WO2007006569A1 - Substituted organopolysiloxanes containing phosphonic groups, methods for the production and use thereof - Google Patents

Abstract

The invention relates to new compounds of Formula (1) XxYyCcDd (Formula 1 ) wherein X is [O3/2SiCH(CH2PO(OR)(OR1))CH2CH2SiO3/2], Y is [O3/2SiCH2CH2PO(OR)(OR1)], C is [O3/2SiV] and D is [O3/2SiW], R and R1 are each independently selected from hydrogen, an optionally complex metal ion Mn+/n and an optionally substituted linear or branched group selected from C1-40-alkyl, C2-40-alkenyl, C2-40-alkynyl group, an aryl and C1-4o-alkylaryl group, V is selected from an optionally substituted linear or branched group selected from C1-40-alkyl, C2-4o-alkenyl, C2-40-alkynyl group, an aryl and C1-40-alkylaryl group, and W is (CH2)SZ where Z is selected from a sulfonic acid group, a Mn+/n sulfonate group, sulfide, sulfoxide, sulfone, amine, polyalkyl amine, phosphine and other phosphorous containing groups and an optionally substituted linear or branched group selected from C1-40-alkyl, C2-40-alkenyl, C2-40- alkynyl group, an aryl and C1-40-alkylaryl group X and Y are always present with at least one of C or D or both present The integers x, y, c and d are such that the ratio of x y+c+d, varies from 0 001 to 100 and d+c x+y varies from 0 001 to 100 The free valences of the silicate oxygen atoms are saturated by one or more of silicon atoms of other groups of Formula (1) , hydrogen, a linear or branched C1-12-alkyl group or by end groups, cross-linking bridge members or by polymer chains comprising known optionally substituted metal oxides The compounds are useful as catalysts for a wide variety of reactions, as cation and anion exchangers, as scavengers for unwanted organic and inorganic compounds in reaction mixtures, as solid phase purification material and enzyme, peptides, proteins or nucleic acids immobilisation supports.

Description

SUBSTITUTED ORGANOPOLYSILOXANES CONTAINING PHOSPHONIC GROUPS, METHODS FOR THE PRODUCTION AND USE THEREOF

The invention relates to new organopolysiloxanes containing phosphonic groups and salts of them and their use, for example as catalysts, cation and anion exchangers, organic and inorganic compound scavengers, solid phase purification or extraction materials, immobilisation materials for bio-molecules, anti-microbial agents, hydrophilicity modifiers, flameproofing agents, antistatic agents, biomedical devices, water repellent films and coatings, solid phase synthesis materials and chromatography materials The invention also relates to precursors of these new products and processes for their production

Catalysts are utilised in the chemical and biochemical industry to conduct a wide range of chemical transformations A range of homogenous and heterogeneous catalysts are used some of which require high temperatures to be effective and some produce considerable amount of bi-products and waste These unwanted products and waste have to be treated and destroyed The drive for more environmentally friendly processes - Green Chemistry - highlights the need for reusable, more effective and selective catalysts Examples of catalysts currently used extensively across manufacturing industries include mineral acids - sulphuric acid, hydrochloric acid, hydrogen fluoride, phosphoric acid - Lewis acids - aluminium trichloride, boron tπfluoride and zinc chloride - and oxidation reagents - permanganate, manganese dioxide and chromium (Vl) Catalysts, particularly solid phase catalysts, suitably have one or more of the following characteristics, good thermal stability, good chemical stability, flexibility to tailor the loading of functional groups to optimise yield and selectivity, they do not swell to a material extent, ease of regeneration and good catalyst life In some acid catalysed reactions it may be desirable to have suitable functional groups attached to an inert support that possess the right level of acidity to catalyse the desired reaction together with reducing or avoiding producing a range of side products and highly discoloured products For example, whilst both sulfuric acid and heterogeneous sulfonic acids are effective acid catalysts they also invariable produce a range of highly coloured unwanted side products that have to be removed

Optimum physical and chemical characteristics may be required for specific reactions for example providing optimum porosity, appropriate loading of the functional group or groups, having materials containing more than one functional group, adjusting the hydrophobic to hydrophilic ratio ease of making different metal derivatives and selective pH ranges An important class of heterogeneous acids are based on an organic, partly cross-linked polystyrene backbone with sulfonic acid groups attached to some of the phenyl rings However the physical and chemical properties of these polystyrene sulfonic acid resins may possess disadvantages, for example poor chemical stability and thermal stability, believed to be due to the organic polymeric backbone Additional problems for example swelling and shrinking in organic solvents as well as the production of highly coloured unwanted side products may also be encountered Generally, due to their poor thermal stability, these polystyrene sulfonic acid resins cannot be used for any length of time above 8O⁰C, thus limiting their general applicability

Other hybrid sulfonated systems for use as acid catalysts include materials where the surface of silica gel is covered with sulfonated cross-linked polystyrene, for example as disclosed in US4140653 and JP0117276 However drawbacks such as low surface area, large bead size, relatively low maximum operating temperature, difficult synthesis and very high cost may arise Sulfonated polysiloxanes have also been disclosed as acid catalysts as described in EP-A-58281 1 , DE 3226093, JP 06100695, JP 92-274801 , EP-A-548821 , EP- A-310843, EP-A-827947, EP-A-765897, EP-A-765851 , EP-A-693470 and EP -A-816323 However the preparation of sulfonated polysiloxanes may be complicated and expensive due to the cost of a typical starting material for the preparation, tπalkoxysilyl propyl mercaptan, the poor conversion of the mercapto group to the sulfonic acid and the reported splitting of the Si-C bond

A range of metals and catalysts have been embedded within or adsorbed on to the surface of silica, and other materials These systems may suffer the drawback of loss of the active functional groups due to their often very weak attachment to the silica A need remains for organo-silica materials which whilst retaining the appropriate function have functional groups that are strongly attached to the support and which bind strongly to a range of metals and catalysts and do not catalyse other reactions to an undesirable extent which may lead to impure and highly coloured products and lower yield and selectivity

As a consequence of stricter environmental regulations there is a growing requirement for more effective systems for the removal and recovery of cations and anions from many sources including a wide spectrum of contaminated solvents and aqueous based wastes and from contaminated waters For example the electronics industry has a particular need for ultra pure water with very low levels of both cations and anions Other industries such as the nuclear industry and the electroplating industry generate substantial quantities of water- based effluent that are heavily contaminated with undesirable metal ions Polymers having an organic, partly cross-linked polystyrene backbone with sulfonate groups attached to some of the phenyl rings are known for use as cation exchangers for removing metal ions from solution The physical and chemical stability and other properties of these materials for example due to the organic nature of the polymeric backbone, may adversely affect their use in cation exchange applications Organophosphonic acid cation exchangers have also been reported in US 5,281 ,631 and US 5,449,462 The feedstock in the manufacture of these materials may be expensive and they have limited applicability due to their physical and chemical properties

Inorganic polymer systems such as silica, aluminium oxide and titanium oxide have also been disclosed as functionalised materials Active functional groups or metals can be attached by a variety of means to these systems However a number of problems may be encountered where the functional groups are only physically adsorbed for example low functional group loading along with limitations in the range of solvents that can be used and removal of the functional groups on use or on standing This is believed to be due to the rather weak attachment between the functional group and the surface atoms on the support Building the functional group into the framework may provide a more robust material and may also permit higher functional group loadings However in this approach there is a significant lack of readily available starting materials as well as precursors for preparing such starting materials In addition there are limited synthetic methodologies for the preparation of suitable starting materials from available precursors A need exists to provide new synthetic methods as well as starting compounds in order to make such functionalised materials

Strong acidic cation exchangers based on sulfonic acid groups attached to an organopolysiloxane backbone have been described in US 4,552,700 and US 5,354,831 The disclosed materials have a general formula of (O_3/2Sι — R¹ — SO₃ )_XM^X where R¹ is an alkyl or cycloalkyl fragment, M is hydrogen or a mono to tetravalent metal ion and where the free valences of the oxygen atoms being saturated by silicon atoms of other groups of this formula and/or by cross-linking bridge members such as SιO_4/2, R¹SιO_3/2 TιO₄/₂, AIO_3/2 Whilst these materials may act as cation exchangers, sulfonic acid groups may be limited in their effectiveness to complex with a range of metals and in comparison to other functional groups In addition, as the sulfonate group is a mono anion, more of such groups are needed to bind to di and multivalent metal ions compared to other functional groups These materials are also expensive to prepare WO02/055587 discloses organopolysiloxanes containing phosphonic groups which are suitable for the removal of metal ions

Functionalised solid materials are used in solution phase organic synthesis to aid rapid purification and workup These materials, also known as scavengers, may remove excess reagents and side products Typically, a scavenger is added to a solution to quench and selectively react with excess or unreacted reagents and reaction side products Substituted polystyrene derivatives are known for use as scavengers but have a number of limitations such as lack of thermal stability, swelling and shrinking in organic solvents and a limited range of functional groups

Palladium mediated reactions enable the organic chemist to conduct a wide range of reactions used in the manufacture of products for a number of industries Typical reactions include Suzuki, Heck, oxidations and reductions In the production of active pharmaceutical agents (APIs), it is often found that the metal complexes to the desired API and a metal content in the range of 600-1000 ppm is not uncommon It is desirable to reduce the level of toxic metals, particularly palladium in APIs significantly Known methods including selective re-crystallisation, repositioning the palladium catalysed reaction to an earlier synthetic step and ion exchange leads to a slight but not generally sufficient lowering of metal content

The inventors have discovered a class of compounds which have a desirable combination of characteristics and make them suitable for use in a range of applications including acting as scavengers for inorganic and organic compounds, solid phase extraction material, bio- molecule immobilisation supports, ion exchanger materials, as anti-microbia! agents, as chromatography materials, as catalysts and catalyst supports, as hydπlicity modifiers, flameproofing agents, antistatic agents, biomedical devices and water repellent films and coatings or which are precursors for these

In a first aspect, the invention provides a compound of General Formula 1

X_xY_yC_cD_d (Formula 1 ) wherein X is [θ_3/2SιCH(CH₂PO(OR)(OR¹))CH₂CH₂Sιθ_3/2], Y is [0_3/2SiCH₂CH₂PO(OR)(OR¹)], C is [O_3Z2SiV] and D is [O_3/2SιW], R and R¹ are each independently selected from hydrogen, an optionally complex metal ion Mⁿ⁺/n and an optionally substituted linear or branched group selected from C_{1 40} alkyl, C_{2 40}-alkenyl, C_{2 40}-alkynyl group, an aryl and C_{1 40}-alkylaryl group, V is an optionally substituted linear or branched group selected from C_{1 40}-alkyl, C_{2 40}-alkenyl, C_{2 40}-alkynyl group, an aryl and C_{1 40}-alkylaryl group, and W is (CH₂)_SZ where Z is selected from a sulfonic acid group, a Mⁿ⁺/n sulfonate group, an optionally substituted linear or branched group selected from C_{1 40}-alkyl, C_{2 40}-alkenyl, C_{2 40}-alkynyl group, an aryl and C_{1 40}- alkylaryl group, sulfide, sulfoxide, sulfone, amine polyalkyl amine, phosphine and other phosphorous containing group,

n is an integer from 1 to 8 and s is an integer from 0 to 10, x, y, c and d are integers wherein x and y are independently 1 or more and c and d are independently 0 or more provided that at least one of c and d is 1 or more and the ratio of x y+c+d, is from 0 001 to 100 and the ratio d+c x+y is from 0 001 to 100, with the proviso that where C or D is C_{1 6}Sι0₃/₂, both c and d are 1 or more and C and D are different, the free valences of the silicate oxygen atoms are saturated by one or more of silicon atoms of other groups of Formula 1 , hydrogen, a linear or branched C_{1 12}-alkyl group, end groups R³ ₃M¹O_1/2, cross-linking bridge members R³ _qM¹(OR²)_rnO_k/₂ AI(OR²)_{3 p}O_p/2 or

R³AI(OR²)_{2 r}O_r/2, chains comprising (R³ _eSιO,_/2)_g, where M¹ is Si or Ti, R² is a linear or branched C_{1 40}-alkyl group an aryl or C_{1 40}-alkylaryl group, and R³ is a linear or branched C_{1 40}-alkyl group or an aryl or C_{1 40}-alkylaryl group, k is an integer from 1 to 4 and q and m are integers from 0 to 2, such that m + k + q = 4, p is an integer from 1 to 3, and r is an integer from 1 to 2, and e is an integer from 2 to 3 and f is an integer from 1 to 2 such that e + f = 4 and g is an integer from 1 to 10⁸, or an oxo metal bridging system comprising a metal selected from zirconium, boron, magnesium, iron, nickel and a lanthanide

