide, lead bmds-triflimide, 2 3 and bismuth bis-triflimide. 2 4

1 L may koe selected from oxos (ssuch as vo%Yy, . 2 phosphDdnes (such as triphenylphosphine), water, 3 halides or ketones. The ligand may originate from 4 a solvent, reagent or by-product in the reaction 5 mixture for making the catalysst or the reaction 6 mixture in which the ligand is used. 7 8 The cormpounds of the present Anvention have not be=en

S produced before. These compounds have been found to be particularly effective catalysts for reactions 11 that axe conventionally catalysed by Lewis acids. 12 They ame suitable for many Lewis acid catalysed or 13 Lewis acid mediated chemical t—ransformations. The=y 14 possess advantages over Lewis acids such as aluminium (III) chloride in that they do not form i6 excessively strong complexes with the reactants or 17 products of a chemical transformation. They are 18 particularly suitable for use in Friedel crafts 19 reactions such as the acylation or alklation of aromatdc compounds. They may also be used for thee . 21 sulfonwlation of aromatic compounds. In Friedel- 22 Crafts acylation reactions the “catalyst” is usual_ly 23 a stoichiometric reagent. Howwever, catalyst loadi.ng 24 can now be lower; as low as 1 mol % metal bis-

1 triflimide can give rise to quanti tative yields in 2 Friedel-Crafts acylation reactions.

The compounds 3 of the present invention will catalyse chemical 4 reactions in concentrations withirm the range ) 0.0000001 to 1000 mol %, preferably within the range 9) of 0.1 to 20 mol% and more preferambly within the 7 range of 0. 5 to 5 mol %. This reduces catalyst 8 waste.

As many of the metal bis-t—riflimide 9 compounds possess metals that can exist in variable oxidation sstates, this makes them suitable for 11 oxidation aand reduction chemical transformations. 12 Other chemical transformations that can be achieved 13 with metal bis-triflimide compounds include, 14 isomerisati_on reactions, coupling reactions, de- coupling, condensation (including the aldol and 16 Claisen cormdensations), polymerisation, 17 oligomerisation, dimerisation, addition, 18 elimination, addition/elimination, hydration, 19 dehydratior, hydrogenation, dehydrogenation, halogenaticon, sulfonation and nitration. 21 . 22 The metal Iois-triflimide compounds of the present 23 invention rmay be soluble or partially soluble or 21 insoluble Zin the reactants or products.

In such a

1 case they can act as both solvent and ca talyst. . 2 They may be soluble, insoluble or partia lly soluble 3 in a molecular solve nt or solvents including 4 supercritical solven ts, or may be dissol ved or suspended in an ioni ¢ liquid (molten sal t that is in 6 a liquid state at th e reaction temperature and 7 usually (but not ess entially) molten at or near room 8 temperature, i.e., 2 0 °C). In all these cases the 9 metal bis-triflimide compound may act as a catalyst or reagent that effe cts chemical transfo rmation. 11 When the compounds o f the present invent ion are 12 soluble or partially soluble in the reac.tants, the 13 ‘reaction can proceed in the absence of a solvent. 14 Alternatively, the ¢ ompounds may be diss olved or suspended in an ioni ¢ liquid and the rea ction can 16 proceed in an altern ative medium to that provided by 17 conventional solvent s such as dichlorome-thane. 18 Therefore the compou nds of the present i nvention 19 provide the advantag e that they can be used in solvent-free conditi ons or in the presen ce of ionic . 21 liquids thus obviati ng the need for the use of 22 explosive solvents s uch as nitromethane and toxic 23 solvents such as dic hloromethane.

Furth ermore, when 24 used reactions in so lvent-free conditiomss or in the

1 presence of ionic li-quids, the metal bis-t riflimides 2 of the present inven—tion are easily recycl ed. } 3 4 In particular, the X—ray crystallographic structure of a new metal bis-triflimide salt, Zn(N( SO,CF3),), 6 kas been investigate«d and it is thought to give rise 7 &o its excellent cat.alytic properties.

The structure 8 of metal bis-triflimide compounds is thoug ht to be 9 similar to that of z_inc bis-triflimide, th e X-ray crystallographic structure of which is shown in 11 figures 5S to 7. 12 13 As can be seen from the structure of zinc( II) bis- 14 ®riflimide, it is maede of two bis-triflimi de groups coordinating to the mmetal through the oxygen atoms 16 of the bis-triflimide ion (and not the nit rogen 17 atom). The two rema_ ining octahedral coord inating 18 sites on the metal atom, are filled with o=xygen 19 atoms from adjacent 2Zn(NTf,). groups.

As some of the ruetal bis-triflimide s compounds are volati le, it is 21 boelieved that the co-ordination from adjace=nt metal . 22 bBois-triflimide group s may be fairly weak.

1 The compounds of t—he present invention =re volatile . 2 and are therefore suitable for use in a process of 3 vacuum deposition of metals or metal cormpounds on 4 solid surfaces. This may be achieved bsy sublimation of the metal compound onto the solid sumface and , 6 if desired, removal of the non-metallic part of the 7 compound. The compounds of the present invention 8 are volatile, part-icularly at temperatumes below 9 1000°C, more parti cularly at temperature s under 400 °C, under vacuum or at atmospheric pressure. Table 1 11 gives the boiling/sublimation points fox metal 12 bistriflimide compounds (dec. means decomposes) 13 Table 1

Metal bis- Bp / °C at 1 mmHg mn

2 This vacuum deposition process has applications in 3 t_he microelectronic and semiconductor industriess. 4 The vacuum deposition process is suitable for army } metal bistriflimide compound which decomposes besfore 6 it boils. 7 8 The present invention &lso provides a process for 9 t_he production of metal bistriflimide compounds wrhich process comprises reacting 11 ( a) hydrogen bistrifli mide with a metal; 12 ( b) hydrogen bistrifli mide with a metal hydroxi.de; 13 ( ¢) hydrogen bistrifli mide with a metal sulfide; or 14 ( d) hydrogen bistrifli mide with a metal carbide.

16 This process is suitabXe for producing both the 17 metal bistriflimide comnpounds of the present 18 i_nvention and already known metal bistriflimide 19 compounds.

The above process is therefore . applicable to metal bistriflimide compounds where M 21 i_s a metal selected from the metals in groups 1 to

1 16 of the periodic t able and the lanthani des and the . 2 actinides. 3 4 Preferably the above= process involves the interaction of a met.al or a metal compourmd with bis- 6 triflimide (bis-tri fluoromethanesulfonimide or 7 (HN (SO,CF3),). Prefe=rably the metal is a transition 8 metal (d block or £ block) or selected from the 9 metals of groups 12 to 16. Preferably thie metal is selected from Sn(IV) , Fe(III), In(III), Hf (IV), 11 Ti(IV) and W(VI). 12 13 The process can be carried out in a solvesnt such as 14 water, alcohol, ester or a molecular supercritical solvent, e.g. carbor dioxide, or ionic solvent.

The 16 reaction may be carried out at room temperature or 17 at an elevated temperature.

If a solvent- is used, ) 18 the metal bis-trifl#imide compound may also be made 19 by the interaction of hydrogen bis-triflimide and a metal compound in tle absence of a solverht.

The : 21 metal bis-triflimide compounds are separated from 22 the solvent by evaporation of the solvent, usually 23 by heating (to drives off water or anothex solvent), 24 preferably under vacuum.

Further purification may

1 be achieved by vacuumn distillation or vacuum

2 sublimation of the metal bis-triflimide cormpound. .

3 Purification can also be achieved by some other

4 physical or chemical process, for example,

crystallisation.

6

7 The metal bis-triflimide compounds of the poresent

8 invention can be genesrated and used in sitwzi for the

9 catalysis of chemical reactions or to bring about chemical transformati.ons.

This involves tke

11 addition of a metal compound (such as a metal

12 halide, such as chloride, bromide, iodide ox

13 fluoride) to a source of the bis-triflimide= ion

14 (such as a bis-trifli.mide ionic liquid). Preferably the metal compound iss a metal chloride.

These in

16 situ metal triflimide= compounds have similar or

17 greater catalytic actzivity to isolated metal

18 triflimide compounds.

The present inventicon

19 therefore provides a process for the producction of a metal bistriflimide catalyst comprising adding a

21 metal or metal compouand to a source of a 22 bistriflimide ion such as a bistriflimide Zionic

23 liquid.

An ionic licguid is a molten salt oor mixture

“4 of salts that is in t-he liquid state at the

1 temperature= of the reaction.

The iomic liquid . 2 consists of two components, which ar-e a positively 3 charged cat ion and a negatively char-ged anion. 4 Preferably the cation is an organic cation and the anion is am organic or inorganic ani on.

That cation (3 for the process is preferably a l-al kylpyridinium 7 (such as l1—hexylpyridinium) or 1, 3- 8 dialkylimidazolium cation such as 1- butyl-3- 9 methylimidamzolium [bmim] or l-ethyl- 3- methylimidazolium [emim]. Other cat ions for this 11 process ares other alkyl- or poly-alk ylpyridinium, 12 alkyl or poly-alkylimidazolium, alkyl or poly- 13 alkylpyrazolium, alkyl or poly-alkyl ammonium, alkyl 14 or poly-alkyl phosphonium, other amm onium, phosphonium cations, alkylated diaza bicyclo-[5,4,0}- 16 undec-7-ene and related cations, or any other cation 17 that gives rise to compounds termed ionic liquids. 18 The anion for the process is preferably one that is 19 stable to chemical alteration duringr the reaction and imparts desirable physical characteristics to . 21 the ionic Riquid.

Some suitable ani ons for the 22 ionic liquid are bis-trifluoromethamesulfonimide, 23 bis~-pentafRuocroethanesulfonimide, 24 hexafluorophosphate(V), tetrafluorol>orate (III),

1 trifl uoromethanesulfonate, cya namide, fluoro or 2 perfl uoroalkylsulfonate, halide, sulfate, 3 hydrogensulfate, alkylsulfate, alkylsulfonate, 4 arylsulfate, arylsulfonate, ni trate, carboxylate, phosphate, hydrogenphosphate, dihydrogenphosphate=, 6 alkyl.phosphate, alkylphosphona te, phosphonate, 7 nitri_te, arsenate, antimonate, haloaluminate, 8 alumi_nate, borate, silcate, ha loindate (III), 9 gallate, alkylborate, halogall ate or any other arxion that gives rise to an ionic li quid.