Suitably the integers x, y, c and d are such that the ratio of x y+c+d is from 0 01 to 100 and may be from 0 02 to 50 Suitably the ratio d+c x+y is from 0 01 to 100 and may be from 0 02 to 50

Compounds of Formula 1 may comprise X, Y and C, X, Y and D, or X, Y, C and D Where the compound comprises X, Y and C and D is not present, V is selected from an optionally substituted linear or branched group selected from C_{7 40}, preferably C_{7 22}-alkyl, C_{2 40}, preferably C_{2 22}-alkenyl, C_{2 40}, preferably C_{2 22}-alkynyl group, an aryl and C_{1 40}, preferably C_{1 22}-alkylaryl group

One advantage of compounds of Formula 1 is that the functional group or groups can be selected to have either a high or low value according to the application Compounds of Formula 1 are advantageous in a number of applications including as catalysts, catalyst immobilisation supports, organic compound scavengers, solid phase purification and extraction material, bio-molecule immobilisation supports, cation and anion exchanger materials, anti-microbial agents and chromatography materials Other advantages include high thermal stability, fixed and rigid structures, good stability to a wide range of chemical conditions, insolubility in organic solvents, high resistance to ageing, easily purified and high reusability In addition the processes for the preparation of compounds of Formula 1 are very flexible, enabling porosity to be tailored from micro to macro porous, the loading of the phosphonic acid and sulfonic acid as well as the other substituents in the fragments V and W to be varied as needed for example to provide high loading of functional groups if required and a wide range of metal derivatives to be made with the added advantage of a high metal incorporation

Furthermore compounds of Formula 1 may advantageously provide effective ion exchange, particularly more effective cation exchange as compared to sulfonate alone Strong metal to phosphonate binding may also advantageously accrue thus reducing or avoiding leaching on operation The acid strength may be tailored according to the application from very strong for the sulfonic acid to around pH 6 for the second acidic proton of the phosphonic acid group Thus by simple adjustment of the acidity level through the relative amount of the sulfonic acid group present in the material along with the phosphonic acid and/or through partial neutralisation using a simple base, such as sodium hydroxide, a heterogeneous catalytic material with the desired acidity for particular chemical reactions can be produced providing optimum yield and selectivity and being chemically and thermally stable, especially as compared to known catalysts

Further advantages have been found for the removal of unwanted chemicals from reaction mixtures where the presence of additional functional groups increases the overall efficacy Materials and films for use as hydrophilicity modifiers, flameproofing agents, antistatic agents, biomedical devices and water repellent films and coatings can be easily made by varying the ratio of end groups, cross linker and polymer chains, for example R³ _qM¹(OR²)_mOκ/₂, to X, Y C and D

The organopolysiloxanes containing sulfonic acids described in US 4,552,700 require the presence of cross-linking agents containing Si, Ti or Al to provide the desired stability Unlike these systems, compounds of Formula 1 do not require these cross-linking agents to possess the desired physical anΦ chemical properties The bridging unit

[θ_3/2SιCH(CH₂PO(OR)(OR¹))CH₂CH₂SιC>3/₂] in Formula 1 is believed to be necessary to provide the excellent stability of the compounds of the invention An additional advantage is that this bridging group is suitably prepared in the actual manufacture of the materials of General Formula 1 Thus the preparation does not produce waste and does not require any purification as regards this component In addition the presence of this bridging group enables a significantly higher functional group loading, for example 1 to 5 mmol/g to be produced compared to materials that require additional cross-linking agents to provide the necessary stability

The optionally substituted linear or branched group selected from C_{1 40}-alkyl, C_{2 40}-alkenyl, C_{2 40}-alkynyl group, an aryl and C_{1 40}-alkylaryl group, R² and/or R³ may independently be linear or branched and/or may be substituted with one or more substituents but preferably contain only hydrogen and carbon atoms If a substituent is present, it may be selected from nitro, chloro, fluoro bromo, nitπle, hydroxyl, carboxylic acid carboxylic esters, sulfides, sulfoxides, sulfones, C_{1 6}-alkoxy, a C_{1 40}-alkyl or aryl di substituted phosphine, amino, amino C_{1 4}o-alkyl or amino di (C-, ₄₀-alkyl) or C_{1 40}-alkyl phosphinic or phosphonic group The organic group R² and R³ may, independently be linear or branched as desired

Preferably, the optionally substituted linear or branched group selected from C_{1 40}-alkyl, C_{2 40}- alkenyl, C_{2 40}-alkynyl group, an aryl and C_{1 40}-alkylaryl group, R² and/or R³ are independently selected from linear or branched C_{1 22} and desirably C_{1 12}-alkyl, C_{2 22}- and desirably C_{2 12}- alkenyl, aryl and a C_{1 22}-alkylaryl group and it is especially preferred that these groups are independently selected from a linear or branched C_{1 8}-alkyl C_{2 8}-alkenyl, aryl and a C_{1 8}- alkylaryl group

Suitably, R² and R³ are independently a C_{1 6}— alkyl group for example methyl or ethyl, or a phenyl group Preferably q is from 0 to 2, k is from 1 to 3 and m is 0 provided that m+k+q =4

Examples of suitable alkyl groups include methyl, ethyl, isopropyl, n-propyl, butyl, terf-butyl, n-hexyl n-decyl, n-dodecyl, cyclohexyl octyl /so-octy), hexadecyl, octadecyl, /so-octadecyl and docosyl Examples of suitable alkenyl groups include ethenyl, 2-propenyl, cyclohexenyl, octenyl, /so-octenyl, hexadecenyl, octadecenyl, /so-octadecenyl and docosenyl

C_{1 6}-alkoxy refers to a straight or branched hydrocarbon chain having from one to six carbon atoms and attached to an oxygen atom Examples include methoxy, ethoxy, propoxy, tert- butoxy and n-butoxy

The term aryl refers to a five or six membered cyclic, 8-10 membered bicyclic or 10-13 membered tricyclic group with aromatic character and includes systems which contain one or more heteroatoms, for example, N, O or S Examples of suitable aryl groups include phenyl, pyridinyl and furanyl Where the term "alkylaryl" is employed herein, the immediately preceding carbon atom range refers to the alkyl substituent only and does not include any aryl carbon atoms Examples of suitable alkaryl groups include benzyl, phenylethyl and pyridylmethyl

In the compounds of Formula 1 , especially those which are catalyst precursors, it is preferred that R and R¹ are each independently selected from hydrogen and an optionally substituted linear or branched group selected from C^o-alkyl, C_{2 4}o-alkenyl, C_2-40-alkynyl group, an aryl and C_1-40-alkylaryl group, and more preferably selected from hydrogen, C_1-12-alkyl, C_2-12- alkenyl, C_{2 12}-alkynyl, aryl and C_1-8-alkylaryl Suitably, V is selected from C_1-12-alkyl, C_2-12- alkenyl, C_{2 12}-alkynyl, and aryl Preferably W is (CH₂)_SZ where Z is selected from an optionally substituted sulfonic acid group, a M^π7n sulfonate group, sulfide, sulfoxide, sulfone, amine, polyalkylamine, phosphine and an organic group selected from C_1-12-alkyl, C_2-12- alkenyl, C₂ i₂-alkynyl, aryl and C_{1 8}-alkylaryl Desirably, Z is selected from a sulfonic acid group, a Mⁿ⁺/n sulfonate group, an amine and a polyalkylamine Desirably, s is an integer from 0 to 6 and preferably from 2 to 4

Compounds in which R and R¹ are each independently selected from hydrogen, C_1-8 preferably C_{1 4}-alkyl, phenyl or C_{1 8}-alkylaryl and V is vinyl or C_L8, preferably C₁.₄-alkyl, phenyl or Ci ₈-alkylary! and W is (CH₂)₂Z where Z is a sulfonic acid group or a Mⁿ⁺/n sulfonate group are especially preferred Among the most useful precursor compounds of Formula 1 are those in which R and R¹ are each independently hydrogen, methyl, ethyl or phenyl and V if present is methyl or vinyl and W is (CH₂)₂Z where Z is a sulfonic acid group

Compounds of Formula 1 in which either or both R and R¹ are hydrogen and V if present is vinyl or C_{1 8} alkyl or phenyl and W is (CH₂)₂SO₃H have been found to be useful for catalysing a wide range of reactions, particularly reactions which are conventionally acid catalysed such as though not limited to condensation reactions of aldehydes and ketones, ketalisation and acetalisation reactions, deketalisation and deacetalisation reactions, dehydration of olefins, a wide range of rearrangement and fragmentation reactions, isomeπsations, esteπfications and trans-esterification of carboxylate esters, acyclic and cyclic ether formation, glycolisation, protection of alcohols as tetrahydropyran derivatives, polymerisations and Friedel Craft alkylations and acylations

If only one of R and R¹ is hydrogen, the other may be C_1-40-and preferably C_1-22 alkyl, C_2-4O- and preferably C₂.₂₂-alkenyl, C₂.₄₀ and preferably C_{1 22}-alkynyl, aryl, C_1-40 and preferably C_1-22- alkylaryl or a metal ion derived from a lanthanide, actinide, main group or transition metal In compounds of Formula 1 in which either or both of R and R¹ are Mⁿ⁺/n, the metal is preferably selected from sodium potassium, calcium, magnesium, cobalt, iron, nickel, cerium, vanadium, chromium, titanium, lanthanum, silver, mercury, gold, manganese, platinum, palladium and rhodium In this case, suitably, V if present is selected from C_{1 12}-alkyl, vinyl, C_{2 12}-alkenyl, C₂ i₂-alkynyl, aryl and C_{1 8}-alkylaryl and W, if present, is a M^π+/n sulfonate group, for example (CH₂)₂SO₃ sulfonic acid, polyalkylamine or amine Such compounds of Formulae 1 provide particularly useful cation exchangers as well as solid immobilisation supports for metal catalysts and complexes and as heterogeneous catalysts for a wide range of reactions, for example oxidations, reductions, alkylations, polymerisations, hydroformylations, arylations, acylations, isomerisations, alkylations, carboxylations, carbonylations, esterifications, transesteπfications and rearrangements

In these compounds, if W is sulfonate Mⁿ⁺/n and only one of R and R¹ is Mⁿ⁺/n, it is preferred that the other of R and R¹ is hydrogen or a C_{1 12}-alkyl, C_{2 12}-alkenyl, C_{2 12}-alkynyl, aryl or C_{1 8}- alkylaryl Preferably the Mⁿ⁺ ions are derived from lanthanide, actinide, main group or transition metals and more preferred M^m ions are derived from lanthanide, main group or transition metals Examples of suitable metal ions include sodium potassium, calcium, magnesium, cobalt, iron, nickel, cerium, vanadium, chromium, titanium, lanthanum, silver, mercury, gold manganese, platinum, palladium and rhodium

A chiral compound of Formula 1 can be used for applications such as asymmetric synthesis and chiral separations, and in these cases it is preferred that one of R and R¹ is hydrogen or Mⁿ⁺/n and that the other is an optionally substituted Ci₂4₀-and preferably C_{12 22}-alkyl, C_{12 4}<r and preferably C_{12 22} -alkenyl C_{12 4}0- and preferably C_{12 2}2-alkynyl, C_{12 40}- and preferably C_{12 22}-alkylaryl or aryl and V, if present is an optionally substituted linear or branched group selected from C_{1 40}-alkyl, C_{2 4}o-alkenyl, C_{2 40}-alkynyl group, an aryl and C_{1 40}-alkylaryl group and W, if present, is (CH₂)_SZ where Z is selected from a substituted sulfonic acid group, a Mⁿ⁺/n sulfonate group, sulfide, sulfoxide, sulfone, amine, polyalkylamine, phosphine and an optionally substituted linear or branched group selected from C_{1 40}-alkyl, C_{2 40}-alkenyl, C_{2 4}o- alkynyl group, an aryl and C, ₄₀-alkylaryl group and s is an integer from two to four Preferred M^π+ are as described above

Where a cross linker is used, it is preferred that the ratio of end group, cross linker or polymer chains to x+y+c+d varies from 0 to 99 1 and more preferably 0 to 50 1

Particularly suitable cross linkers or polymer chains are derived from orthosilicates, titanium alkoxides, aluminium trialkoxides and alkyl alkoxy silanes Examples of end groups are trialkylalkoxysilane, cross linkers include tetraethyl orthosilicate, aluminium tπethoxide, aluminium tributoxide and titanium isopropoxide and for polymer chains alkyl alkoxy silanes The end group or cross linking bridge or polymer chain member is preferably (R³)₃SιOi_/2 or S1O₄/₂ or R³SιO_3/2 or (R³)₂Sι0₂/₂ or T1O4/2 or R³TιO_3/2 or (R³ )₂TιO_2/2 or AIO₃₇₂ or R³AIO_2/2 R³ is preferably C_{1 4}-alkyl or aryl, most preferably methyl, ethyl or phenyl