Preferably t he 11 ionic liquid or the catalyst or the ionic liquid and 12 catal yst combination is insoluble in low- or non— 13 polar organic solvents such as diethyl ether or 14 hexame.

16 An ex=zample of the preformed bi s-triflimide cataly=sis 17 and #n situ formed catalysis of the acylation of i 18 toluene with benzoyl chloride is shown below:

In situ catalysis FeCl (1 mol %) + . CH; oi Ey ] [N(SS02CF3)] ? + > ’ 150 mol % 100 mol % HC J

Preformed catalysis

CH; COClI Q

Cr . $i tron(111) bis-triflimide (1 moll %)

TT) 1 150 mol % 1 00 mol % 2 3 4

In this reaction, iron(III) chloride will not 6 catalyse the reaction (very low yields are obtained) 7 since the product (a ketone) forms a strong complex 8 with the i rxon(III) chloride and renders it almost 9 inactive. The addition of iron (III) chloride to a bis-triflimide source (hydrogen bis-%riflimide 11 {HN (SO,CF3) »,} or a bis-triflimide sal® or ionic 12 liquid results in the formation of am iron (III) 13 triflimide complex (or iron(III) chlero bis- 14 triflimide compounds or complexes). These iron k 15 (III) trif limide complex (or iron(II) chloro bis- 16 triflimide compounds or complexes) can then be used 17 as catalysts for chemical reactions, with acylation 18 being an example. The rates of the xeactions given

1 in the above reaction scheme are similar and give 2 high wields (99 3%). ] 3 4 This Zn situ catalyst method carx be used for the synthesis and use of metal trifl imide compounds 6 allowss metals that are not usual ly associated with 7 Friedel-Crafts chemistry to be used as catalysts. 8 Also difficult to isolate bis-triflimide compounds 9 can be made and used as catalysts.

11 In many cases, the in situ method of forming metal 12 bis-triflimide compounds is preferred over the 13 isolation of the metal triflimide compound.

For 14 example, tin(IV) bis-triflimide is a difficult compound to isolate.

If tin(IV) chloride is 16 dissolved in a triflimide ionic liquid (for example 17 [bmim] [NTf,]), the resulting mix ture catalyses 18 Friedel-Crafts acylation reactions.

This is shown 19 in Figure 4, where the yield versus time, of five in situ rmetal triflimide compounds that catalyse the 21 reaction of benzoyl chloride with toluene is shown 22 (Exampoles 45-50).

VWVO0 02/072260 PCT/GB02/00989 1 The present invention is illustrated in tzhe . 2 following examples. Examples 1 to 26 are examples 3 of the reactivity of the new metal bistri_flimide 4 compounds according t o the present invent-ion.

Examples 27 to 50 are methods of preparing metal 6 bistriflimide catalys ts according to the present 7 invention. 8 9 Figure 1 shows the variation of yield witch time in the metal bis-triflimide catalysed reaction of al benzoyl chloride with. toluene. az as Figure 2 shows the variation of yield witch time in a4 the 1% FeCl; and 1% Fe(III} bistriflimide= catalysed a5 reaction of benzoyl chloride with toluene in im [bmim] [NT£,]. a7 718 Figure 3 shows the variation of yield with time in 9 the synthesis of phemyl-4-chlorophenyl sulfone. : 21 Figure 4 shows the variation of yield with time for 22 five reaction catalyssed by 1 mol% metal chlorides 23 dissolved in [bmim] [NITf,] for the reacticon of

1 toluene with benzoyl chloride to give methyl 2 benzophenone at 110*C. . 3 4 Figures 5, 6 and 7 show the structure of Zn (NT*£f,) 6 ¥Example 1: The reaction of toluene with benzoy 1 7 e<hloride with cobalt (II) bis-triflimide cataly st. 8 9 Cobalt (II) bis-trifl imide (0.13 g, 0.21 mmol) =was &dded to toluene (3. 0g, 32.5 mmol) and benzoyl 11 —hloride ( 3.0 g, 21 .3 mmol) in a 25 cm? round 12 IDottomed flask equip ped with a magnetic stirrer and 13 r—eflux condenser. The mixture was heated under 14 reflux for 3 hours ( judged to be at least 99 § complete by gas chrommatographic analysis), and 16 —ooled to room tempe rature. Petroleum ether (15 17 =m’, bp = 40-60°C) was added and the catalyst 18 Precipitated out of =olution. The solution of the 19 pproduct was decanted and the flask washed with a

Further 15 cm’ of petzroleum ether. The solvent was 21 esvaporated from the combined petroleum ether 22 e-xtracts and the product purified by vacuum . 23 d.istillation (bp = 160-170 °C @ 1 mmHg) in a 24 K-ugelrohr apparatus. This gave methylbenzopheraone

1 (4.05 g, 97 % isolated yield). The catalyst «can be : 2 reused immediately by adding toluene and benz oyl 3 chloride to the flask (containing the precipi tate) 4 and repeating the reaction. 6 Example 2: The reactior of toluene with benzo yl 7 chloride with cobalt (IX) bis-triflimide catal yst in 8 [emim] [NTf,]. 9

Cobalt (II) bis-triflimdde (0.13 g, 0.21 mmol) was 11 added to l-ethyl-3-methylimidazolium bis- 12 trifluoromethanesulfonsimide ({emim] [NTf,)) (2 .0 Qg) 13 in a 25 cm® round-bottomed flask equipped with a 14 magnetic stirrer and reflux condenser, and time mixture stirred until the catalyst dissolved. 16 Toluene (3.0g, 32.5 mmol) and benzoyl chloridke ( 3.0 17 g, 21.3 mmol) were added. The mixture was he=ated 18 under reflux for 0.5 hours (judged to be at least 99 19 $ complete by gas chrormatographic analysis), and cooled tc room temperature. Petroleum ether (15 . 21 cm®, bp = 40-60°C) was added and the catalyst and 22 ionic liquid formed a separate phase. The solution 23 of the product was decanted and the flask 24 (containing the ionic Jdiquid and catalyst) washed

Wa 02/072260 PCT/GB02/00989 a three times with 1 5 cm? of petroleum ether. The 2 solvent was evapor ated from the combined petroleum i 3 ether extracts and the product purified by vacuum a distillation (bp = 160-170 °C @ 1 mmHg) in a

S Kugelrohr apparatus. This gave methylbenz«phenone <5) (4.02 g, 96 %). The catalyst and ionic liquid = combination can be reused immediately by adding 8 toluene and benzoyl chloride toc the flask and

S repeating the reac tion, without loss of activity. 1a Examples 1 and 2 s how that the acylation of toluene 12 with benzoyl chlor ide can be carried out with a 13 cobalt (II) bis-tri flimide catalyst and that this can 14 be performed with or without an ionic liqu id present. However, with the ionic liquid, faster 16 reaction rates are obtained and the cataly st can be 177 recycled more easi ly. Without the ionic 1 iquid, the 18 products of this reaction are obtained in 19 quantitative yield using 1 mol % catalyst after 3 hours heating under reflux (example 1). T he 271 reaction time is reduced to 30 minutes whe n the : 22 reaction is carrieed out in the ionic liqui d 23 [emim] [NTf;] ([emixn] = l-ethyl-3-methylimicdazolium) 244 (example 2).

1 Example 3: The reaction of toluene wwith benzoyl . 2 chloride with nickel (II) bis-triflimmide catalyst in 3 (emim] (NT£,]. 4

Nickel (II) bis—triflimide (0.13 g, 0.21 mmol) was 6 added to l-ethy?l-3-methylimidazoliu m bis- 7 trifluorometharaesulfonimide ([emim] [NT£,]) (2.0 g) 8 25 cm’ in a rou nd-bottomed flask egwuipped with a 9 magnetic stirrer and reflux condensser, and the mixture stirred until the catalyst dissolved. 11 Toluene (3.0g, 32.5 mmol) and benzoyl chloride (3.0 12 g, 21.3 mmol) were added. The mixt-—ure was heated 13 under reflux for 1 hour (judged to be at least 99 % 14 complete by gass chromatographic analysis), and cooled to room temperature. Petroleum ether (15 16 cm®, bp = 40-60°C) was added and thme catalyst and 17 ionic liquid f ormed a separate phasse. The solution 18 of the product was decanted and thes flask 19 (containing th e ionic liquid and catalyst) washed three times wi th 15 cm® of petroleuam ether. The . 21 solvent was ev-aporated from the commbined petroleum 22 ether extracts. and the product pur ified by vacuum 23 distillation (bp = 160-170 °C @ 1 —mmHg) in a 24 Kugelrohr apparatus. This gave me thylbenzophenone

1 (4.04 g, 97 % isolated yield). The catalyst and 2 ionic liquid combination can be reused immediately 3 by adeding toluene and benzoyl chloride to the fX ask 4 and repeating the reactiorm, without loss of activdty. 6 7 The re=sults from Examples 2 and 3 are shown in Table 8 1. 9

Table 1, The gas chromatogzxaphic (GC) yields of 11 benzopohenones derived from the reaction of benzoyl 12 chloride with toluene with 1% metal bis-triflimide 13 catalyst in {[emim] [NTL;].

EE

14

Example 4 16 anisole (0.30 cm®, 2.8 mmol), acetic anhydride (0.50 17 cm?®, 5 .0 mmol), M(NTf;), catalyst (0.1375 mmol (M = 18 Al, n—=3; M=2n, n=2; M= Yb, n=3; M=Y, n= . 19 3)) we=re dissolved in the ionic liquid [bmim] [PF sg] -

These four reactions were heated at 30 °C for 24 21 hours. The course of the reaction was determine<i by

1 HPLC analysis of the reaction mialxture and the yiel ds . 2 are shown in Table 2. 3 4 Table 2, The variation of GCyield with time for t he acetylattion of anisole with acet-ic anhydride with 6 metal b-is-triflimide catalysts An [(bmim] [PFs].

Catalyst |% vield $ Yield % Yield $ vield = ad EB Li i I I Li

A EE i 7 8 Example 5 9 Anisole (0.50 cm’, 4.6 mmol), benzoic anhydride (1.15 g, 5.06 mmol), M(NTfz), ca talyst (0. 23 mmol (M 11 = al, n=3, 0.20 g; M =Ce, n = 4, 0.29 g)) were 12 dissolv-ed in the ionic liquid [Bomim] [NTf,] (2.0 g) . 13 These t-wo reactions were heated at 60 °C for 24 14 hours. The course of the react ion was determined by gas chr omatographic analysis of the reaction mixtuare : 16 and the yields are shown in Tab le 3.