It is particularly preferred that the ratio of x y is from 1 100 to 100 1 more preferably from 1 50 to 50 1 and desirably 1 20 to 20 1 It is preferred that the ratio of c+d x+y is from 1 100 to 100 1 and more preferably from 1 50 to 50 1 and desirably 1 20 to 20 1 Components X and Y together are desirably present at a level of at least 1 % of the compound of Formula 1

The metal salts of Formula 1 are also useful as cation and anion exchangers and suitably either or both of R and R¹ are Mⁿ7n for example, sodium potassium and iron and V is vinyl or Ci ₈-alkyl and W is a Mⁿ⁺/n sulfonate group, for example (CH₂)₂SO₃

The preparation of compounds of General Formula 1 will now be discussed in greater detail

Compounds of Formula 1 may be prepared by a two-step process involves the formation of a compound of Formula 1 where R and R¹ are hydrogen and V is vinyl and D is not present It is known that free radical reactions involving alkenes may not proceed in high yield or selectivity as, depending on the particular starting materials unwanted dimers and higher tellomers may undesirably be produced for example as disclosed in Org Reactions, VoI 13, page 218 - 222 and the references provided therein However there is a lack of simple and effective synthetic methodology for the preparation of functionalised organic or inorganic polymers or materials where there are two reactive groups together in one molecule Cross- linking may produce stable solid polymer materials that otherwise would not have the required chemical and physical properties to be utilised

The present inventors have found that the hitherto unwanted dimerisation and tellomerisation, in the radical addition to olefins, provides a means to prepare stable functionalised solid materials

The invention further provides a process for the preparation of a compound of Formula 1 comprising contacting a vinyl trialkoxysilane with a phosphorous acid under free-radical addition reaction conditions and in the presence of a free-radical initiator to produce a compound of Formula 1 The ratio of X, Y and C, where V is vinyl may be tailored by varying the ratios of starting materials and reaction parameters such as temperature and stirring rate The reaction proceeds via a free radical addition of phosphorous acid to vinyl trialkoxy silane in the presence of a free radical initiator Increasing the ratio of phosphorous acid to the vinyl trialkoxy silane reduces the relative amount of C, in which V is vinyl, in the product A wide range of free radical initiators can be used for this reaction and preferred are the peroxides and in particular the alkyl peroxides Addition of a very small amount of the initiator every few minutes improves the overall yield Reaction temperatures between 6O⁰C and 17O⁰C can be used, though a reaction temperature of between 100⁰C and 140⁰C is preferred Although a wide range of solvents, well known to those skilled in the art of organic chemistry, can be used it is preferred to conduct this reaction without solvent Overall reaction times of between 15 minutes to 48 hours have been used with 2 to 14 hours preferred

This vinyl containing material can undergo free radical addition reactions with various generated radicals (Z), such as sulfur, oxosulfur and phosphorous containing groups, to give the (CH₂)₂Z fragment in D Treatment of the vinyl product from the above first step with an aqueous solution of sodium or ammonium sulfite in the presence of a free radical initiator gives, on acidification compounds of Formula 1 where R and R¹ are hydrogen and where V is vinyl and W is (CH₂)₂SO₃H The relative proportions of V and W depend on the initial concentration of the vinyl group, the concentration of sodium or ammonium sulfite and the reaction time Thus it is possible to tailor the level of the sulfonic acid group in these materials

A further process for the preparation of compounds of Formula 1 involves first the preparation of the fragments [O3/2SiCH(CH₂PO(OR)(OR¹))CH₂CH₂SiC>3/₂]_x and [O_3/2SιCH₂CH₂PO(OR)(OR¹)]_y following the procedure described in WO02/055587 This mixture is then suitably treated with the one or more appropriately substituted silyl groups to produce via sol-gel technology compounds of Formula 1 Typical substituted silyl groups include VSi(OR)₃ and WSi(OR)₃ where V and W are as described above

M A Brook in Silicon in Organic, Organometallic and Polymer Chemistry Chapter 10, page 318, John Wiley & Sons, lnc , 2000, G A Scherer in Sol-gel science the physics and chemistry of sol-gel processing, Boston Academic Press, 1990, and J D Wright in Sol-gel materials chemistry and applications, Amsterdam Gordon & Breach Science Publishers, 2001 and the references contained within describe sol-gel technology and the hydrolysis of silicon esters Acids and bases may be used to catalyse the hydrolysis of the silicon esters to produce the organopolysiloxane phosphonate esters of Formula 1 A range of solvents, known to those skilled in the art of organic chemistry, can be used to conduct this reaction Alcohols are the preferred solvents particularly methanol and ethanol After standing for a period of time the solution can be warmed to speed up the formation of the glass Ratios from 100 to 0 01 , by weight, of the alcohol solvent to the combined weight of the reagents can be used, with ranges from 2-10 being preferred A range of acids may be used to aid hydrolysis with hydrochloric acid in concentrations ranging from 0 1 to 4 M being preferred Hydrochloric acid, 1 molar, is especially preferred Ratios, from 0 0001 to 10, of hydrochloric acid, 1 molar, to the combined weight of the reagents are suitably be used, with a ratio from 0 01 to 1 being preferred The reaction mixture may be left to stand at a temperature in the range 0°C-120°C to aid hydrolysis and the formation of the SI-O-SI bonds Temperatures between 20-90°C are preferred and suitably warming is continued until all the solvent has evaporated and a clear glass is obtained

In addition to X and Y precursors to end groups, cross-linking bridge or polymer chain members such as (R³)₃Sι0_1/2 or SiO₄₇₂ or R³Sι0_3/2 or (R³)₂SιO_2/2 or TiO₄₇₂ or R³TiO₃₇₂ or (R³ )₂Tι0_2/2 or AIO₃₇₂ or R³AIO₂₇₂, where R³ is as defined above but is preferably methyl or ethyl or phenyl, or other oxo metals where the metal is zirconium, boron, magnesium, iron, nickel or one of the lanthanides may be added in a desired ratios, suitably at the sol gel stage, to produce compounds of Formula 1 Suitable precursors include orthosilicates, dialkoxy dialkylsilanes, alkoxy trialkylsilanes, titanium alkoxides and aluminium trialkoxides, for example tetraethyl orthosilicate, sodium silicate, dimethoxy dimethylsilane, tπmethyl methoxysilane, aluminium tπbutoxide, and titanium isopropoxide

Templates to aid the preparation of pores with particular sizes and distributions in compounds of Formula 1 can be added at this stage On preparation of the solid organopolysiloxane phosphonate esters of Formula 1 these templates can be washed out

The organopolysiloxane phosphonate esters glasses of Formula 1 are broken up and ground to very fine particles prior to hydrolysis if glass is formed Known crushing methods are used

Compounds of Formula 1 can also be prepared by treating a material such as silica or aluminium oxide with (R²O)₃SιCH(CH₂PO(OR)(OR¹))CH₂CH₂Sι(OR²)₃,

(R²O)₃SICH₂CH₂PO(OR)(OR¹) and (R²O)₃SiV, and (R²O)₃SiW if required, along with other end groups, cross linkers or polymers chains if required, in varying ratios in a solvent The monoesters of Formula 1 , where R is H and R¹ is C_{1 12}-alkyl, alkylaryl or aryl and V and W as described above are prepared by dilute basic or acidic hydrolysis of the corresponding phosphonate diesters of Formula 1 Bases such as sodium or potassium hydroxide in concentrations ranging from 0 1 to 20% by weight in water can be used with 1-5% being preferred Reaction temperatures of between 20-100⁰C can be used with 30-50°C being preferred Reaction times for complete hydrolysis are suitably from 1 -48 hours with 2-6 hours being preferred

The organopolysiloxane phosphonic acids of Formula 1 where R and R¹ are hydrogen and V and W in C and D are as described above are prepared by direct hydrolysis, suitably utilising the procedure of G H Barnes and M P David, J Org Chem , 25, 1191 , (1960), from the corresponding organopolysiloxane phosphonate esters of Formula 1 Suitably, a five to tenfold excess by volume or weight of hydrochloric acid, preferably from 2 molar to concentrated, to the organopolysiloxane phosphonate ester is used and the mixture is stirred under reflux for between 1-24 hours After cooling the compounds of Formula 1 where R and R¹ are hydrogen are filtered off and washed with de-ionised water till the washings are pH 7 The solids are washed with ethanol and then ether and dried at between 20-100°C under reduced pressure 0 001-5mm of Hg

Differential Scanning Caloπmetry (DSC) is a known technique for determining the thermal stability of compounds and materials No thermal events were observed on heating any of the samples of Formula 1 , prepared as described herein, up to a temperature of 400°C under an atmosphere of nitrogen gas A Perkin Elmer DSC 700™ instrument was used for these measurements Thus compounds of Formula 1 possess very good thermal stability

The presence of both fragments X and Y in compounds of Formula 1 containing either or both C and D is evident from a detailed analysis of a series of ¹H, ¹³C and ³¹P nmr experiments performed on the sodium salts of these compounds conducted on a Bruker AMX 600™ For the fragment X the signals due to the methine carbon and its proton occur at ό_c 21 1 and δ_H 0 99 with the methylene carbon and its associated protons next to phosphorus are at δ_c 31 0 and δ_H 1 63 and 1 27 For the fragment Y the signals due to the methylene carbon and its protons next to phosphorus occur at δ_c 22 6 and δ_H 1 36 For the product in Example 1 below the presence of the vinyl group was evident from peaks at δ_H 6 1 and 5 85 in the ¹H nmr spectrum in D₂O For the product in Example 3 below the presence of the ethylsulfonic acid was evident from peaks at δ_H 2 85 and 0 8 corresponding to CH₂SO₃ and SiCIH₂ methylene protons and the vinyl group was evident from peaks at δ_H 6 1 and 5 85 in the ¹H nmr spectrum in D₂O Compounds of Formula 1 have a wide range of uses The present invention provides a process for treating a feed material comprising contacting a compound of Formula 1 with a feed material ι) to effect a chemical reaction by catalytic transformation of a component of the feed material to produce a desired product, ιι) to remove a component of the feed material so as to produce a material depleted in the removed component, or in) to remove an ionic species in the feed material in an ion exchange process

The feed material may be a continuous stream for example a continuous process reaction feedstock, or may be in the form of a batch of material for discrete treatment The feed material, for example a waste water or waste process stream, may be treated to selectively remove a components of the feed The removed component may be an undesirable material in the feed and the process acts to provide a desired composition for the feed material which has been depleted in the selectively removed component after contact with compounds of Formula 1 This process may be used for example in removing unwanted species from a feed material in a pharmaceutical manufacturing or formulation process to improve the purity level of the pharmaceutical product as regards the removed material, for example metal species

The process may be employed to remove desired species from a feed material for subsequent processing or analysis, for example a biological molecule such as an enzyme, peptide, protein and nucleic acid may be removed from a feed material to enable further processing or analysis of the removed components

The invention also provides an antimicrobial composition comprising a compound of Formula 1 and a carrier

Compounds of Formula 1 where either or both of R and R¹ are hydrogen and V and W are as described above are especially beneficial in catalysing a wide range of acid promoted reactions In particular compounds of Formula 1 where R and R¹ are hydrogen and W is (CH₂^SO₃H and C if present with V is vinyl or methyl are preferred In addition these compounds of Formula 1 possess good thermal and chemical stability and reactions can be catalysed at much higher temperatures than functionalised polystyrene materials One of the advantages of these catalysts is that on completion of the reaction they can be simply filtered off and reused No apparent loss of activity was observed Following filtration and washing with solvents such as acetone, alcohols, water and others well known to those skilled in the

I 4 art of organic chemistry and drying at temperatures ranging from 20°C-12O⁰C under reduced pressure the compounds of Formula 1 can be used to catalyse other reaction types without apparent loss of activity

An additional advantage is that these catalysts, which contain three acidic protons (PK₁, pK₂ and pK₃), can by simple manipulation provide a suitable acid catalyst to enable the desired reaction to proceed quickly and smoothly without any rearrangement or decomposition in the reactants or products These catalysts can be thus be tuned to avoid the problems of highly coloured side products in the desired product The acidic strength of these catalysts is varied through the percentage content of the ethyl sulfonic acid as well as via partial neutralisation utilising a base such as sodium hydroxide For example the acid strength of the catalysts in Examples 3, 4 or 5 ranges from very strong - sulfonic acid - through to weak, the second phosphoric acid proton A further advantage is that compounds of Formula 1 have very high functional group loadings compared to other functionalised polymers thus less catalyst is required These catalytic reactions can be conducted with or without solvent The solvents that can be used include those well known to those skilled in organic and inorganic chemistry

The following examples illustrate the catalytic activity of compounds of Formula 1 but are not intended to limit the scope of their capability to catalyse a wide range of reactions

Compounds of Formula 1 catalyse the esterification of carboxylic acids For example treatment of oleic acid in refluxing ethanol with compounds of Formula 1 , particularly where R and R¹ are hydrogen V is methyl, vinyl or phenyl and W is (CH₂)₂SO₃H, gave the ester, ethyl oleate in quantitative yield Using either sulfuric acid or a sulfonic acid in this reaction leads to a highly coloured product containing the desired ethyl ester and a range of side products Compounds of Formula 1 , particularly where R and R¹ are hydrogen V is methyl, vinyl or phenyl and W is (CH₂)₂SO₃H have further advantages of significantly shorter reaction times and producing the desired ethyl ester in high yield and purity with no highly coloured side products A further advantage of this procedure is that the catalyst can simply be filtered off and reused without any apparent reduction in activity

Substituted ester derivatives are known lubricity additives for diesel fuel and are described in WO94/17160 These fuel additives are prepared via treatment of long chain fatty acids with a mono, dι, tri or poly alcohol in the presence of an acid catalyst Treatment of a fatty acid with ethylene glycol and compounds of Formula 1 , particularly where R and R¹ are hydrogen V is methyl, vinyl or phenyl and W is (CH₂)₂SO₃H, gave a colourless mixture of the dι-ester of ethylene glycol and the monoester alcohol The presence of the former was evident from a peak at δ_H 4 22 due to the four methylene protons (OCH₂CH₂O) and the latter from a peak at δ_H 3 6 due to two methylene protons (OCH₂CH₂OH)

Compounds of Formula 1 catalyse the trans-esterification of carboxylate esters For example treatment of ethyl oleate in butanol at temperatures between 60-140⁰C with compounds of Formula 1 , particularly where R and R¹ are hydrogen V is methyl, vinyl or phenyl and W is (CH₂)₂SO₃H, gives colourless butyl oleate Using either sulfuric acid or a sulfonic acid in this reaction leads to a highly coloured mixture containing the desired butyl ester and a range of side products Compounds of Formula 1 , particularly where R and R¹ are hydrogen V is methyl, vinyl or phenyl and W is (CH₂)₂SO₃H have further advantages of significantly shorter reaction times and producing the desired butyl ester in high yield and purity with no highly coloured side products Similar advantageous results were obtained in other esterification and trans-esteπfication reactions using the mixed phosphonic and sulfonic acid catalyst A further advantage of this procedure is that the catalyst can simply be filtered off and reused without any apparent reduction in activity

Compounds of Formula 1 , where R and R¹ are hydrogen or R is hydrogen and R¹ is a C_{1 40}- and preferably C_{1 22}-alkyl, C_{2 40}- and preferably C_{2 22}-alkenyl, C_{2 40}- and preferably C_{2 22}- alkynyl, aryl or C_{1 22}- and preferably C_{1 8}-alkylaryl fragment and where C and D are as described above, readily catalyse the condensation between aldehydes and aldehydes, aldehydes and ketones and ketones with ketones, reactions known as the Aldol condensation and the Claisen-Schmidt reaction Of particular importance are compounds of Formula 1 where R and R¹ are hydrogen V is methyl, vinyl or phenyl and W is (CH₂)₂SO₃H Standard conditions were used to conduct these reactions For example heating under a Dean and Stark apparatus a 1 1 molar equivalent mixture of benzaldehyde and acetophenone in benzene or toluene in the presence of such compounds of Formula 1 gave the desired colourless condensed product, 1 ,3-dιphenyl prop-2-enone, in quantitative yield An advantage of this procedure is that the catalyst can simply be filtered off and reused without any apparent reduction in activity

Utilising known reaction conditions compounds of Formula 1 , particularly where R and R¹ are hydrogen V is methyl, vinyl or phenyl and W is (CH₂J₂SO₃H, readily catalyse the ketalisation of ketones in very high yields and purity Standard conditions were used to conduct these reactions For example heating under a Dean and Stark apparatus acetophenone and an excess of ethylene glycol in benzene or toluene in the presence of compounds of Formula 1 gave the desired product 2-methyl - 2-phenyl-1 , 3-dιoxolane in quantitative yield Utilising known reaction conditions compounds of Formula 1 , particularly where R and R¹ are hydrogen V is methyl, vinyl or phenyl and W is (CH₂)₂SO₃H, readily catalyse the acetalisation of aldehydes Standard conditions were used to conduct these reactions For example treatment of benzaldehyde in methanol, with commonly used drying agents, in the presence of acidic compounds of Formula 1 gave the desired product, 1 , 1-dιmethoxy-1 -phenyl methane, in quantitative yield An advantage is that for both reactions, ketalisation and acetalisation, the catalyst can simply be filtered off and reused without any apparent reduction in activity Using aqueous conditions these catalysts of Formula 1 can be used to remove both types of protection groups

Compounds of Formula 1 readily catalyse the dehydration of olefins Standard conditions were used to conduct these reactions For example heating cyclohexanol in the presence of compounds of Formula 1 , particularly where R and R¹ are hydrogen V is methyl, vinyl or phenyl and W is (CH₂)₂SO₃H, gave the desired cyclohexene In a similar fashion treatment of 1-phenyl-1-propanol in toluene with catalysts of Formula 1 , particularly where R and R¹ are hydrogen V is methyl, vinyl or phenyl and W is (CH₂)₂SO₃H, in toluene at 75⁰C gave β-methyl styrene in greater than 90% yield An advantage of this procedure is that the catalyst can simply be filtered off and reused without any apparent reduction in activity

Acids are widely used to catalyse a wide range of rearrangements and fragmentations Likewise compounds of Formula 1 , particularly where R and R¹ are hydrogen V is methyl, vinyl or phenyl and W is (CH₂)₂SO₃H, readily catalyse a wide range of such reactions For example heating 2,3-dιmethyl butan-2,3-dιol at between 130-180⁰C without solvent in the presence of the acid catalysts from Examples 3, 4 or 5 gave 3,3-dιmethy! butan-2-one in high yield The reaction can also be conducted in a variety of solvents, well known to the practitioners of organic chemistry The catalyst can be filtered off and reused without any apparent reduction in activity

The monovalent to octavalent optionally complex metal ion salts of Formula 1 are suitably prepared by first reacting the corresponding derivatives of Formula 1 with dilute base to a pH of approximately 8-9 The white solid is then filtered off and washed well with water and then with ethanol The salt is then dried under reduced pressure A solution containing the desired metal ion and/or complex is then suitably added to a suspension of the salt in a solvent and the metal derivatives of Formula 1 are subsequently filtered off A wide range of bases and solvents, may be used in this reaction with sodium or potassium hydroxide and water respectively preferred The monovalent to octavalent optionally complex metal ion salts of Formula 1 can also be prepared in a range of non-aqueous solvents and by the use of appropriate bases and metal salts In this manner a range of metal salts for example lanthanides, actinides, main group and transition metals of Formula 1 were prepared Thus an important application of compounds of Formula 2 is their use as solid immobilisation supports for metal catalysts/complexes

Metal salt/complexes of Formula 1 can catalyse a wide range of reactions well known to practitioners of organic and inorganic chemistry Examples include but not limited to oxidations, reductions, alkylations, polymerisations, hydroformylations, arylations, acylations, isomerisations, alkylations, carboxylations, carbonylations, esterifications, trans- esteπfications and rearrangements These organopolysiloxane compounds of Formula 1 have many advantages for example they provide a support with very high thermal stability, good stability to a wide range of chemical conditions, a designable structure to facilitate selective reactions, and high loading of the active metal functional group or groups Furthermore the hydrophobic to hydrophilic nature of these compounds of Formula 1 can be easily varied through the incorporation of alkyl, alkenyl or aryl groups in V In addition these catalysts can be filtered off and reused Thus an important application of the metal derivatives of Formula 1 is their use as heterogeneous catalysts

The vanadyl metals salts of compounds of Formula 1 can be used to epoxidise a wide range of olefins For example treatment of cyclohex-2-en-1-ol with terf-butyl hydrogen peroxide in an organic solvent gave the corresponding syn epoxide in greater than 80% yield and 99% selectivity A range of organic solvents, well known to practitioners of synthetic chemistry, can be used in this reaction The catalyst can be simply filtered off and reused without any apparent reduction in activity

Cerium (IV) salts of compounds of Formula 1 can be used to oxidise a range of organic compounds For example, alcohols, depending on their structure, can be oxidised to either ketones or carboxylic acids Benzylic alcohols in the presence of cerium salts of Formula 1 and sodium bromate, as the re-oxidant, in an aqueous organic solvent mixture gave the corresponding benzoic acids in very high yield In a similar fashion 1-phenyl ethanol was oxidised to the acetophenone in 90% yield A range of organic solvents, well known to practitioners of synthetic chemistry can be used in this reaction The catalyst can be simply filtered off and reused without any apparent reduction in activity

Cerium (IV) and chromium (III) salts of compounds of Formula 1 can be used to selectivity oxidise sulfides to sulfoxides For example treatment of thioanisole with cerium or chromium salts of Formula 1 and sodium bromate or (erf-butyl hydrogen peroxide, as the re-oxidant, gave the corresponding methyl phenyl sulfoxide Again the catalyst can be simply filtered off and reused without any apparent reduction in activity

Cobalt salts of compounds of Formula 1 can be used for allylic oxidation For example, treatment of the steroid pregnenolone acetate with a cobalt salt of Formula 1 with an alkyl hydrogen peroxide in solvents such as acetonitπle and benzene gave the corresponding 5- ene-7-one derivative in 70% yield The catalyst can be simply filtered off and reused without any apparent reduction in activity

An important application of these new products is based on the ability of the compounds of Formula 1 to exchange ions, that is to say, their application as a cation or anion exchanger that can be used for all purposes and has the advantages of the matrix which is highly resistant to temperatures and solvents, of strongly fixed phosphonate and sulfonate groups which resist cleavage, of the resistance to swelling in aqueous and organic mediums, and their applicability in organic media also

Therefore, another object of the invention is the use of the organopolysiloxanes that carry phosphonate and other substituents such as alkyl, alkenyl, sulfonic, alkylsulfur and alkyl amino groups as cation and anion exchangers The combination of the phosphonate and the other substituents gives enhanced performance either in terms of greater overall efficacy or speed of action

The new ion exchangers described herein can also be characterized with the aid of elementary analyses and their decomposition point exceeds 400⁰C under protective gas atmosphere The latter is evident from DSC analysis where no thermal events are seen below 400°C

The mono, di and tπ-anion phosphonic sulfonic derivatives of Formula 1 act as very effective cation exchangers for a wide range of metals of known oxidations state These include the lanthamdes, actinides, main group and transition metals The tri-anion phosphonic sulfonic derivatives of Formula 1 are particularly effective for the removal of metal ions due to the combination of these functional groups due to enhanced speed of action

The mono, di and tπ-anion derivatives of Formula 1 are prepared by treatment with dilute base A range of bases and solvents, well known to those skilled in the art of chemistry, can be used such as aqueous metal hydroxides, alcoholic metal hydroxides, metal alkoxides and metal hydrides Aqueous sodium or potassium hydroxides are the preferred bases for aqueous reactions Fast and very effective cation exchange occurs following treatment of these derivatives with a wide variety of metal salts dissolved in various solvents Numerous different analytical techniques, well known to those skilled in the art of chemistry, can be used to determine the extent of cation exchange

For example 0 1 grams of a di or tπ-sodium salt of Examples 38, 39 or 40 below on contact with a solution containing 100ppm of either toxic Co(II) or Cd(II) ions lower the concentration to levels of 0 04ppm and 0 Oδppm respectively in less than 10 minutes Such compounds of Formula 1 are equally effective for other lanthanides, actinides, main group and transition metal ions and complexes Copper ions can cause significant problems in power plants due to corrosion Starting with a I OOOppm solution of Cu⁺² ions these tπ-sodium salts rapidly reduce the concentration to below 1 ppm Compounds of Formula 1 , particularly the tπ sodium salts have equal high intrinsic activity with the added advantage of faster kinetics