1 Table 3, The variation of GC yie 1d with time for 2 the benzowlation of anisole with benzoic anhydride ] 3 with metall bis-triflimide catalysts in [bmim] [PF¢]. %&= Yield $ Yield $ Yield $ Yield i I KN EN 4

Example 6 6 Fluoroben zene (5.77 g, 60 mmol), 4-fluorobenzoyl 7 chloride (4.75 g, 30 mmol), ZnCl, (1.36 g, 10 mmol) 8 and [emim ] [NTf,] were placed in arm autoclave and 9 heated with stirring for 48 hours at 160 °C. The reactor was cooled and the pressu re (HCl gas) 11 released. Gas chromatographic an alysis showed that 12 a 99 % comversion to a mixture of 2,4'- 13 difluorob-enzophenone, 3,4’-difluo robenzophenone, 14 4,4’ -difluorobenzophenone in 17 : 8 : 75 ratio respectively. The difluorobenzop henones were 16 isolated by solvent extraction wi th petroleum ether 17 (bp = 40 - 60 °C), followed by evaporation of the 18 solvent. The ionic liquid / zinc. chloride catalyst 19 system co uld be used in further reactions, with . similar a ctivity. This result sh.ows that the 21 classical ly unreactive aromatic compound

1 fluorobenzene can be acylated with 4-fluorobemzoyl . 2 chloride to give isomers of 2-, 3-, or 4-4'- 3 difluorcbenzophenone in [emim] [NTf;] using an in 4 situ zinc catalyst.

This catalyst was generated by dissolving zinc(II} chloride in the [emim] [NT =] 6 ionic liquid.

The reaction gave a 95 % yield (17 : 7 8 : 75 o-, m—-, p- isomer ratio). 8 9 Example 7 1.0 Benzoic acid (0.31 g, 2.5 mmol), m-xylene (0. 53 g, 1.1 5.0 mmol), [bmim][NTf,] (0.50 g) and M(NTf;); (M = Co 12 (0.14 g, 0.25 mmol), or Zn (0.15 g, 0.25 mmol ) were 1.3 placed in flasks equipped with stirrers and 1.4 condensers.

The contents of the flask were h eated 1.5 under reflux (ca 140 - 150 °C) for 2 days, then 1.6 cooled to room temperature.

The products wer e 1.7 analysed by gas chromatographic analysis and found ) 1.8 to give 93 and 87 % conversions (for Co and Zn bis- 1.9 triflimide reactions respectively) to 2,4- dimethylbenzophenone and, it is believed to be, 2,6- , 21 dimethylbenzophenone (11 : 1 isomer ratio in both 22 cases). The results show that zinc and coba lt bis- 23 triflimide have been found to catalyse the 24 benzoylation of m-xylene with benzoic acid.

The

1 reaction is slower that the corresponding reaction =2 with benzoyl chloride. The catalyst was recsycled } 3 and the reaction was repeated. The results of the 4 repeat experiment are shown in Table 4. © Table 4, The yields of benzophenones derived fxrom the 7 reaction of benzoic acid with m-xylene with 102

ES) recycled metal bis-triflimide catalyst in nt} [bmim] [NTf,] at 140 °C for 48 hours.

EE le 13 These are remarkable results given the low 12 reactivity of benzoic acid. It is to be noted that 13 this reaction produces water s a byproduct and as 1-4 such it is a very environmentally friendly reaction.

Furthermore, it utili ses a non-corrosive starting le material (benzoic acid) and therefore is a safer 177 reaction to perform than the corresponding reaction 18 with benzoyl chloride. It can be concluded that . 1 this is superior way to produce dimethylbenzophenone.

W-0 02/072260 PCT/GB02/00989 1 Example 8: The reaction of toluene with benzoyl : 2 chloride with zinc(II) or copper (II) bi=s-triflimide 3 catalyst in [emim]] [NTf.]. 4

Copper or zinc (IX) bis-triflimide (0.13 gq, 0.21 6 mmol) was added to a mixture of toluene (3.0g, 32.5 7 mmol) and benzoyl chloride (3.0 g, 21.3 mmol). The 8 mixture was heated under reflux for 72 Thours (the 9 reaction was monitored by gas chromatog raphic 1.0 analysis, by takimg a drop of the react ion mixture 11 and suspending it in petroleum ether (b .p. = 40- 12 60°C) and filterimg off the catalyst. The starting a3 materials and products, which are solub le in the nd petroleum ether extract, were cooled to room

R25 temperature. Pet xoleum ether (15 cm®, lop = 40-60°C) iN was added and the catalyst and formed a separate a7 phase. The solut ion of the product was decanted and 38 the flask (contaiming the catalyst) was hed three a9 times with 15 cm® of petroleum ether. "The solvent was evaporated fr om the combined petrol. eum ether . 21 extracts and the product purified by va cuum 22 distillation (bp = 160-170 °C @ 1 mmHg) in a 23 Kugelrohr apparat us. This gave methyllwenzophenone 24 (4.0 g, 95 %). The catalyst can be rewmsed (A

1 immediately by adding toluene and benzoyl chloride 2 t o the flask and repeat ing the reaction, without 3 1 oss of activity. The yields as determined bx gas 4 chromatographic analysis are shown in Table 5 . 6 Table 5, the yields of benzophenones derived from the 7 r-eaction of benzoyl chloride with toluene with 1 % 8 ceopper (II) or 1 % zinc(II) bis-triflimide catallysts. 9 The figure in brackets xefers to the o-, m- and p- i somer ratios.

Time / h Yield with Yield with

I ro i 11 12 Z inc(II) and copper(II) bis-triflimide compouncds were 13 f-ound to be effective acylation catalysts for the 14 b-enzoylation of toluene . 16 Example 9: The reaction of o-xylene with benzoyl . 17 chloride with an aluminium (III) bis-triflimide i8 catalyst. 19

Aa

1 Aluminium (III) bis-triflim—de (0.10 g) was adde=d to . 2 a mixture of o-xylene (3.0g. 28.2 mmol) and ben=oyl 3 ¢c hloride (3.0 g, 21.3 mmol) . The mixture was heated 4 at 120 °C for 18 hours (the reaction was monitomred b y gas chromatographic anal=ysis, by taking a drop of 6 t he reaction mixture and suspending it in petroleum 7 e ther (b.p. = 40-60°C) and filtering off the 8 c atalyst.

The starting materials and product ame 9 s oluble in the petroleum ether extract), and cooled t o room temperature.

Petroleum ether (15 cm’) wzas 11 a dded and the catalyst and formed a separate phase. 12 T he yields as determined by gas chromatographic 13 a nalysis was 99% with a 6.0 : 1 3,4- to 2,3- 14 d_imethylbenzophenone isomer ratio.

Aluminium(IZTII) bis-triflimide was found to be an effective catalyst 16 for the benzoylation of o-x—vylene.

The reaction gave 17 a quantitative yield of two isomers of the 18 corresponding benzophenone (6 : 1 3,4- to 2,3- 19 i somer ratio) after 18h at 120 °C, using 1 mol =% of catalyst. . 21 22 Exxample 10: The reaction of toluene with benzoyl 23 chloride with metal bis-tri flimide catalyst. 24 y

1 Various metal (l-ethyl-3-methylimidazol ium, Li, Mg, 2 Ca, Mn, Co, NA, Cu, Zn, Sn, Pb, Al) bis—triflimide 3 salts (1 mol ®) was added to a mixture of toluene 4 (3.0g, 32.6 mrnol) and benzoyl chloride (3.0 g, 21.3 mmol). The mixture was heated at 110 °C for up to 6 120 hours. The reaction was monitored at regular 7 intervals by gas chromatographic analysis and the 8 reaction stopped when the reaction was —judged to be 9 99 % complete by cooling to room temperature.

Petroleum ether (15 cm’) was added and the catalyst 11 and formed a separate phase. The product was 12 isolated be deecanting the petroleum ether extract, 13 followed by Kuagenrohr distillation at 1 mm Hg. The 14 yields after warious time intervals are given in

Table 6. The product formed is methylbesnzophencone. 16 In all these reactions, the isomer ratio was found to 17 be approximately 76 % para and 24 % ortho. This 18 results are shown in Table 6. Table 1 ldsts the 19 times required. for Co and Ni bis-triflimzide in [emim] [NTZ£;]. 21 22 Table 6, The y ields of benzophenones derived from the 23 reaction of be nzoyl chloride with toluenes with 1% 24 metal bis-trif limide catalyst. \ BS

I SE ki A A

EE SA

ER SE

ER SE

EEE SE

EEE SE

EEE SE

REE SE

1 2 From Tab_le 6, a remarkable diff erence in reactiv=ity 3 between —the compounds chosen is observed. Of tmese, 4 four compoounds appear to have u nexpectedly high reactivi-ty, namely those of man ganese, cobalt, 6 nickel amd lead, whereas compou nds such as zinc bis- 7 triflimicde and aluminium bis-tr iflimide have 8 relatively modest activity. Th is is completely 9 different to “conventional Frie del-Crafts chemisstry” which wowild suggest that the Al bistriflimide shmould 11 be the be=st catalyst. Of parti cular remark is t_he

1 catalytic reactivity of Co and Plo. Lithium and 2 calcium bi_s-triflimide in contrasst show very poor : 3 activity and with ([emim] (bis-trZiflimide], little or q no reaction was observed. 6 Example 1X: The reaction of chlorobenzene with 7 benzoyl chloride with nickel (II) bis-triflimide 8 catalyst Zn [bmim] [NTf,]. 9

Nickel (II®» bis-triflimide (0.062 g, 0.1 mmol) was 11 added to A -butyl-3-methylimidazo lium bis- 12 trifluorornethanesulfonimide ([bm_ im] [NTf,]) (1.0 g) 13 in a 25 crn® round-bottomed flask equipped with a 14 magnetic stirrer and reflux cond enser, and the mixture stcirred until the cataly st dissolved. 16 Chloroben=ene (1.68 g, 15 mmol) and benzoyl chloride 17 (1.41 g, 710 mmol) were added. T he mixture was 18 heated under reflux for 72 hours and was analysed by 19 gas chromatographic analysis as in previous examples. The reaction was coole-d to room 21 temperature. Petroleum ether (1 5 cm?, bp = 40-60°C) . 22 was added and the catalyst and ionic liquid formed a 23 separate phase from the petrolewxm ether layer. The 24 solution of the product (in petroleum ether) was

1 decanted and the flask (containing the ionic liquid : 2 and catalyst) washed three times with 15 cm’ of 3 petroleum ether. Concentration of the crganic 4 extract, fol lowed by Kugenrohr distillation at 1 mm

Hg (bp = 170-190 °C), gave chlorobenzopohenone (1.65 6 g, 74 %). GC analysis showed 78 % yield after 72 7 hours, with a 70 : 8 4- to 2- isomer ratio. This is 8 a remarkable result, as chlorobenzene =—is known to be 9 classically unreactive in acylation reactions. It has not previously been possible to iseolate 11 significant quantities of the products of the 12 acylation of chlorobenzene. i3 14 Example 12: The reaction of chlorobenz ene with benzoyl chloride with cobalt(II) bis-t riflimide or 16 zinc(II) bis-triflimide catalyst in [bemim] [NTf;]. 17 In two separate reactions, either zinc=(II)} bis- 18 triflimide (0.16 g, 5 mol %) or cobalt (II) bis- 19 triflimide (0.15 g, 5 mol %) was added to 1-butyl-3- methylimida=zolium bis-trifluoromethanessulfonimide . 21 ([bmim] [NT£f2]) (1.0 g) 25 cm’ in a rourhd-bottomed 22 flask equipped with a magnetic stirrer— and reflux 23 condenser, and the mixture was heated gently and 24 stirred unt il the catalyst dissolved.