Compounds of Formula 1 can also be used to remove excess reagents and side products from organic reactions used in the chemical and pharmaceutical industries Compounds prepared in Examples 1-8, 10-14 and 23-24 can readily remove all types of basic organic compounds such as amines, hydrazines and heteroaromatic amines The mono, di and tri salts of Formula 1 can removed reactive acid chlorides, such as acetyl chloride, and other reactive organo halide containing reagents from reaction mixtures Compounds prepared in Examples 38-40 can remove metal ions and complexes, Lewis acid reagents and catalysts such as aluminium chloride, boron trifluoπde and tin halides, inorganic and organic acids and acylating reagents Unlike the polystyrene based scavengers, compounds of Formula 1 can work in all solvents and are not limited in their application to reaction temperatures below 8O⁰C and do not suffer from or require swelling

Compounds of Formula 1 can also be used to remove precious metals from various different solutions For example treatment of a palladium acetate solution in dichloromethane with the product from Example 15 resulted in the complete removal of the palladium ions from solution For palladium chloride the product from Example 16 is equally effective

Compounds of Formula 1 can also be used for the separation or removal of gases, including the removal of malodorous volatile organic compounds

Compounds of Formula 1 can be used both to immobilise biological molecules such as enzymes, polypeptides, proteins and nucleic acids as well as for their separation and purification In addition nucleic acids immobilised on compounds of Formula 1 can be used for conducting high volume nucleic acid hybridization assays

Compounds of Formula 1 can be used as anti-microbial agents and can be applied as thin films onto a variety of surfaces

Compounds of Formula 1 can be used as materials for solid phase extraction where a desired product is purified through selective retention on the functionalised materials whilst the impurities are removed and then it is subsequently released For example compounds of Formula 1 particularly where R and R¹ are hydrogen and W is (CH₂^SO₃H can remove wanted amines from reaction mixtures whilst washing out the side products The desired amines are then released from the acidic medium using methanolic ammonia

Compounds of Formula 1 can also be used for solid phase synthesis through first attachment of the starting material to the carbonyl group, a number of chemical reactions can then be conducted and in each step purification is facile through simple filtration At the end of the sequence the desired material is released from the solid phase .

Compounds of Formula 1 can be used as a chromatography medium to separate desired products or to analyse mixtures In particular compounds of Formula 1 can be used as materials for gel filtration and high speed size-exclusion chromatography as well as for high pressure liquid chromatography for the purification and identification of organic and biological compounds For example the materials of Formula 1 can be used in the separation of amines, including optically active amines Compounds of Formula 1 can also be used for chiral separations whereby desired enantiomers can be separated from a reaction mixture

In addition compounds of Formula 1 can be used as hydrophilicity modifiers, flameproofing agents, antistatic agents, biomedical devices, water repellent films and coatings

The invention will now be described in detail with reference to practical examples of the variants according to the invention, taking into account the starting materials that are fundamentally the most significant Example 1

A solution containing trimethoxyvinyl silane (148 0 g, 1 mol), phosphorous acid (123 g, 1 5 mol) was heated quickly with rapid overhead stirring to 12O⁰C under an atmosphere of nitrogen Once the temperature reached 5O⁰C dι- rert-butyl peroxide (6 drops) was added every 2 minutes After 2 h the reaction mixture solidified to give a colourless glass Water (2 L) was added and the mixture was stirred under reflux for 12 h On cooling the solid was filtered and washed well with de-ionised water, crushed and then washed again with de- ionised water to afford a white solid (105 g) where the ratio of X Y C is 1 2 1 where C is (O_3/2Sι)vιnyl - Catalyst A Example 2

A solution containing triethoxyvinyl silane (190 0 g, 1 mol), phosphorous acid (84 g, 1 mol) was heated quickly with rapid overhead stirring to 120⁰C under an atmosphere of nitrogen Once the temperature reached 5O⁰C dι- tert-butyl peroxide (6 drops) was added every 2 mm After 2 h the reaction mixture solidified to give a colourless glass Water (2 L) was added and the mixture was stirred under reflux for 12 h On cooling the solid was filtered and washed well with de-ionised water, crushed and then washed again with de-ionised water to afford a white solid (102 g) where the ratio of X Y C is 1 2 2 where C is (O₃/₂Sι)vιnyl Example 3

A mixture containing the product from Example 2 (10 g) in water (100 ml) was adjusted to pH 12 with 1 M sodium hydroxide The resultant solution was then adjusted to pH 7 with 1 M hydrochloric acid and a solution of ammonium sulfite monohydrate (30 g, 0 22 mol) in water (100 ml) was added The resultant mixture was stirred under reflux for 48 h Di- /ert-butyl peroxide (6 drops) was added every four hours to the reaction mixture On cooling the solution was acidified with concentrated sulphuric acid and then filtered The white solid was washed with de-ionised water (1 L) and then with methanol and ether to give a phosphonic acid ethyl sulphonic acid silica compound of Formula 1 (8 1 g) - Catalyst B - where the ratio of X Y C D is 1 2 0 4 1 6 and where C is (O_3/2Sι)vιnyl and D is (0_3/2Si)CH₂CH₂SO₃H ¹H nmr (600 MHz, D₂O) SiCH₂CH₂SO₃H - SiCH₂ δ 0 8 and CH₂SO₃H δ 2 85 Example 4

A mixture containing the product from Example 1 (20 g) in water (150 ml) was adjusted to pH 12 with 1 M sodium hydroxide The resultant solution was then adjusted to pH 7 with 1 M hydrochloric acid and a solution of sodium sulfite monohydrate (40 g) in water (150 ml) was added The resultant mixture was stirred under reflux for 40 h Di- te/?-butyl peroxide (6 drops) was added every two hours to the reaction mixture On cooling the solution was acidified with concentrated sulphuric acid and then filtered The white solid was washed with de-ionised water (1 L) and then with methanol and ether to give a phosphonic acid ethyl sulphonic acid silica compound of Formula 1 (16 1 g) - Catalyst C - where the ratio of X Y C D is 1 2 0 0 3 0 7 and where C is (O_3/2Sι)vιnyl and D is (0_3/2Si)CH₂CH₂SO₃H ¹H nmr (600 MHz, D₂O, NaOD) SiCH₂CH₂SO₃H - SiCH₂ δ 0 8 and CH₂SO₃H δ 2 85 Example 5

A mixture containing the product from Example 1 (20 g) in water (150 ml) was adjusted to pH 12 with 1 M sodium hydroxide The resultant solution was then adjusted to pH 7 with 1 M hydrochloric acid and a solution of sodium sulfite monohydrate (60 g) in water (150 ml) was added The resultant mixture was stirred under reflux for 60 h Di- terf-butyl peroxide (6 drops) was added every two hours to the reaction mixture On cooling the solution was acidified with concentrated sulphuric acid and then filtered The white solid was washed with de-ionised water (1 L) and then with methanol and ether to give a phosphonic acid ethyl sulphonic acid silica compound of Formula 1 (16 5 g) - Catalyst D - where the ratio of X Y D is 1 2 0 1 0 and where D is (0_3/2Si)CH₂CH₂SO₃H ¹H nmr (600 MHz, D₂O, NaOD) SiCH₂CH₂SO₃ - δ 0 8 SiCH₂ and δ 2 85 CH₂SO₃ Example 6

A mixture of diethyl 2,4-dι-(tπmethoxysιlyl) butylphosphonate and diethyl 2-tπmethoxysιlyl ethylphosphonate (30 1 g) and tπmethoxy vinyl silane (9 5 g, 0 068 mol) were dissolved in methanol (140 ml) containing 1 M HCI (14 ml) The solution was left at 55⁰C for 100 h The resultant glass (20 0 g) was crushed and then added to concentrated HCI (200 ml) The mixture was gently refluxed with stirring for 10 h and then cooled to room temperature The solid was filtered and first washed with distilled water till the washings were neutral and then with methanol and finally ether After drying at 100⁰C at 0 1 mm of Hg a pale white solid was obtained (16 0 g) - Catalyst E - where the ratio of X Y C is 1 1 8 0 6 and where C is (O_3/2Sι)vιnyl Example 7

A mixture of diethyl 2,4-dι(trιethoxysιlyl) butylphosphonate and diethyl 2-trιethoxysιlyl ethylphosphonate (55 1 g), methyl tπethoxysilane (8 9 g, 0 05 mol) and vinyl triethoxysilane (1 9 g, 0 01 mol) were dissolved in methanol (220 ml) and then 1 M HCI (22 ml) was added with stirring The solution was left at 55⁰C for 100 h The resultant glass (34 0 g) was crushed and then added to HCI (5M, 340 ml) The mixture was gently refluxed with stirring for 10 h and then cooled to room temperature The solid was filtered and first washed with distilled water till the washings were neutral and then with methanol and finally ether After drying at 100⁰C at 0 1 mm of Hg a white solid (26 0 g) - Catalyst F - was obtained where the ratio of X Y C D is 1 1 7 0 3 0 06 where C is (O_3/2Sι) methyl and D is (O₃₇₂Si) vinyl Example 8

A mixture of diethyl 2,4-dι(tπethoxysιlyl) butylphosphonate and diethyl 2-tπethoxysιlyl ethylphosphonate (58 6 g) and phenyl triethoxysilane (9 6 g, 0 04 mol) were dissolved in methanol (260 ml) and then 1 M HCI (28 ml) was added with stirring The solution was left at 55⁰C for 200 h The resultant glass (36 0 g) was crushed and then added to concentrated HCI (305 ml) The mixture was gently refluxed with stirring for 10 h and then cooled to room temperature The solid was filtered and first washed with distilled water till the washings were neutral and then with methanol and finally ether After drying at 100⁰C at 0 1 mm of Hg a white solid (28 0 g) - Catalyst G - was obtained, where the ratio of X Y C is 1 2 1 0 4 where C is (O_3/2Si) phenyl Example 9

A mixture of diethyl 2,4-dι(tπethoxysιlyl) butylphosphonate and diethyl 2-trιethoxysιlyl ethylphosphonate (28 3 g) and 3-amιnopropyl triethoxysilane (9 6 g) were dissolved in methanol (120 ml) and then 1 M HCI (15 ml) was added with stirring The solution was left at ambient temperature for 2 h and then at 55⁰C for 260 h The resultant glass (19 1 g) was crushed and then added to 5M HCI (100 ml) The mixture was gently refluxed with stirring for 10 h and then cooled to room temperature The solid was filtered and first washed with distilled water till the washings were neutral and then with methanol and finally ether After drying at 100⁰C at 0 1 mm of Hg a white solid (15 0 g) - Catalyst H - was obtained, where the ratio of X Y C is 1 3 1 0 6 where C is (O₃/₂Sι) 3-amιnopropyl Example 10

A mixture of diethyl 2,4-dι(trιethoxysιlyl) butylphosphonate and diethyl 2-trιethoxysιlyl ethylphosphonate (48 1 g) and 3-chloropropyl triethoxysilane (9 6 g, 0 04 mol) were dissolved in methanol (280 ml) and then 1 M HCI (22 ml) was added with stirring The solution was left at ambient temperature for 48 h and then at 55°C for 100 h The resultant glass (36 0 g) was crushed and then added to concentrated HCI (310 ml) The mixture was gently refluxed with stirring for 10 h and then cooled to room temperature The solid was filtered and first washed with distilled water till the washings were neutral and then with methanol and finally ether After drying at 10O⁰C at 0 1 mm of Hg a white solid (24 0 g) was obtained, where the ratio of X Y C is 2 1 0 4 where C is (O_3/2Sι) 3-chloropropyl - Catalyst I Example 11

A mixture of diethyl 2,4-dι -triethoxysilyl butylphosphonate, diethyl 2-tπethoxysιlyl ethylphosphonate (40 g, 1 5 ratio), diethyl 3-trιethoxysιlylpropylphosphonate (6 g) and phenyl triethoxysilane (0 05 mol) was dissolved in methanol (150 ml) and then 1M HCI (12 m!) was added with stirring The solution was left at ambient temperature for 4 h and then at 55°C for 200 h The resultant glass (39 g) was crushed and then added to HCI (5M, 200 ml) The mixture was gently refluxed with stirring for 10 h and then cooled to room temperature The solvent was removed under reduced pressure and the solid was filtered and washed with distilled water till the washings were neutral and then with methanol and finally ether After drying at 100⁰C at 0 1 mm of Hg a white solid (20 g) - Catalyst J - was obtained, where the ratio of X Y C D is 1 5 0 5 0 4 where C is (O_3/2Sι) phenyl and D is (O_3/2Sι) propylphosphonic acid