1 Ch lorobenzene (0.68 g, 6 mmol) and benzoyl chloride 2 (0 .72 g, 5 mmol) were added. The mixture was heated . 3 un der reflux for 18 hours and was analysed by gas 4 ch romatographic analysis as dn previous examples.

Th € reaction was cooled to room temperature. 6 Cy clohexane (15 cm’) was added and the catalyst and 7 iomic liquid formed a separate phase. The solution 8 of the product was decanted and the flask 9 (ceontaining the ionic liquid and catalyst) washed three times with 15 cm? cyclohexane followed by 11 Kucgelrohr distillation at 1 mm Hg (bp = 180-200 °C). 12 Thos gave a mixture of 2- and 4-chlorobenzophenone. 13 GC yield = 97 % (6.8 : 1 p- to o- isomer ratio) for 14 coboalt catalyst and 55 % (6.5 : 1 p- to o- isomer ra®& io) for the zinc catalyst. 16 17 Thee reaction of chlorobenzene with benzoyl chloride 18 wass investigated, as chlorobenzene is much more 19 disfficult to acylate. Although reasonable yields corald be obtained with 1 mol % catalyst, it was 21 found that 5-mol % catalyst gave more acceptable . 22 reaction rates. The reaction was found to be 95 % 23 cornplete with cobalt bis-triflimide after 18 hours 24 ancd 55 % complete with zinc bis-triflimide (Table

1 7). The catalyst was found to be less active after : 2 extracting the product with boiling cyclohexane and 3 recycling tthe ionic liquid / catalwst. The activity 4 of the catalyst was restored by adding a trace of hydrogen bi s-triflimide (0.1 mol %3. 6 7 Table 7, The yields of benzophenone s derived from the 8 reaction off benzoyl chloride with chlorobenzene with 9 5% metal bis-triflimide catalyst in. [bmim] [NTf,]. * 11 Example 13 : The reaction of toluene with benzoyl 12 chloride w ith hydrogen and metal I»is-triflimide 13 catalyst. 14 Various me tal bis-triflimide compounds: Sr(II},

Ba(II), In (III), In(III) in [bmim]} {(NTf;], Cr(III), 16 Ce(IV), Yb» (III), and hydrogen bis—triflimide 17 {HN (SO,CF3®,} (1 mol %) were added to a mixture of : 18 toluene (1..38 g, 15.0 mmol) and benzoyl chloride 19 (1.41 g, 1.0.0 mmol). The mixture was heated at 110 °C for up to 120 hours. The reactzion was monitored 21 at variouss intervals by gas chromatographic analysis

SE

1 and th e reaction stopped after 5 days. The yields 2 of met hylbenzophenone with res pect to time are sh_own 3 in Figure 1. The reaction of benzoyl chloride an.d 4 toluene gave 2- and 4-methylbe nzophenone. All th. ese compoumds were found to be act ive Friedel-Crafts 6 catalysts, but with considerab ly different 7 activities. Of these, the act ivities of indium(I II) 8 and iron (III) (Example 14) are the most notable, as 9 they axe exceptionally good ca talysts. The p~ to o- selectdvities were in the range 3.9 to 4.4 to 1, 11 with the indium and iron catalysts giving 4.4 : 1 12 selectdvity. 13 14 Example 14: The reaction of toluene with benzoyl chloride with iron(III) bis-tr3flimide or iron(II) 16 chloride dissolved in [bmim] [NTT£f,]. 17 In two separate reactions, either iron(III) bis- 18 triflimide (1 mol %) or iron(III) chloride (1 mol %) 19 was added to l-butyl-3-methylirmnidazolium bis- trifluoromethanesulfonimide ([lomim] [NTf£,]) (1.0 gq) 21 25 cm® in a round-bottomed flask equipped with a _ 22 magnetic stirrer and reflux cordenser, and the 23 mixture was heated gently and stirred until the 24 catalyst dissolved. Toluene (1.38 g, 15 mmol) ard

1 benzoyl chlo ride (1.41 g, 10 mmol ) were added.

The : 2 mixture was heated under reflux feor 48 hours and was:

3 analysed by gas chromatographic amalysis as in

4 previous examples.

The yield of rmethylbenzophenone with respect to time is shown in Figure 2. Here, 6 the activity of the iron catalyst was tested in two

7 separate way s: (a) with 1% FeO(NT=;) in [bmim] [NTf:]

8 and (b) 1% FeCl; in [bmim] [NTf,]. In both cases, the 9 activity and selectivity were sim-lar, indicating that FeCl; amd FeQ(NTf,) are possi bly precursors to

11 catalyst, wh en dissolved in excess=s [bmim] [NTf;].

12

13 Example 15: The reaction of toluerme with methane

14 sulfonyl chl oride with zinc(II} bods-triflimide.

1é Zinc (II) bis -triflimide (0.13 g, 22.5 mol %) was

17 added to a r ound-bottomed flask ecguipped with a

- 18 magnetic sti rrer and reflux conderser.

Toluene 19 (1.38 g, 15 mmol) and methane sul=fonyl chloride (1.14 g, 10 mummol) were added.

The mixture was . 21 heated under reflux for 24 hours &=nd was analysed by- 22 gas chromato graphic analysis as im previous 23 examples.

A ll the methane sulfonyl chloride had 24 reacted and three isomers of (2-, 3- and 4-

1 methylphenyl)methylsulfone had formed (yield = 99 2 %), isommer ratio = 35 : 18 : 47 for the o-, m- and ) 3 p- isomers. The product was extracted from the 4 catalyst by dissolving it in cyclohexane (20 cm?) followed by decantation of thie cyclohexane extract. : © The cat=lyst was washed with cyclohexane (2 x 20 7 cm’) and the combined cyclohexane extracts were 8 concentmxated on a rotary evaporator. The product 9 was Kugeslrohr distilled at 100-110°C to give 1.62 g of a colourless oil (96 % isolated yield). 11 12 Example 16: The reaction of Ibenzene with benzene 13 sulfonyl chloride with zinc(II) bis-triflimide. 14

Zinc (II ) bis-triflimide (0.02 g, 1 mol %) was 16 dissolv-ed in [bmim] [NTf,] (1-0 g) in a round- 17 bottome-d flask equipped with a magnetic stirrer and 18 reflux condenser. Benzene (1.56 g, 20 mmol) and 19 benzene sulfonyl chloride (1 .76 g, 10 mmol) were added. The mixture was heated under reflux for 18 21 hours a nd was analysed by ga s chromatographic 22 analysi s as in previous examples. All the benzene 23 sulfony-1l chloride had reacted diphenyl sulfone had 24 formed (yield = 99 %). The product was extracted

1 from the catalyst and ionic liqu id by dissolving it . 2 in boilimg cyclohexane (5 x 30 cm’) followed by 3 decantat don of the cyclohexane e xtract.

The 4 diphenyl=sulfone crystalised on <ooling and was collected by filtration (2.03 g, 93 % isolated 6 yield). The reaction of benzene: with benzene 7 sulfonyl chloride gave the expeccted diphenyl sulfone 8 in 99% y ield with a Zn (NTf,), catalyst (18 h at 9 reflux). The diphenyl sulfone wras extracted with boiling <yclohexane and the ioni.c liquid and 11 catalyst could be reused. 12 13 Example 17: The reaction of m-xy~slene with benzene 14 sulfonyl chloride with zinc(II) bis-triflimide. 2inc (II) bis-triflimide (0.062 <, 1 mol %} was 16 dissolve d in (bmim] [NTf,] (1.0 g) in a round- 17 bottomed flask equipped with a mnagnetic stirrer and 18 reflux condenser and m-xylene (2.12 g, 20 mmol) and 19 benzene sulfonyl chloride (1.76 g, 10 mmol) were added.

The mixture was heated under reflux for 18 . 21 hours ard was analysed by gas chromatographic 22 analysis as in previous exampless.

All the benzene 23 sulfonyl. chloride had reacted ard mostly 2,4- 24 dimethyl diphenylsulfone had forrmed (yield = 99 %, 20

1 : 1 isomeer ratio {by NMR}). The major product is 2 shown below, the structure of th e minor isomer is 3 not knowr but is believed to be the 2,6-dimethyl 4 isomer.

CH, ci CH;0 0 [ 1% Zn(NTH), Ns’ +~ 0=8S=0 _—_—— ta cae 5 CH; 18 h/ 130°C H;C 2 8 The produact was extracted from the catalyst and 9 ionic liquid by dissolving it in boiling cyclohexane (5 x 30 cm?) followed by decantation of the 11 cyclohexane extract. The 2,4- 12 dimethyldiphenylsulfone crystalised on cooling and 13 was collected by filtration. 14

Example IL 8: The reaction of chlomrobenzene with - 16 benzene sulfonyl chloride with metal bis-triflimide 17 catalystss. 18 19 In three separate reactions, either magnesium(IT) bis-trifl imide (0.058 g, 0.1 mol», aluminium(III) 21 bis-trifl imide (0.87 g, 0.1 mmold or cobalt(II) bis- 22 triflimice (0.062 g, 0.1 mmol) was dissolved in

1 {bmim] (NT£,] (0.5 g) in a round-I=ottomed flask . 2 equipped wvith a magnetic stirrer and reflux 3 condenser — Chlorobenzene (1.68 g= 15 mmol) and 4 benzene sualfonyl chloride (1.76 og, 10 mmol) were

S added. Whe mixture was heated winder reflux for 1 44 6 hours and monitored by gas chromatographic analysis 7 as in prewious examples. The yields with respect to 8 time are given in Figure 3. The product was 9 extracted from the catalyst and donic liquid by dissolvincgg it in boiling cyclohexane (4 x 10 cm?) 11 followed boy decantation of the ¢ yclohexane extract... 12 The 2- anced 4-chlorodiphenylsulfo ne (9:1 p- to o- 13 isomer ratio) crystalised on coo ling and was 14 collected by filtration. The sel ectivity was 9:1 ffor the p- ise-omer and the o- isomer was the minor isomer 16 in all ca ses. Coincidently, the reaction of benzoyl 17 chloride with chlorobenzene also gave the same 18 selectivi ty and similar reactiom rates. Phenyl-4-— 19 chlorophe nylsulfone is an insect-icide. The reaction was found. to be slow using 1 mol. % catalyst, but 5S : 21 mol % cat alyst gave acceptable r-eaction rates. The 22 metal sal_ts chosen were aluminiuvam (III), cobalt (IID 23 and magne=sium (II) bis-triflimide, in the ionic 24 liquid [lonim] [NTf,]. All three catalysts were fouand

1 to be ef fective for this reacti on. The reaction is 2 shown be low. } 3 cl AP c 3 % M(NTH)), M= Co,n=2

Cr + 0=$=0 grr ro M= Al,n=3 4 Ph reflux Cl M= Mg, n=2 6 Example 119: The reaction of ben zene with oct-1l-ene 7 with nickel (II) bis-triflimide. 8 9 Nickel (II) bis-triflimide (0.06 g, 0.1 mmol) was dissolved in [bmim] [NTf,;] (1.0 g) in a round- 11 bottomed flask equipped with a magnetic stirrer and 12 reflux condenser. Benzene (3. 90 g, 50 mmol) and 13 oct-l-ene (1.12 g, 10 mmol) wer-e added. The mixture 14 was heated under reflux for 18 “hours and was analysed by gas chromatographic analysis as in 16 previous examples. The oct-l-en-e peak disappeared 17 and threes isomers of octylbenzeme were formed (70 %, 18 20:26:54 2- to 3- to 4- isomer ratio) as well as 19 octene ddmer (30 %). The less «dense product phase was decarmted from the ionic / csatalyst phase and 21 purified by Kugelrohr distillat. jon. The ionic 22 liquid ard catalyst were prepare«ed for reuse by 23 heating &t 60 °C under vacuum feor 1 hour. The ionic

1 liquid and catalyst were used for further resactions : 2 of benzene with octt-l-ene without loss of activity. 3 This is an alkylati.on of benzene with an all<ene 4 using a metal bis-triflimide catalyst. Benzesne and oct-l-ene react in the presence of 1% nickel l(II) 6 bis-triflimide in fbmim] [NTf,] to form three isomers 7 of octyl benzene and a small amount of hexacdecene 8 (unknown isomeric distribution). This is skiown 9 below: 11 @ ~~ 1 mol % Ni(INTf), [bmim][NTH;] reflux, 224 h

Shan + ys + ~~ 12 13 The alkylation of benzene with oct-1l-ene. 14

The reaction gave a 70 % yield (by GC) of t hree 16 isomers of octylbemnzene. The isomer ratio was 17 determined to be 0.75 : 1.00 : 2.03, with t he 4- 18 phenyloctene as the major product and 2-phe nyloctene 19 as the minor product. During the course of the reaction, isomerat ion of oct-l-ene to a nurmmber of 21 isomers of octene was observed, and the rat.e of this

SE

1 isomerisation process was considerably faster thaw 2 the alkylation reaction. It was found that the iomic } 3 liquid / catalyst combination remained active on & 4 second run. To confirm that the minor product of the reaction was an octene dimer, the same reaction 6 was performed, but without any benzene present 7 (shown below). 1 mol % Ni(NTf;), Rel Lae. [mim] [NT] reflux, 24 h ees

Prelonged reaction times results in further alkene -— bond migration

Obtain a mixture of isomers + some trimer 8 9 11 The dimerisation of oct—1l-ene. 12 13 The reaction proceeded initially with isomerisaticn 14 of octene to a mixture of 4 isomers of octane.

After 18 hours, the reaction was almost complete (> 16 95 % conversion). The products were a large number

V&/0 02/072260 PCT/GB02/00989

1 of isomers of dimerised and trimerised c=ctene.

As . 2 the reaction was left to run for 6 days, a 3 broadening of the cluster of GC peaks for the dimer 4 and trimer was ob served, indicating that further isomerisation was occurring. 6 7 Example 20: The dimerisation of oct-l-erae with 8 nickel (II) bis-tr-iflimide. 9 a0 Nickel (II) bis-tr-iflimide (0.062 g, 0.1 mmol) was a1 dissolved in [bmim] [NTf,] (0.5 g) in a r-ound- a2 bottomed flask equipped with a magnetic stirrer and 3 reflux condenser.

Oct-l-ene (1.12 g, 10 mmol) was 4 added.

The mixture was heated under reXlux for 18 a5 hours and was analysed by gas chromatographic 6 analysis as in previous examples.

The oct-1l-ene peak 7 disappeared and three isomers of octene (oct-2-ene, 18 oct-3-ene and oct-4-ene) were formed.

HMydrogen bis- 19 triflimide was added (0.0028 g, 0.1 mmol) and the mixture was heated for a further 18 houxs.

Gas 21 chromatographic analysis showed that the reaction 22 was almost complete (> 99%), and gave a mixture of 23 isomers of hexadecene and tetracosene ( trimer of 24 octene). The less dense product phase was decanted

1 E£rom the ionic / catalyst phase and purified boy 2 Kugelrohr distillation &at 1 mm Hg. The ionic liquid } 3 and catalyst were prepared for reuse by heatirmg at 4 60 °C under vacuum for 1 hour. The ionic liquaid and catalyst were used for Further dimerisation 6 ‘reactions of oct-l-ene without loss of activitcy. 7 8 Ezxample 21: The Fries rearrangement of 4- 9 maethylphenoxybenzoate with hydrogen and metal bis- t riflimide compounds. 11 12 Y tterbium(III) bis-trifl imide (0.1 g) and hydrogen 13 bris-triflimide (0.01 g) was dissolved in (n-H; oCia(n-— 14 H 13C6)3P] [NTf2] (1.0 g) im a round-bottomed flask e quipped with a magnetic stirrer and reflux 16 condenser. 4-methylphenoxybenzoate (1.0 g) weas 17 a dded. The mixture was heated under reflux for 24 18 h ours at 60 °C and was analysed by gas 19 c hromatographic analysis as in previous examples.

T he product of the reaction was 2-hydroxy-5- 21 m.ethylbenzophenone (90 % yield). The isomerisaation 22 o f 4-methylphenoxybenzoate to 2-hydroxy-5- 23 methylbenzophenone is skhaxown below. .

Ome OX] ° 1% Yb(NTf); ~ HNTf; Ci ® ry I [n-HasC 14(r-H 13C3PIINTE] pee 1 HC 0) 2 3 4 Example 22: The reaction of o-xy-lene, m-xylene, mesitylene, and toluene with cyclohexene with meta l 6 bis-triflim ide compounds. 7 8 In four sep arate reaction vessel s, ytterbium(III) 9 bis-triflimide (0.1 g) was dissolved in [n-HzoCis(n -

H13Ce) 3P] [NT£;] (2.0 g) in a rouncd-bottomed flask 11 equipped wi th a magnetic stirrer- and reflux 12 condenser. Either o-xylene (1.06 g, 10 mmol), m— 13 xylene (1.06 g, 10 mmol), mesit—ylene (1.20 gq, 10 14 mmol), or t-oluene (0.92 g, 10 mmol) were added to the separate flasks followed by addition of 16 cyclohexene (0.82 g, 10 mmol) . The mixtures were 17 heated at 80 °C for 12 hours and were analysed by 18 gas chromatographic analysis as in previous 19 examples. The cyclohexene peak disappeared and peak (s) due to alkylation of the aromatic compound ’ 21 and peaks due to dimerisation resactions of 22 cyclohexene were formed (see Example 26). The iormic 23 liquid and catalyst were preparead for reuse by

1 heating at &0 °C under vacuum fo r 1 hour. The ionic 2 liquid and catalyst were used fo r further reactions . 3 of benzene wwith cyclohexene with out loss of 4 activity. 6 Example 23: The reaction of benz ene with dodec-l-ene 7 with metal I»is-triflimides, trif lates and hydrogen 8 bis-triflim=ide. 9

In ten sepa—xate reaction vessels (a multi-cell glass 11 reactor wit¥ar stirrers and conden. sers) metal 12 triflimide or metal triflate compounds (see Table 13 below) were added together with hydrogen bis- 14 triflimide (0.01 g) to [n-HzgCi4{-n-H13Cs)3P] [NTE2] (2.0 g) and stirred until the metal compound had 16 dissolved. Benzene (3.8 g, 50 mmol) and dodec-1- 17 ene (0.84 g, 5.0 mmol) were addeed. The mixtures 18 were heated at 80 °C for 24 hours. The excess 19 benzene was distilled off. The mixture was analysed by NMR upon cooling to room temperature. The ionic 21 liquid and catalyst were prepared for reuse by 22 heating at 60 °C under vacuum fcr 1 hour. The ionic 23 liquid and catalyst were used for further reactions

1 of benzene with dodec-1l-ene without loss of . 2 activity. The results are shown in Table 8 below. 3 Table 8

Compound Mass / g Unreacted Isomerised | Dodecyl

Rr i EY A

IE hI

EE A EE SE

IE A A

FE EA EN i A CA

RE

I

I I CC

ERA Ra A GN 4

Example 24: The reaction of toluene with benzoyl 6 chloride with metal compounds dissoXved in 7 (bmim] [NT£,] - 8 9 In five separate reactions, either tzitanium(IV) chloride (1 rwl %) or tin(IV) chloride (1 mol %), or 11 tungsten(VI) chloride, or hafnium(I\U) chloride or 12 palladium(II ) chloride was added to 1l-butyl-3-

1 methylirnidazolium bis-trifluoromethanesulfonimide 2 ( {bmim] INTf,)) (2.0 g) 25 cm® im a round-bottomed 3 flask equipped with a magnetic stirrer and reflux 4 condenser, and the toluene (2.81 g, 30 mmol) and benzoyl chloride (2.84 gq, 20 mmol) were added.