Example 12

A mixture of diethyl 2 4-dι(tπethoxysιlyl) butylphosphonate and diethyl 2-trιethoxysιlyl ethylphosphonate (5 8 g, ratio 1 2 5), diethyl 3-trιethoxysιlyl propylphosphonate (3 g) and vinyl triethoxy silane (3 8 g, 0 02 mol) was dissolved in methanol (30 ml) and then 1M HCI (3 ml) was added with stirring The solution was left at 55⁰C for 200 h The resultant glass (7 2 g) was crushed and then added to HCI (5M, 50 ml) The mixture was gently refluxed with stirring for 10h and then cooled to room temperature The solid was filtered and first washed with distilled water till the washings were neutral and then with methanol and finally ether After drying at 100°C at 0 1 mm of Hg a white solid (5 1 g) was obtained - Catalyst K - and where the ratio of X Y C D is 1 2 5 1 0 8 where C is (O_3/2Sι)vιnyl and D is (O₃₇₂Si) propylphosphonic acid Example 13

A mixture of diethyl 2,4-dι(tπethoxysιlyl) butylphosphonate and diethyl 2-trιethoxysιlyl ethylphosphonate (42 g, ratio 1 3), methyl tπethoxysilane (7 12 g, 0 04 mol) and tetraethyl ortho silicate (6 0 g) was dissolved in methanol (240 ml) and then 1 M HCI (18 ml) was added with stirring The solution was left at 55⁰C for 200 h The resultant glass (29 2 g) was crushed and then added to HCI (5M, 250 ml) The mixture was gently refluxed with stirring for 4 h and then cooled to room temperature The solid was filtered and first washed with distilled water till the washings were neutral and then with methanol and finally ether After drying at 100⁰C at 0 1 mm of Hg a white solid (21 3 g) was obtained - Catalyst L Example 14

A mixture of diethyl 2,4-dι(trιethoxysιlyl) butylphosphonate and diethyl 2-trιethoxysιlyl ethylphosphonate (82 g, ratio 1 2) and vinyl tπethoxysilane (10 g) was added to hydrochloric acid (5M, 900 ml) The mixtures was stirred and heated at reflux for 10 h and then cooled to room temperature The mixture was concentrated and water (1 L) was added to the residue This process was repeated a further 4 times to give a compound (41 g) of Formula 1 where R and R¹ are hydrogen and C is (O_3/2Sι) vinyl - Catalyst M Example 15

A mixture of diethyl 2,4-dι(tπethoxysιlyl) butylphosphonate and diethyl 2-tπethoxysι!yl ethylphosphonate (34 1 g), tetraethyl orthosilicate (60 5 g) and 3-mercaptopropyl tπethoxysilane (8 6 g) were dissolved in methanol (280 ml) and then 1 M HCI (32 ml) was added with stirring The solution was left at ambient temperature for 48 h and then at 55⁰C for 100 h The resultant glass (34 0 g) was crushed and dried at 100⁰C at 0 1 mm of Hg Example 16

A mixture of diethyl 2,4-dι(trιethoxysιlyl) butylphosphonate and diethyl 2-trιethoxysιlyl ethylphosphonate (48 1 g) and 3-mercaptopropyl triethoxysilane (8 6 g) were dissolved in methanol (280 ml) and then 1 M HCI (22 ml) was added with stirring The solution was left at ambient temperature for 48 h and then at 55⁰C for 100 h The resultant glass (36 0 g) was crushed and then added to HCI (5M, 310 ml) The mixture was gently refluxed with stirring for 10 h and then cooled to room temperature The solid was filtered and first washed with distilled water till the washings were neutral and then with methanol and finally ether After drying at 100⁰C at 0 1 mm of Hg a white solid (24 0 g) was obtained, where the ratio of X Y C is 2 1 0 4 where C is (O_3/2Sι) 3-mercaptopropyl

Example 17

Hydrochloric acid (1 M, 20 ml) was added to a solution containing dimethoxy dimethyl silane

(40 6 g), tπmethyl chloro silane (1 ml) and dimethyl 2-trιethoxysιlyl ethylphosphonate and diethyl 2,4 - di trimethoxysilyl butylphosphonate (2 1 , 21 2 g) in methanol (240 ml) The solution was left at 8O⁰C for 26 h to give a clear glass (31 9 g)

Example 18

Hydrochloric acid (1 M, 2 ml) was added to a methanol (35 ml) solution containing trimethoxy vinyl silane (6 06 g), trimethoxy methylsilane (3 0 g) and diethyl 2-trιethoxysιlyl ethylphosphonate, and diethyl 2,4— di triethoxysilyl butylphosphonate (3 1 , 1 0 g) The solution was left at 5O⁰C for 70 h to give a clear resin (6 2 g)

Example 19

Hydrochloric acid (1 M, 4 2 ml) was added to a solution containing dimethoxy dimethyl silane

(13 2 g), trimethyl methoxy silane (1 0 g), diethyl 3-trιethoxysιlyl propylphosphonate (1 1 g) and diethyl 2-tπethoxysιlyl ethylphosphonate and diethyl 2,4 - di triethoxysilyl butylphosphonate (3 1 , 1 5 g) in methanol (30 ml) The solution was left at 5O⁰C for 70 h to give a clear resin (7 6 g)

Example 20

Hydrochloric acid (1 M, 30 ml) was added to a solution containing trimethoxy phenyl silane

(20 6 g), dimethoxy dimethyl silane (10 6 g), and dimethyl 2-trιethoxysιlyl ethylphosphonate and diethyl 2,4 - di trimethoxysilyl butylphosphonate (2 1 , 41 7 g) in methanol (280 ml) The solution was left at 8O⁰C for 36 h to give a clear resin (35 4 g) that was crushed to give a white powder

Example 21

Hydrochloric acid (1 M 31 ml) was added to a solution containing trimethoxy phenyl silane

(10 6 g), trimethoxy vinyl silane (4 ml), tetraethyl orthosilicate (43 ml) and dimethyl 2- tπethoxysilyl ethylphosphonate and diethyl 2,4 - di trimethoxysilyl butylphosphonate (2 1 ,

41 2 g) in methanol (400 ml) The solution was left at 8O⁰C for 45 h to give a clear glass

(31 1 g) that was crushed to give a white powder

Example 22

Hydrochloric acid (1 M, 28 ml) was added to a solution containing dimethoxy dimethyl silane

(40 6 g), trimethoxy vinyl silane (3 ml) and dimethyl 2-tπethoxysιlyl ethylphosphonate and diethyl 2,4 - di trimethoxysilyl butylphosphonate (2 1 , 33 2 g) in methanol (300 ml) The solution was left at 8O⁰C for 43 h to give a clear glass (34 9 g)

Example 23 Hydrochloric acid (5M, 70 ml) was added to a well ground up sample of diester from Example 17 (8 1 g) and the mixture was stirred under reflux for 12 h The white resin was filtered off and washed very well with water and then ethanol and finally with ether to give the di acid (6 9 g) - Catalyst O Example 24

Hydrochloric acid (5M, 80 ml) was added to a well ground up sample of diester from Example 22 (9 4 g) and the mixture was stirred under reflux for 6 h The white resin was filtered off and washed very well with water and then ethanol and finally with ether to give the di acid (7 2 g) - Catalyst P Example 25

A mixture of benzaldehyde (2 12 g, 20 mmol), Catalyst A (0 10 g) and pre-dπed molecular sieves (2 0 g) in methanol (10 ml) was stirred at ambient temperature for 10 h After filtration the solution was concentrated under reduced pressure to leave 1 ,1-dιethoxy phenylmethane (3 0 g) as a white solid in 98 % yield A ¹H nmr spectrum of the liquid indicated that the reaction had gone to completion δ_H 3 32 (6H, s OCH₃) Repeated with Catalyst B - 97% yield, Catalyst C - 95% yield, Catalyst D - 97% yield, Catalyst E - 97% yield, Catalyst F - 97% yield, Catalyst G - 96% yield, Catalyst I - 98% yield, Catalyst J - 97% yield, Catalyst K - 99% yield, Catalyst L - 99% yield, Catalyst M - 97% yield, Catalyst N - 97% yield, Catalyst O - 97% yield Example 26

A mixture of acetophenone (4 8 g, 40 mmol), ethylene glycol (6 ml) and Catalyst A (0 4 g) in toluene (30 ml) was refluxed under a Dean and Stark condenser for 4 h The reaction mixture was cooled, filtered and washed with water (3 x 50 ml) and then dried over magnesium sulphate On concentration 1-methy!-1 -phenyl 1 , 3 dioxolane was obtained as a solid (6 0 g) in 93% yield M p 61⁰C, lit 61-62°C Repeated with Catalyst B - 96% yield, Catalyst C - 97%, Catalyst D - 95% yield, Catalyst F - 97% yield, Catalyst G - 97% yield, Catalyst I - 97% yield Catalyst J - 97% yield, Catalyst K - 97%, Catalyst L - 95% yield, Catalyst M - 92% yield, Catalyst N - 97% yield, Catalyst P - 97% yield Example 27

A mixture of 2,3-dιmethyl 2,3-butanedιol (8 0 g) and Catalyst D (0 2 g) was warmed with stirring to 15O⁰C for 12 h under nitrogen The reaction flask was then set for distillation containing a small fractionating column and 3,3-dιmethyl 2-butanone (5 8 g) was obtained as a colourless liquid B p 106⁰C, Lit b p 106⁰C Repeating this reaction with the filtered catalyst from this experiment gave the ketone in a similar yield No apparent reduction was observed in catalyst efficiency over many runs Very similar yields were obtained using Catalysts B or C Example 28

A mixture containing Catalyst C (0 2 g) and oleic acid (2 82 g, 10 mmol) and ethanol (15 ml) was refluxed with stirring for 5 h On cooling ether (50 ml) was added and the catalyst was filtered off The organic washings were combined and concentrated to give ethyl oleate as a colourless oil, (2 78 g, 90% yield) δ_H 5 33 (2H, m, olefinic hydrogens), 4 1 1 (2H, q, J 8Hz, OCH₂), 2 29( 2H, t, J 9Hz, CH₂CO) The filtered catalyst was added to oleic acid (2 82 g, 10 mmol) and ethanol (15 ml) and the procedure was repeated No loss in catalytic activity was observed and ethyl oleate (2 77 g) was obtained as a colourless oil Example 29

A mixture containing Catalyst D (0 2 g) and oleic acid (10 mmol) and ethylene glycol (15 ml) was refluxed with stirring for 12 h On cooling ether (50 ml) was added and the catalyst was filtered off and washed with ether (50 ml) The organic washings were combined and washed with water (2 x 50 ml) and then dried over magnesium sulphate The filtered solution was concentrated to give a 2 1 mixture of 1 ,2-dι oleate ethane and 2-oleate-1 -ethanol as a colourless oil (90% yield) δ_H 4 22 (4H, bs, OCH₂CH₂O) for the dι-ester and δ_H 4 22 (2H, bs, OCH₂CH₂OH) and 3 6 (2H, bs, OCH₂CH₂OH) for the mono-ester mono alcohol Example 30 -

A mixture containing Catalyst D (0 2 g) and ethyl oleate (3 1 g, 10 mmol) and butanol (10 ml) was refluxed with stirring for 10 h On cooling ether (30 ml) was added and the catalyst was filtered off The organic washings were combined and concentrated to give butyl oleate as a colourless oil (3 2 g, 91 % yield) δ_H 5 33 (2H, m, olefin hydrogens), 4 01 (2H, t, J 8Hz, OCH₂), 2 27(2H, t, J 9Hz, CH₇CO) Example 31

A mixture of acetophenone ketal (1 04 g, 6 3mmol) and Catalyst G (0 07 g) was stirred in acetonitπle water (1 1 , 16 ml) at 8O⁰C for 2 h On cooling to room temperature, the catalyst was filtered and washed with ethyl acetate (70 rnl) The combined organic washings were washed with water, dried over magnesium sulphate, concentrated to give acetophenone (0 7 g) δ_H 2 58 (3H, COCH₃, s) The filtered Catalyst G was added to acetophenone ketal (1 04 g, 6 3mmol) in acetonitπle water (1 1 , 16 ml) and the above procedure was repeated to give acetophenone (0 7 g) Example 32

A mixture of glucose (1 0 g) and Catalyst D (0 10 g) and butanol (10 ml) was stirred in at 100-1 10⁰C for 12 h On cooling, the catalyst was filtered and washed with ether (50 ml) The solvent was removed under reduced pressure to afford a mixture of butyl glucofuranoside and butyl glucopyranoside (1 1 g) Example 33