The 6 mixturess was heated under reflux for 24 hours and 7 was anallysed by gas chromatographic analysis as in 8 previouss examples.

The conversion of starting 9 materials to methylbenzophenone was quantitative except Kor the palladium(II) catalysed reaction (75 11 $ yieldDd . The variation of yield with time in the 12 reactiorh of several new metal b>is-triflimide jalis 13 in the meaction of benzoyl chloride with toluene in 14 given im Figure 4. These reactions were performed in parallel, and the yields were determined by GC 16 analysiss.

This reaction are gi.ven in more detail in 17 exampless 45 to 50. 18 19 In this invention, the use of & metal halide dissolveed in a bis-triflimide ionic liquid can be 21 used for reactions such as the Friedel-Crafts 22 reactioms.

This is useful where a particular metal 23 bis-tri=flimide salt is difficult to prepare or eC 24 isolate . In this invention, five metal halides

1 (chloricdes) (1 mol % with resp ect to the reactaants) . 2 were disssolved in [bmim] [NTf,] . This combinati on 3 was used to catalyse the react ion of toluene wi th 4 benzoyl chloride to give methy lbenzophenone. The yield woth respect to time is given in Figure A. 6 All of the metals chosen gave the expected products 7 in good yield, but the combina tion of 1% mol t&n(IV) 8 chlorides in [bmim] [NTf,] was a particularly 9 effectiwe catalyst. This process of using metal compouncds dissolved in an ionic liquid (usuallwy bis- 11 triflim.dde) can also be used wisith compounds of other 12 metals (particularly transition metals (d-block) or 13 f-block metals)) not listed ira Figures 3 or 4. 14

Example 25 16 A numbe r of aromatic sulfonylation reactions wesre 17 performed. These reactions arte very similar teo 18 Friedel -Crafts acylation react-ions and are per formed 19 under s imilar conditions. The key difference is that a -30,-X group replaces aa -CO-X (X = leaving . 21 group) . In most cases, the selectivities, 22 reactiv-ities and yields were —found similar to the 23 correspoonding acylation react=-on. The reaction of 24 sulfury=l chloride with benzene resulted in the

1 formation ©f chlorobenzene (quant itatively) and SO,. 2 This is as is found in many other reactions of S0,Cl, . 3 with aromatzic compounds performed. in molecular 4 solvents.

CH;

Cl 1% Zn(NTf), + O=S=0 — SO,CHj;

CH [bmim][NTf,] 3 H;C oOo. .0

Cl \/

I 1% Zn(NTfy), >sZ + 0=8=0 —_— mim][NTY;

Ph [bmim][NTf]

Cl 1% Co(NT£,), cl + 0=S8=0 —_— [bmim][NT£] 6 Cl 7 8 Example 26 9 The alkylatzion of various aromati c¢ compounds with ” 10 cyclohexene in a phosphonium ioni ¢ liquid with 10 $% 11 ytterbium(¥. II) bis-triflimide wit h a trace of 12 hydrogen bi_s-triflimide were carr ied out. A side 13 reaction al _so takes place that re sults in the 14 formation of a dimer of cyclohexe ne (see below) and this results in a slight reduction in the yield of 16 the Friedel -Crafts reaction. How ever, is should be

1 noted that this demonstrates that met=l triflimide : 2 compounds can be used for dimerisatiorm and 3 oligomerisa tion reactions. 4

CH; Cyclohexene 1% Yb(NTf;); / (trace) HNTE, 82% _ Cm . [1n-H29C14(n-H13C6)3 PINTS] HAC 46 : 54 isome=r ratio 3

CH; Cyclohexene H;C gi 1% Yb(NTH,)s / (trace) HNT, 86 % _— -H59C14(n-H,3Cg)3P}[NTH; 90 :10 isome=r ratio

CH; (n-H29C14(n-H,3C6)3P) [NTH] HiC

CH; Cyclohexene 1% Yb(NTf); / (trace) HNTf 85%

EE ———. gave | isomer -Ha6C14(n-H3Cg)3P]INTT: [7-H29Ca(n-H13Ce)3P][NTE] HC CH

CH;

H;C CH, Cyclohexene H;C CH; 1% Yb(NT{;)3 / (trace) HNTf; [n-H29C14(n-Hy3Ce)3P][NTL] ° 6 7 The reaction of aromatics with cycloh-exene in a 8 phosphonium ionic liquid for 12 hours at 80 °C is 9 shown abovee. Below is shown the dime risation of cyclohexene. 11

1 Example 27 2 Preparation of magnesium bis-triflimide. 3 Magnesium (0.048 g, 2.0 mmol) was added to a 4 solutzion of (hydrogen) bis-triflimide (HN (S0,CF3),, 1.12 g, 4.0 mmol) in distilled water (5 g) in a 25 6 cm® round bottomed flash equipped with a magnetic 7 stirrer.

The mixture was stirred for 1 hour (judged 8 to be complete when the evolution of hydrogen 9 ceased), and was filtered.

The water was evaporated on a rotary evaporator, and the magnesium bis- 11 trif limide dried by heating at 150 °C at 1 mmHg for 12 4 houurs in a vacuum drying apparatus, to give a 13 white powder (1.10g, 95 %). The magnesium bis- 14 triflimide was purified by vacuum sublimation at 300 °C at 1 mmHg in a Kugelrohr apparatus.

The 16 unpumrified magnesium bis-trifl imide was found to be 17 a Friedel-Crafts catalyst for tthe reaction of 18 anisole and benzoyl chloride.

The catalytic activity 19 was similar to that of 2Zn(NTfx),. Mg(NTf;); was found to bee a good sulfonation catalsyst in the reaction of 21 benzene sulfonyl chloride with chlorobenzene. 22 23 Example 28 . 24 Preparation of aluminium (III) lois-triflimide.

1 Aluminium dust (0.030 g, 1.15 mmol) was added to a : 2 solution of bis-triflimide (HN (SO2CF3)2, 0.84 g, 3. 0 3 mmeol) in distilled water (5 g) in a 25 cm® round 4 bok tomed flash equipped with a magnetic stirrer.

Thos was heated under reflux for 0.5 hours. The 6 mi==ture was cooled to rcom temperature and was 7 fi _ltered to remove excess aluminium. The water waas 8 evaporated on a rotary evaporator, and the alumini um 9 bi s-triflimide dried by heating at 150 °C at 1 mmHg fo r 4 hours in a vacuum drying apparatus, to give a 11 wh ite powder (0.83 g, 96 %) . The aluminium bis- 12 tr iflimide was purified by vacuum sublimation at 350 13 °C at 1 mmHg in a Kugelrohr apparatus (some 14 de-composition occurred). The unpurified aluminiutam bi _s-triflimide was found to be a Friedel-Crafts 16 ca.talyst for the reaction of anisole or xylene and 17 be=nzoyl chloride. The catalytic activity was simiZlar 18 too Zn (NTE). i9

Example 29 21 Pr-eparation of manganese (II) bis-triflimide. 22 Manganese (II) carbonate (0.18 g, 1.6 mmol) was ad ded 23 to a solution of bis-trifl imide (HN(SO,CF;),, 0.84 g, 24 3_0 mmol) in distilled water (5 g) in a 25 cm’

1 round bottomed flash equipped with a magnetic 2 stirrer. This was stirred for 0.5 houmxs (until the 3 evolution of CO, ceased. The mixture wzas filtered 4 to remove excexss manganese carbonate. The water was evaporated on a rotary evaporator, and the 9] manganese (II) bis-triflimide dried by keating at 150 7 °c at 1 mmHg for 4 hours in a vacuum drying 8 apparatus, to give an almost white powder (0.90 gq, 1°] 97 %). The manganese (II) bis~triflimicde was purified by vacuum distillation / sublA mation at 280 11 °c at 1 mmHg in a Kugelrohr apparatus «this 12 temperature and pressure appears to be very close to 13 the triple point of this material ie mmelting point 14 = boiling point). The unpurified manganese (II) bis-triflimide was found to be an excel lent Friedel- 16 Crafts catalyst for the reaction of toX.uene and 17 benzoyl chloride. The catalytic activity was greater 18 than Zn(NT£f;).- 19

Example 30 21 Preparation of nickel(II) bis-triflimicie. 22 Nickel(II) hydroxide (0.15 g, 1.6 mmol) was added to 23 a solution of bis-triflimide (HN(SO.CF;)., 0.84 g, 24 3.0 mmol) in distilled water (5 g) in a 25 cm’

1 round bosttomed flash equipped with a magnetic : 2 stirrer. This was stirred fom 1 hour (until the 3 hydroxide mostly dissolved to give a green 4 solutiom). The mixture was f-iltered to remove excess rmickel hydroxide. The water was evaporat ed 6 on a rot-ary evaporator, and the nickel (II) bis- 7 triflimi_ de dried by heating a-t 150 °C at 1 mmHg for 8 4 hours in a vacuum drying apparatus, to give a very 9 pale yel low powder (0.90 g, 9 7 %). The nickel (LI) bis-triflimide was purified b y vacuum distillati on / 11 sublimation at 280 °C at 1 mm Hg in a Kugelrohr 12 apparatias (see Figure 6). The unpurified nickel (II) 13 bis-triflimide was found to b e an excellent Friedel- 14 Crafts «catalyst for the react ion of toluene and benzoyl chloride. The catalyt ic activity was greater 16 than Zn (NTf;),. 17 18 Example 31 19 Preparation of cobalt(II) biss-triflimide.

Cobalt (II) carbonate (0.19 g, 1.6 mmol) was added to 21 a solut don of bis-triflimide (HN(SO.,CF3),, 0.84 cg, 22 3.0 mmol) in distilled waterz (5 g) in a 25 cm’ 23 round b-ottomed flash equipped with a magnetic 24 stirrer . This was stirred for 1 hour (until thee

1 evolution o £ CO; ceased to give & pink solution). 2 The mixture was filtered to remowe excess cobalt } 3 carbonate. The water was evaporz=&ated on a rotary 4 evaporator, and the cobalt(II) bAs-triflimide dried by heating at 150 °C at 1 mmHg for 4 hours in a 6 vacuum dryimng apparatus, to give a pale pink powder 7 (0.90 g, 97 %). The cobalt(II) lois-triflimide was 8 purified by vacuum distillation ,/ sublimation at 300 9 °c at 1 mmHg in a Kugelrohr apparatus. The unpurified —obalt(II) bis-triflimide was found to be 11 an excellent Friedel-Crafts catalyst for the 12 reaction of toluene and benzoyl chloride. The 13 catalytic activity was greater tlaan Zn(NTf;):. Also 14 this is one of the few Friedel-Crafts acylation catalysts that was found to catalyse the acylation 16 of chlorobenzene with benzoyl chl oride. 17 18 Example 32 19 Preparation of copper(II) bis-tri flimide.