A mixture of acetophenone (2 4 g, 20 mmol), benzaldehyde (2 12 g, 20 mmol) and Catalyst B or D (0 2 g) in toluene (20 ml) was refluxed for 20 h under a Dean and Stark apparatus After cooling, ether (100 ml) was added and the catalyst was filtered off and the filtrate concentrated under reduced pressure to give an oily solid On re-crystallisation from hexane-ethyl acetate 1 ,3-dιphenyl prop-2-en-1-one was obtained as colourless crystals (3 9 g) in 94% yield M p 6O⁰C, lit 58-62⁰C

Example 34

A mixture containing 1 ,4-butanedιol (30 ml) and Catalyst D (0 5 g) was stirred and heated at

12O⁰C Tetrahydrofuran and water was rapidly distilled from the reaction mixture Very similar yields were obtained using catalysts B, C, O or P

Example 35

A mixture of 1-phenyl-1-propanol (0 48 g) and Catalyst D (50 mg) or E (0 2 g) in toluene (4 ml) was stirred and heated at 75⁰C for 10 h under nitrogen Ether (40 ml) was added and the mixture was filtered to remove the catalyst The organic washings were concentrated under reduced pressure at room temperature to afford β - methyl styrene as a colourless oil (0 39 g,

92%) δ_H 7 4-7 1 (5H, m), 6 4 (1 H, d, J 12Hz), 6 25 (1 H, dq, J₁ 12Hz, J₂ 6Hz) and 1 87 (3H, d, J 6Hz) Very similar yields were obtained using catalysts N, O or P

Example 36

A mixture of cyclohexanol (5 g) and Catalyst D (50 mg) was stirred and heated at 12O⁰C under nitrogen Cyclohexene was distilled from the reaction mixture

Example 37

A mixture of 4-methylbenzyl alcohol (0 6g, 5 mmol), dihydropyran (4 fold molar excess) and

Catalyst B, C or D (50 mg) was stirred in ether (15 ml) for 12h The reaction was followed by

TLC, using a mixture of 95% pet ether and 5% ethyl acetate as eluant On completion the catalyst was filtered off and washed with ether (20 ml) The organic layer was concentrate under reduced pressure to give the tetrahydro pyran derivative as an oil (0 7 g) Identical yields were obtained using Catalysts N, O or P

Example 38

The product from Example 7 (8 g) was suspended in de-ionised water (80 ml) and the mixture was then adjusted to pH 13 with 1 M sodium hydroxide After 5 mm the mixture was filtered and the solid was washed well with de-ionised water and then with ethanol The di sodium salt (8 4 g) of Example 7 was then dried at 6O⁰C at 0 1 mm of Hg for 6h

Example 39

The product from Example 5 (5 g) was suspended in de-ionised water (50 ml) and the mixture was then adjusted to pH 13 with 1 M sodium hydroxide After 2 mm the mixture was filtered and the solid was washed well with de-ionised water and then with ethanol The tri sodium salt (4 4 g) of Example 5 was then dried at 6O⁰C at 0 1 mm of Hg for 6 h

Example 40

The product from Example 6 (10 g) was suspended in de-ionised water (100 ml) and the mixture was then adjusted to pH 13 with 1 M sodium hydroxide After 5 mm the mixture was filtered and the solid was washed well with de-ionised water and then with ethanol The di sodium salt (10 4 g) of Example 6 was then dried at 6O⁰C at 0 1 mm of Hg for 6 h

Example 41

An aqueous solution of cobalt nitrate hexahydrate (2 91 g) was added to the product (2 0 g) of Example 39 After stirring for 2 h the purple solid was filtered off and washed well with de- ionised water and then with ethanol The cobalt(li) salt (2 4 g) of Example 39 was then dried at 6O⁰C at 0 1 mm of Hg for 6 h

Example 42

An aqueous solution of cerium ammonium nitrate (2 IA g) was added to the product (2 0 g) of Example 39 After stirring for 2 h the yellow solid was filtered off and washed well with de- ionised water and then with ethanol The cerιum(IV) salt (2 3 g) of Example 39 was then dried at 60⁰C at 0 1 mm of Hg for 6 h

Example 43

An aqueous solution of cerium ammonium nitrate (2 74 g) was added to the product (2 0 g) of Example 39 After stirring for 2 h the yellow solid was filtered off and washed well with de- ionised water and then with ethanol The cerιum(IV) salt (2 3 g) of Example 39 was then dried at 6O⁰C at 0 1 mm of Hg for 6 h

Example 44

An aqueous solution of vanadyl sulfate (1 63 g) was added to the product (2 0 g) of Example

39 After stirring for 2 h the solid was filtered off and washed well with de-ionised water and then with ethanol The vanadyl(ll) salt (2 2 g) of Example 39 was then dried at 6O⁰C at 0 1 mm of Hg for 6 h

Example 45

An aqueous solution of chromium nitrate nonahydrate (2 7 g) was added to the product (2 0 g) of Example 39 After stirring for 2 h the solid was filtered off and washed well with de- ionised water and then with ethanol The chromιum(lll) salt (2 4 g) of Example 39 was then dried at 6O⁰C at 0 1 mm of Hg for 6 h

Example 46

A solution of zinc chloride (1 36 g) in ether (50 ml) was added to the product (2 0 g) of

Example 40 After stirring for 2 h the white solid was filtered off and washed well with ether

The zιnc(ll) salt (2 2 g) of Example 40 was then dried at 60⁰C at 0 1 mm of Hg for 5 h Example 47

A solution of ferric chloride (1 26 g) in ether (100 ml) was added to the product (2 0 g) of Example 40 After stirring for 2 h the solid was filtered off and washed well with ether The ferπc(lll) salt (2 3 g) of Example 40 was then dried at 60⁰C at 0 1 mm of Hg for 5 h Example 48

A solution of aluminium chloride (1 33 g) in ether (100 ml) was added to the product (2 0 g) of Example 39 After stirring for 2 h the solid was filtered off and washed well with ether The alumιnιum(lll) salt (2 3 g) of Example 39 was then dried at 6O⁰C at 0 1 mm of Hg for 5 h Example 49

A mixture of the Ce(IV) catalyst from Example 31 (0 04 g), sodium bromate (0 15 g) and methyl heptyl sulfide (0 292g, 2 mmol) in acetonitrile water (2 1 , 6 ml) was stirred at 3O⁰C for 3 h under an atmosphere of nitrogen On cooling ethyl acetate (70 ml) was added and the catalyst was filtered off The organic layer was separated and the aqueous phase was extracted with ethyl acetate (2 x 50 ml) The combined organic extracts were washed with water (25 ml), dried with anhydrous magnesium sulphate and concentrated to give methyl heptyl sulfoxide (0 3 g, 95%) with greater than 99% selectivity Example 50

A mixture of the Ce(IV) catalyst from Example 42 or 43 (0 04 g), sodium bromate (0 15 g) and thioanisole (0 248g, 2 mmol) in acetonitrile water (2 1 , 6 ml) was stirred at 30⁰C for 3 h under an atmosphere of nitrogen On cooling ethyl acetate (70 ml) was added and the catalyst was filtered off The organic layer was separated and the aqueous phase was extracted with ethyl acetate (2 x 50 ml) The combined organic extracts were washed with water (25 ml), dried with anhydrous magnesium sulphate and concentrated to give methyl phenyl sulfoxide (0 26 g, 93%) with greater than 99% selectivity The separated catalyst was added to a fresh batch of sodium bromate (0 3 g) and 4 thioanisole (0 248g, 2 mmol) in acetonitrile water (2 1 , 6 ml) The above procedure was repeated to give methyl phenyl sulfoxide (0 26 g, 93%) with greater than 99% selectivity Example 51

A mixture of the Cr(III) catalyst from Example 45 (0 04 g), sodium bromate (0 15 g) and thioanisole (0 248g, 2 mmol) in acetonitrile water (2 1 , 6 ml) was stirred at 30⁰C for 3 h under an atmosphere of nitrogen On cooling ethyl acetate (70 ml) was added and the catalyst was filtered off The organic layer was separated and the aqueous phase was extracted with ethyl acetate (2 x 50 ml) The combined organic extracts were washed with water (25 ml), dried with anhydrous magnesium sulphate and concentrated to give methyl phenyl sulfoxide (0 26 g, 93%) with greater than 99% selectivity Example 52

A mixture of Ce(IV) catalyst from Example 43 (0 08 g), sodium bromate (0 3 g) and 1- phenylethanol (0 244 g, 2mmol) in acetonitπle water (2 1 , 6 ml) was stirred at 80°C for 20 h under an atmosphere of nitrogen On cooling ether (70 ml) was added and the catalyst was filtered off The organic layer was separated and the aqueous phase was extracted with ether (2 x 50 ml) The combined organic extracts were washed with water (25 ml), dried with anhydrous magnesium sulphate and concentrated to give acetophenone as a colourless liquid (0 23 g, 96%) Example 53

A mixture of cyclohex-2-en-1 -ol (1 mmol) and tert-butyl hydroperoxide (5 equivalents in decane) and the catalyst from Example 44 (0 04 g) in acetonitrile (5 ml) was stirred and heated at 70⁰C under an atmosphere of nitrogen for 4 h The catalyst was filtered off and washed well with ether (80 ml) The combined organic layers were washed well with water (2x40 ml) and then dried over magnesium sulphate After filtration the solvent was removed under reduced to give the cis epoxide as an oil in 80% yield Example 54

To a mixture under nitrogen containing 5-pregnene-3β-acetoxy-20-one (0 716 g, 2 mmol) and the cobalt(ll) catalyst from Example 41 (70 mg) in acetonitrile (15 ml) was added tert- butyl hydroperoxide (5M in decane, 2 4 ml) The reaction mixture was warmed to 50-60°C and stirred for 24 h On cooling the reaction mixture was poured onto water (25 ml) and extracted into ethyl acetate (4 x 25 ml) The combined organic extract was washed with bicarbonate solution and with brine and then dried over magnesium sulphate On concentration the residue was eluted from a flash silica column with ethyl acetate-pet ether to give the 5-ene-7-one derivative in 70% yield Example 55

The product from Example 15 (1 0 g) was added to an orange solution of palladium acetate (0 02 g) in THF (50 ml) The mixture was stirred for 1 h and then filtered to give a colourless solution that on analysis contained less than 0 05ppm palladium Example 56

The product from Example 5 (2 0 g) was added to a solution containing pyridine (4 mmol) in ether (25 ml) The mixture was stirred for 1 h at room temperature and then filtered The solid was washed with ether (25 ml) and the combined organic fractions were evaporated There was no trace of any pyridine In a similar fashion benzylamine (4 mmol) and substituted benzylammes (4 mmol) were removed from a variety of solvents (25 ml) such as hydrocarbons, aromatics, ethers and chlorinated solvents Following an identical procedure, the product from Example 2 was equally effective in removing a wide range of amines from a variety of solvents Example 57

The product from Example 39 (0 1 g) was added to an aqueous solution containing 100 ppm

Co(II) ions The mixture was stirred for 1 h and then filtered Analysis via atomic absorption indicated a concentration of 0 02 ppm Co(II) In a similar procedure using the product from

Example 40 left a Co(II) concentration of 0 04ppm

Example 58

The product from Example 39 (0 1 g) was added to an aqueous solution containing 100 ppm

Cd(II) ions The mixture was stirred for 1 h and filtered and analysis via atomic absorption gave 0 04ppm Cd(II) In a similar procedure using the product from Example 38 left a Cd(II) concentration of 0 Oδppm

Example 59

A mixture containing the product from Example 23 (3 0 g) and sodium hydroxide (1 M, 30 ml) in water (20 ml) was stirred at room temperature for 1 h The mixture was filtered and the solid was washed with water (400 ml) and with methanol and then dried to give the di sodium salt of Example 23 (3 21 g)

Cerium catalyst - A mixture containing this di sodium phosphonate salt (3 21 g) and cerium ammonium nitrate (1 5 g) in, water (50 ml) was stirred for 3 h and then filtered The pale yellow solid was washed well with water and then with dry ether to give the cerium phosphonate catalyst Cobalt catalyst - A mixture containing this di sodium phosphonate salt

(3 0 g) and cobalt nitrate (1 5 g) in water (50 ml) was stirred for 1 h and then filtered The blue solid was washed well with water and then with dry ether to give the cerium phosphonate catalyst

Example 60

To a mixture under nitrogen containing fluorene (0 66 g, 4 mmol) and the cobalt catalyst from

Example 59 (70 mg) in acetonitπle (25 ml) was added tert-butyl hydroperoxide (5M in decane, 4 8 ml) The reaction mixture was warmed to 50-60⁰C and stirred for 24 h On cooling the reaction mixture was poured onto water (25 ml) and extracted into ethyl acetate