Copper (11) carbonate (0.20 g, 1.6 mmol) was added to 21 a solution of bis-triflimide (HN{ SO,CF;3)., 0.84 gq, 22 3.0 mmol) in distilled water (5 g) in a 25 cm? 23 round bottomed flash equipped wit h a magnetic 24 stirrer. This was stirred for 1 hour (until the

1 evolution of CO, ceased to give a blue/green 2 solution) . The mixture was filtered to remove 3 excess co pper (11) carbonate. The water was 4 evaporate d on a rotary evaporator, and the copper(II ) bis-triflimide dried k»y heating at 150 °C 6 at 1 mmHg" for 4 hours in a vacuum drying apparatus, 7 to give a very pale green / blue powder (0.89 g, 95 8 %$). The copper(II) bis-triflimicde was purified by 9 vacuum di_stillation / sublimatiora at 180 °C at 1 mmHg in a Kugelrohr apparatus {partial decomposition 11 occurs dwmring sublimation and approximately half the 12 copper(I bis-triflimide is lost) . The unpurified 13 copper (II_) bis-triflimide was fouand to be a Friedel- 14 Crafts caatalyst for the reaction of toluene, anisole and xylerae with benzoyl chloride (activity was less 16 than Zn (XJTf;)2) . The copper(II) bis-triflimide was 17 also fournhd to be a good Friedel-Crafts alkylation 18 catalyst — 19

Example 33 21 Preparation of zinc(II) bis-trif limide. 22 Zinc (0.713 g, 2.0 mmol) was added to a solution of 23 bis-triflimide (HN (SQ,CF3)2, 0.84 g, 3.0 mmol) in 24 distilled water (5 g) in a 25 cm™ round bottomed

1 flash equipped with a magnetic stirrer.

This was 2 stirred for 1 hour (until the ewolution of H, ceased 3 to give a colourless solution). The mixture was 4 filtered to remove excess zinc.

The water was evaporated on a rotary evaporator, and the zinc(II) 6 bis-triflimide dried by heating at 150 °C at 1 mmHg 7 for 4 horurs in a vacuum drying &pparatus, to give a 8 white crystals (0.91 g, 97 %&). One of these crystals 9 was submitted for x-ray crystallographic analysis and its structure shown in Figures 5 to 7. The 11 zinc(II) bis-triflimide was puri.fied by vacuum 12 distilla tion / sublimation at 260 °C at 1 mmHg in a 13 Kugelroh r apparatus.

The unpurified zinc(II) bis- 14 triflimi de was found to be a goood Friedel-Crafts catalyst for the reaction of toEuene, anisole and 16 xylene with benzoyl chloride, ard benzoic acid with 17 xylene.

Also this is one of the few Friedel-Crafts 18 acylation catalysts that was fouand to catalyse the 19 acylation of chlorobenzene with benzoyl chloride.

21 Example 34 22 Indium (I II) Bis-triflimide 23 5.0g of Indium (III) hydroxide was dissolved in 50 24 ml of wa ter and to which 27.0g of HNTf, was added

1 and stirred at room temperature for 24 hour—s. The 2 reaction mixture was filtered and the filtr—ate was 3 concentrated on a rotary evaporator and dri ed under 4 vacuum (1 mmHg) for 3 days at 120 °C. The wmnpurified indium(III) bis-triflimide was found to be an 6 excellent Friedel-Crafts catalyst for the r-eacticn 7 of toluene, anisole and x=ylene with benzoyl chloride 8 or benzoic anhydride. 9

Example 35 11 Gallium (III) Triflamide 12 2.5 g of Gallium (III) oxide was suspended in 50 ml 13 of water to which 24.0 g trifluoromethane 14 sulfonimide was added and heated at 100 °C for two days. The reaction mixtuare was filtered an._d the 16 filtrate was concentrated on a rotary evapoerator and 17 dried under vacuum (1 mmHg) for 3 days at 1 20 °C. - 18 The unpurified gallium(IXI) bis-triflimide was found 19 to be an excellent Friedel-Crafts catalyst for the reaction of toluene, anissole and xylene wit h benzoyl 21 chloride or benzoic anhydride. 22 23 Example 36 24 Calcium Bis-triflimide

1 1.0 g of calcium (II) carbonate was suspended in 50

2 mL of water, to which freshly prepared HNTTf, (5.6 gq) 3 was added and stirred at room temperature for 24

4 hours.

The reaction mixture was filtered &and the filtrate was concentrated on a rotary evaporator and

6 “dried under vacuum (1 mmHg) for 4 hours at= 150 °C.

7 The unpurified calcium bis-triflimide was found to

8 display poor catalytic activity in Friede® -Crafts

9 reactions.

11 Example 37

12 Strontium (II Bis—triflimide

13 1.0g of strontiumm(II) carbonate was suspernded in 50

14 ml of water, to which freshly prepared HN Tf; (3.8 g)

was added and st irred at room temperature for 24

16 hours.

The react ion mixture was filtered &nd the

17 filtrate was con centrated on a rotary evagorator and

18 dried under vacuum (1 mmHg) for 4 hours at 150 °C.

19 The unpurified s trontium(II) bis-triflimi«de was found to display poor catalytic activity in Friedel-

21 Crafts reactions , but was slightly more a ctive than 22 the calcium anal ogue.

23

1 Example 38 . 2 Barium Bis-triflimide 3 1.0g of Barium(II) carbonate was suspended in 50 mL 4 of w ater, to which freshly p repared HNTf, (2.8 gq) was added and stirred at room temperature for 24 6 hour s. The reaction mixture was filtered and “the 7 filt rate was concentrated on a rotary evapora tor and 8 drie d under vacuum (1 mmHg) for 4 hours at 15 0 °C. 9 The unpurified barium(II) bi s-triflimide was found to d isplay some catalytic ac tivity in Friedel -Crafts 11 reac tions, and was more acti ve than the calci um and 12 stro ntium analogues. 13 14 Example 39

Tin( II) bis-triflimide proce dure 1 16 Tin metal (5.0 g, 99.9 % pur ity) lumps were 17 susp ended in water (50 mL) a nd hydrogen bis- 18 trif limide (HNTf,) (10 g) wa=s added. This mi=xture 19 was heated under reflux for 72 hours. The re sultant mixt ure was cooled, filtered and concentrated. on a 21 rota ry evaporator to give a colourless soluti on that 22 crys talised on standing. Th. e off white cryst als 23 were: heated at 150 °C at 1 mamHg to remove the 24 resi.dual water and hydrogen bis-triflimide. T he

Ww 0 02/072260 PCT/GB02/00989

1 unpurified t£n (II) bis-triflimide wa s found to 2 display cataEytic activity in Friede 1-Crafts ] 3 reactions (ec 1% Sn (NTf;), + toluene + benzoyl 4 chloride gave 99 % yield after 48 hours under reflux). The reactivity was similar to that of zinc 6 bis-triflimicde. - : — 8 Example 40 - Tin(II) Bis-t—riflimide procedure 2 la Tin (II) oxide (1.0 g) powder was suspoended in water 171 (50 mL) and mydrogen bis-triflimide (HNTf,) (5.0 g) 122 was added.

T'his mixture was heated under reflux for 13 48 hours.

Thme resultant slurry was cooled, filtered led and concentrated on a rotary evaporator to give a colourless sc=lution that gave an off white 1& precipitate on standing.

The off white precipitate 177 was heated att 150 °C at 1 mmHg to rermove the ] 1s residual water and hydrogen bis-trifA imide.

The 19 unpurified ti n(II) bis-triflimide wass found to display catal ytic activity in FriedeX Crafts 271 reactions (egw 1% Sn(NTf;), + toluene ~+ benzoyl 22 chloride gave 99 % yield after 6 hours under 23 reflux).

1 Example 41 - 2 Lead (II) Bis-triflimide 3 13 .0g of lead(II) carbonate was taken in 50 mL of 4 water, to which freshly prepared 28.0g of HNTf; was=s added and stirred at room temperature for 24 hours . 6 The reaction mixture was filtered and the filtrate 7 was concentrated on a rotary evaporator and dried 8 under vacuum (1 mmHg) for 3 days at 120 °C. The

S unpurified lead (II) bis-trifl-dmide was found to di splay good catalytic activity in Friedel-Crafts 11 re actions (eg 1% Pb(NTf;), + t oluene + benzoyl 12 ch loride gave 99 % yield after 48 hours under 13 re flux). The catalytic activity was better than 14 zinc(II) bis-triflimide. 16 Example 42 17 Charomium (III) Bis-triflimide 18 Chxromium metal (1.0 g, 99.95 $% purity) pieces were 19 suspended in water (20 mL) an d hydrogen bis- tr-iflimide (HNTf,) (5 g) was added. This mixture . 21 was heated under reflux for 1 44 hours. The 22 reesultant mixture was cooled, filtered and 23 concentrated on a rotary evapoorator to give a gre-en 24 solid. The solid were heated at 150 °C at 1 mmHg to

1 remove the residual water and hydrogen bis- 2 triflimide. The solid was thought to contain an oxo . 3 chromium bi s-triflimide species CrO(NT £,) from the 4 mass of HNT"f,; produced in drying process. The unpurified chromium(III) bis-triflimide was found to 6 display. cat alytic activity in Friedel-Crafts 7 reactions, and was similar in activity to Zn (NTf,;),. 8 9 Example 43

Tungsten Bi s-triflimide 11 Tungsten metal (1.0 g, 99 % purity) filings were 12 suspended im water (20 mL) and hydrogeri bis- 13 triflimide (HNTf,) (5 g) was added. Tlais mixture 14 was heated wander reflux for 144 hours. The resultant slurry was cooled, filtered &nd 16 concentrated on a rotary evaporator to give a 17 colourless solution that crystalised ora standing. 18 The crystals were heated at 150 °C at XI mmHg to 19 remove the mesidual water and hydrogen bis- triflimide. The precise structure of the catalyst 21 is not knowr, but it was found to be tthe best of all 22 isolated met=al bis-triflimide catalysts tested in 23 the reactiora of benzoyl chloride with t—oluene.

1 Example 44 . 2 Iron(II) Bis-triflimide 3 Iron metal (5.0 g, 99.95 % pu rity) lumps were 4 suspendexd in water (50 mL) an d hydrogen bis- triflimi de (HNTf;) (10 g) was added. This mixtumre 6 was heated under reflux for 7 2 hours. The resultant 7 slurry wzas cooled, filtered a nd concentrated on a 8 rotary e=vaporator to give a p ale yellow solutior 9 that cry stalised on standing. The pale yellow crystals were heated at 150 ° C at 1 mmHg to remove 11 the resi dual water and hydrog en bis-triflimide. 12 13 Example 45 14 Iron(IIT) Bis-triflimide i5 This compound can be isolated. in two forms as e-Zither 16 cream ccaloured crystals (thou ght to be 17 Fe (NTf,) = (OH) (OH2)) or a brown solid (thought to be 18 FeO(NTf, )). To a solution of iron(III) nitrate (10 19 g) in water was added sodium hydroxide solution (1

M) until a brown precipitate had formed. The . 21 precipitate of hydrated iron( III) hydroxide was 22 collecte=d by vacuum filtratio n and washed with 23 water. The precipitate (appr oximately 5 g) was 24 suspende=d in distilled water and excess hydrogerm

1 bis-triflim—-ide was added (20 gq). The precipitate 2 slowly dissolved to give a clear pale brown ) 3 solution.

TThe solution was filtered and 4 concentratecl on a rotary evaporator, and transferred to a kugelroohr distillation appaxatus.

The 6 unreacted hwdrogen bis-triflimide was distilled out 7 at 100 °C, T1 mmHg, leaving a cream coloured 8 crystalline solid of hydrated iron (III) bis- 9 triflimide.

Further heating at 170 °C, 1 mmHg for 4 hours, resulted in the evolution of hydrogen bis- 11 triflimide, and a brown solid wa= formed 12 (FeO (NTL) ) - Both of these sclicds were found to be 13 excellent Friedel-Crafts catalyst®ts for the reaction 14 of toluene wwith benzoyl chloride at 1 mol$% concentratieon. 16 17 Example 46 "The in situ preparation metal bis- 18 triflimide ecompounds, based on palladium(II) and 19 bis-triflim—de ions.

21 Palladium(I I) chloride (0.035 g) was added to 1l- . 22 butyl-3-metZhylimidazolium bis- 23 trifluorome—thanesulfonimide ([bmdm] [NTf2]) (2.0 g) 24 25 cm® in a round-bottomed flask, equipped with a

1 mag netic stirrer and reflusxx condenser. This was 2 hea ted gently, with stirrirag until the palladium (II) 3 chl«oride had dissolved, to give an yellow / orange 4 coloured clear solution. This solution was then usecd as a Friedel-Crafts acylation catalyst. 6 7 The catalytic activity of t he palladium(II) chloxide 8 / [komim] [NTf,] combination was tested in the 9 reacction of toluene (2.81 g, 30 mmol) with benzowyl chloride (2.84 g, 20 mmol). The mixtures was heated 11 undeer reflux for 24 hours a nd was analysed by gas 12 chromatographic analysis. “This gave methyl 13 benzophenone (75 % yield an-d 4.5 : 1 p- to o- 14 rat® 0). 16 Example 47 The in situ preparation metal bis- 17 triflimide compounds, based on tungsten(IV) and kois-~ 18 trifflimide ions. 19

Tungsten (VI) chloride (0.079 g) was added to 1- ) 21 butyrl-3-methylimidazolium bds- 22 triffluoromethanesulfonimide ({bmim] [NTf,]) (2.0 g) 23 25 cm’ in a round-bottomed f£1lask, equipped with a 24 magnetic stirrer and reflux condenser. This was

1 heated gently. with stirring until th e tungsten(VI) 2 chloride had dissolved, to give an cl ear solution. } 3 This solution was then used as a Frie del-Crafts 4 acylation catalyst. 6 The catalytic activity of the tungste n(VI) chloride 7 / [bmim] ([NTf,] combination was tested in the 8 reaction of toluene (2.81 g, 30 mmol) with benzoyl 9 chloride (2.84 g, 20 mmol) . The mixt ures was heated under reflux for 24 hours and was ana lysed by gas 11 chromatographic analysis. This gave methyl 12 benzophenone (99 % yield and 4.1 : 1 p- to o- 13 ratio). 14

Example 48 The in situ preparation metal bis- 16 triflimide coampounds, based on tin(IV) and bis- 17 triflimide io ns. 18 19 Tin (IV) chlor ide (0.052 g) was added to 1l-butyl-3- methylimidazo lium bis-trifluorometharmesulfonimide 21 ( [mim] [NT£,] D) (2.0 g) 25 cm’ in a rownd-bottomed : 22 flask, equipped with a magnetic stirrer and reflux 23 condenser. Th is was stirred until thes tin(IV) 24 chloride had dissolved, to give an clear solution.

1 This solution was then used as a Friedel-Crafts . 2 acylation catalyst. , 4 The «<atalytic activity of th e tin(IV) chloride / [bmirmn] [NTf,] combination was tested in the reacstion 6 of toluene (2.81 g, 30 mmol) with benzoyl chlomide 7 (2.844 g, 20 mmol). The mixt ures was heated under 8 reflux for 24 hours and was analysed by gas 9 chrormnatographic analysis.

T his gave methyl benzophenone (99 % yield and 4.2 : 1 p—- to o- 11 ratio). 12 13 Example 49 The in situ preparation metal bis- 14 trifdimide compounds, based eon titanium(IV) and bis- trifdimide ions. 16 17 Titarmium(IV) chloride (0.038 g) was added to 1— 18 butyl -3-methylimidazolium bis=s- 19 trifRuoromethanesulfonimide ([bmim] [NTf;}) (2.0 g) cm’ in a round-bottomed fl ask, equipped wit h a . 21 magnetic stirrer and reflux ccondenser.

This was 22 stirred until the titanium (IW) chloride had 23 dissolved, to give an clear solution.

This sol ution

1 was then used as a Friedel-Crafts acylation

2 catalyst. 3

4 The catalytic activity of the titanium(IV) chloride / [bmim] [NTf, ] combination was tested in the

6 reaction of toluene (2.81 g, 30 mmol) with benzoyl

7 chloride (2.84 g, 20 mmol). The mixtures was heated

8 under reflux for 24 hours and was analysed by gas

9 chromatograptmic analysis.

This gave methyl benzophenone (99 % yield and 4.5 : 1 p- to o-

11 ratio).

12

13 Example 50 The in situ preparation metal bis-

14 triflimide compounds, based on hafnium (IV) and bis-

triflimide ions.

16

17 Hafnium(IV) chloride (0.064 g) was added to l-butyl-

18 3-methylimid=zolium bis-trifluoromet hanesulfonimide

19 ([bmim] [NT£f,] ) (2.0 g) 25 cm’ in a round-bottomed flask, equipped with a magnetic stirrer and reflux

21 condenser.

TEnis was stirred until time hafnium(IV) . 22 chloride had dissolved, to give an czlear solution.

23 This solutiomn was then used as a Fri.edel-Crafts 24 acylation catalyst.

1

2 The catalytic act ivity of the hafnium(IV) chloride /

3 [bmim] [NTf,] combination was tested in the reaction 4 of toluene (2.81 g, 30 mmol) with benzoyl chloride

(2.84 g, 20 mmol) . The mixtures was heated wnder

6 reflux for 24 hours and was analysed by gas

7 chromatographic analysis.

This gave methyl

8 benzophenone (99 % yield and 4.42 : 1 p- to o-

9 ratio).

Claims (13)

1 CIAIMS 2

3 1. A metal bis-triflimide compound having the 4 formula : [My ]™ [(N(SO2CF3) 2) (nx-yz) J "V7 [Ly] ™ 6 7 where M is a metal sele cted from the metals in 8 groups 5 to 10, 12 and 14 to 16 and Cu, Au, Ca, 1°] Sr, Ba, Ra, ¥Y, La, Ac, Hf, Rf, Ga, In, Tl, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu 11 and the actinides; 12 L is a negative or neut ral ligand; 13 n is 2,3,4,5,6,7 or 8 ; 14 X 1s greater than or egual to 1 y is 0,1,2,3,4,5,6,70r 8; and 16 z is 0, 1,2,3 or 4. 17 18 2. A compound according toe claim 1 wherein M is 19 selected from the metal s in groups 7, 8 , 9, 10, 12 and 14 of the periodlic table. 21 3 22 3. A compound according to claim 1 wherein M is 23 selected from Mn, Fe, Co, Ni, In, Zn and Pb. } }

1 4. A compound according to claim 3 wherein M is 2 seelected from Mn (II), Fe(III), Co(II), Ni(II) 3 ard In(II).

4

5. A process for carrying out an electrophillic 6 substitution reaction of ari an aromatic ring or 7 ar isomerisation, polymerisation or 8 rearrangement to a chemical compound or 8 molecule which process is catalysed by the compound of any one of claims 1 to 4. 11 12

6. A process for the vapour deposition of metals 13 orato solid surfaces which process utilises a 14 me=2tal bis-triflimide compowmnd according to any ome of claims 1 to 4. 16 17

7. A process for purifying a mmetal bis-triflimid e 18 cosmpound according to any osne of claims 1 to 4 19 by~ sublimation. ) 21

8. A process for the production of metal 22 bi striflimide compounds whi ch process compris-es ) 23 re acting 24 (a) hydrogen bistriflimide with a metal;

1 (b) hydrogen bistriflimide wzith a metal 2 hydroxide; 3 (c) hydrogen bistriflimide wiith a metal 4 sulfide; or (d) hydrogen bistriflimide with a metal 6 carloide. : 7 8

9 A process for the production of a metal 9 bisttriflimide catalyst comprising adding metal compound to a source of a bistriflimide ion 11 such as a bistriflimide ionic liquid. 12 13

10 A pmocess according to claim 9 wherein the 14 metal compound is a metal halide. 16

11 A pxocess according to claim 9 or claim 10 17 wherein the source of bistri=flimide ion is an - 18 ionic liquid having bis- 19 tri fluoromethanesulfonimide «or bis- pentafluoroethanesulfonimide is an anion.

21 . 22

12 A p rocess according to any o ne of claims 9 to 23 11 wherein the metal bis-tri flimide is 24 rec overed by sublimation.

, 2

13. A bistriflimide catalyst® obtainable by the 3 process of any one of claims 9 to 12.