(4 x 25 ml) The combined organic extract was washed with bicarbonate solution and with brine and then dried On concentration the residue was eluted from a flash silica column with ether - pet ether to give 9-fluorenone in 80% yield

Example 61

A mixture containing thioanisole (1 mmol), sodium bromate (0 3 g) and the ceπum(IV) catalyst (50 mg) from Example 59 in acetonitπle (4ml) and water (1 ml) was stirred for 15 mm and then filtered The solid was washed with ethyl acetate (40 ml) and the combined organic extracts were washed with water and then dried On concentration methyl phenyl sulfoxide was obtained as an oil (0 135 g, 96%)

Claims

1 A compound of General Formula 1

X_xY_yC_cD_d (Formula 1 ) wherein X is [O_3/2SiCH(CH₂PO(OR)(OR¹))CH₂CH₂SiO_3/2], Y is [O₃/2SiCH₂CH₂PO(OR)(OR¹)], C is [O_3Z2SiV] and D is [O_3/2SιW], R and R¹ are each independently selected from hydrogen, an optionally complex metal ion Mⁿ⁺/n and an optionally substituted linear or branched group selected from C_{1 40}-alkyl, C_{2 40}-alkenyl, C_{2 40}-alkynyl group, an aryl and C_{1 40}-alkylaryl group, V is an optionally substituted linear or branched group selected from C_{1 40}-alkyl, C_{2 40}-alkenyl, C_{2 40}-alkynyl group, an aryl and C_{1 40}-alkylaryl group, and W is (CH₂)_SZ where Z is selected from a sulfonic acid group, a Mⁿ7n sulfonate group, an optionally substituted linear or branched group selected from C_{1 40}-alkyl, C_{2 40}-alkenyl, C_{2 40}-alkynyl group, an aryl and C_{1 4}o- alkylaryl group, sulfide, sulfoxide, sulfone, amine, polyalkyl amine, phosphine and other phosphorous containing group, n is an integer from 1 to 8 and s is an integer from 0 to 10, x, y, c and d are integers wherein x and y are independently 1 or more and c and d are independently 0 or more provided that at least one of c and d is 1 or more and the ratio of x y+c+d, is from 0 001 to 100 and the ratio d+c x+y is from 0 001 to 100, with the proviso that where C or D is C_{1 6}SιO_3/2, both c and d are 1 or more and C and D are different, the free valences of the silicate oxygen atoms are saturated by one or more of silicon atoms of other groups of Formula 1 , hydrogen, a linear or branched C_{1 12}-alkyl group, end groups R³ ₃M¹O_1/2, cross-linking bridge members R³ _qM¹(OR²)_mO_k/2 AI(OR²)_{3 p}Op_/2 or R³AI(OR²)_{2 r}O_r/2, chains comprising (R³ _eSι0_f/2)g, where M¹ is Si or Ti, R² is a linear or branched C_{1 40}-alkyl group an aryl or C_{1 40}-alkylaryl group, and R³ is a linear or branched C_{1 40}-alkyl group or an aryl or C_{1 40}-alkylary! group, k is an integer from 1 to 4 and q and m are integers from 0 to 2, such that m + k + q = 4, p is an integer from 1 to 3, and r is an integer from 1 to 2, and e is an integer from 2 to 3 and f is an integer from 1 to 2 such that e + f = 4 and g is an integer from 1 to 10⁸, or an oxo metal bridging system comprising a metal selected from zirconium, boron, magnesium, iron, nickel and a lanthanide

2 A compound as claimed in claim 1 comprising both C and D

3 A compound as claimed in claim 1 or claim 2 in which R and R¹ are each independently selected from hydrogen, an optionally complex metal ion Mⁿ⁺/n and an optionally substituted linear or branched C_{1 22}-alkyl, C_{2 22}-alkenyl, aryl and a C_{1 22}-alkylaryl group A compound as claimed in claim 3 in which R and R¹ are each independently selected from hydrogen, an optionally complex metal ion M^π+/n and a linear or branched C_{1 12}-alkyl, C_{2 12}-alkenyl, C_{2 12}-alkynyl, aryl and a C_{1 22}-alkylaryl group

A compound as claimed in any one of the preceding claims in which R and R¹ are each independently selected from hydrogen and an optionally substituted linear or branched group selected from C_{1 4}o-alkyl, C_{2 40}-alkenyl, C_{2 40}-alkynyl group, an aryl and C_{1 40}-alkylaryl group, V is selected from C_{1 12}-alkyl, C_{2 12}-alkenyl, C_{2 12}-alkynyl, aryl, C_{1 8}-alkylaryl and W is (CH₂)_SZ where Z is selected from an optionally substituted sulfonic acid group, a M^π+/n sulfonate group, sulfide, sulfoxide, sulfone, amine, polyalkylamine, phosphine, C_{1 12}-alkyl, C_{2 12}-alkenyl, C_{2 12}-alkynyl, aryl and Ci ₈-alkylaryl

A compound as claimed in claim 5 wherein R and R¹ are each independently selected from hydrogen, C_{1 8}-alkyl, phenyl and C_{1 8}-alkylaryl and with at least one of C or D or both present where V is an optionally substituted C_{1 12}-alkyl, vinyl, aryl and W is (CH₂)_SZ where Z is a sulfonic acid group or a substituted C_{1 12}-alkyl, vinyl, an aryl or C_{1 12}-alkyl or alkylaryl sulfide, sulfoxide, sulfone, polyalkylamine, amine, or phosphine or other phosphorous containing group and s is an integer from 2 to 6

A compound as claimed in claim 5 or claim 6 in which R and R¹ are each independently selected from hydrogen, C_{1 4}-alkyl, phenyl or C_{1 8}-alkylaryl and V is vinyl or d_-8-alkyl, phenyl or C_{1 8}-alkylaryl and W is (CH₂)₂Z where Z is a sulfonic acid group or a Mⁿ7n sulfonate group

A compound as claimed in any one of the preceding claims in which either or both of R and R¹ are hydrogen, V is selected from C_{1 12}-alkyl, vinyl, C_{2 12}-alkenyl, C_{2 12}-alkynyl, aryl and C_{1 8}-atkylaryl and W is a Mⁿ⁺/n sulfonate group, sulfonic acid, polyalkylamine or amine

A compound as claimed in claim 8 in which V is vinyl or C_{1 8}-alkyl or phenyl and W is (CH₂)₂SO₃H

A compound as claimed in claim 8 or claim 9 wherein one of R or R¹ is hydrogen and the other is C_{1 4}-alkyl, phenyl, C_{1 8}-alkylaryl and with at least one of C or D or both present where V is methyl, ethyl, vinyl or phenyl A compound as claimed in any one of claims 1 to 4 in which either or both of R and R¹ are Mⁿ7n, V is selected from d.₁₂-alkyl, vinyl, C₂-i₂-alkenyl, C₂.₁₂-alkynyl, aryl and C_L8- alkylaryl and W is a Mⁿ7n sulfonate group, sulfonic acid, polyalkylamine or amine

A compound as claimed in any one of claims 1 to 4 or 1 1 in which either or both of R and R¹ are Mⁿ7n selected from sodium potassium, calcium, magnesium, cobalt, iron, nickel, cerium, vanadium, chromium, titanium, lanthanum, silver, mercury, gold, manganese, platinum, palladium and rhodium

A compound as claimed in any one of the preceding claims, the compound being chiral and for use in asymmetric synthesis or chiral separation, in which one of R and R¹ is hydrogen or Mⁿ7n and the other of R and R¹ is an optionally substituted C₁₂.₄₀-alkyl, C₁₂^o- alkenyl, C₁₂.₄₀-alkynyl, Ci₂.₄₀-alkylaryl or aryl and V is selected from an optionally substituted linear or branched group selected from Ci.₄₀-alkyl, C_{2 40}-alkenyl, C₂.₄₀-alkynyl group, an aryl and C_{1 40}-alkylaryl group and W is (CH₂)_SZ where Z is selected from a substituted sulfonic acid group, a Mⁿ7n sulfonate group, sulfide, sulfoxide, sulfone, amine or polyalkylamine, phosphine, an optionally substituted linear or branched group selected from Ci.₄₀-alkyl, C_{2 40}-alkenyl, C₂.₄₀-alkynyl group, an aryl and C₁.₄o-alkylaryl group and s is an integer from two to four

A compound as claimed in any one of the preceding claims in which the ratio of x y is from 1 100 to 100 1

A compound as claimed in any one of the preceding claims in which the ratio of x y is from 1 50 to 50 1

A compound as claimed in any one of the preceding claims in which the ratio of c+d x+y is from 1 50 to 50 1

A compound as claimed in any one of the preceding claims in which the ratio of x y+c+d, varies from 0 01 to 100 and d+c x+y varies from 0 01 to 100

A compound as claimed in any one of the preceding claims in which n is 1 to 4 and s is from 0 to 6 A compound as claimed in claim 1 in which C is present and D is not present wherein C is [O_3/2SiV] and V is an optionally substituted, linear or branched group selected from C_{7 40}- alkyl, C_{2 40}-alkenyl, C_{2 40}-alkynyl, an aryl and C_{1 40}-alkylaryl group

A compound as claimed in claim 19 in which V is an optionally substituted linear or branched C_{7 22}-alkyl, C_{2 22}-alkenyl, aryl and a C-i ₂₂-alkylaryl group

A compound as claimed in claim 1 in which D is present and C is not present wherein D is [O_3/2S1W], W is (CH₂)_SZ and Z is selected from an optionally substituted sulfonic acid group, a Mⁿ7n sulfonate group, sulfide, sulfoxide, sulfone, amine, polyalkylamine, phosphine and an organic group selected from C_{1 12}-alkyl, C_{2 12}-alkenyl, C_{2 12}-alkynyl, aryl and C_{1 8}-alkylaryl,

A compound as claimed in any one of the preceding claims which includes one or more end groups, cross linking bridge members or chains wherein the ratio of the said groups, members and/or chains to x+y+c+d is from 0 001 to 999 1

A compound as claimed in any one of the preceding claims that includes an end group derived from a trialkyl or tπaryl alkoxysilane, or a cross linking bridge member or a polymer chain derived from an orthosilicate, a titanium alkoxide, an aluminium trialkoxide, a mono alkyl or mono aryl trialkoxysilane or a di alkyl or di aryl dialkoxysilane

A compound as claimed in claim 23 wherein the end group where present is R³ ₃Sι0_1/2 the cross linking bridge where present is selected from SiO^₂, R³Sι0_3/2, R³ ₂Sι0_2/2, T1O_4/2, R³TiO_3Z2, R³ ₂TιO_2/2, AIO_3/2, R³AIO_2/2, and, where present the chain is (R³ ₂SιO₂z₂)_g where g is an integer from 1 to 10⁸ wherein R³ is as defined in claim 1

A compound as claimed in claim 24 wherein g is from 1 to 100

A compound as claimed in claim 24 or claim 25 wherein R² and R³ are independently selected from linear or branched C_{1 22}-alkyl, aryl and a C_{1 22}-alkylaryl group

A compound as claimed in claim 26 wherein R² and R³ are independently selected from a linear or branched C_{1 8}-alkyl, aryl and a C_{1 8}-alkylaryl group

A process for the preparation of a compound of Formula 1 comprising contacting a vinyl trialkoxysilane with a phosphorous acid under free-radical addition reaction conditions and in the presence of a free-radical initiator to produce a compound of Formula 1

29 A process for the preparation of a compound of Formula 1 in which R and R¹ are each independently hydrogen, a linear or branched C_1-40-alkyl, C₂.₄o-alkenyl or C₂.₄₀- alkynyl group, an aryl or C_1-40-alkylaryl group or an optionally complex metal ion Mⁿ7n and with X, Y and D or X, Y, C and D present where V is C₂-4o-alkenyl and W is (CH₂)₂SO₃H, which comprises contacting ammonium or metal sulfite with compounds containing groups X and Y where R and R¹ are each independently hydrogen, a linear or branched Ci.₄o-alkyl, C_{2 40}-alkenyl or C₂.₄₀-alkynyl group, an aryl or C_{1 40}-alkylaryl group or an optionally complex metal ion Mⁿ⁺/n and V is C₂.₄₀-alkenyl under free radical addition reaction conditions

30 A process for the preparation of a compound of Formula 1 containing X, Y and C in which R and R¹ are both hydrogen and V is d^o-alkyl, C₂.₄₀-alkenyl, C₂.₄₀-alkynyl, aryl or Ci-₄₀-alkylaryl comprising hydrolysing a compound of Formula 1 containing groups X and Y in which both R and R¹ are Ci i₂-alkyl, alkylaryl or aryl and V is C^o-alkyl, C₂.₄₀-alkenyl, C₂_₄o-alkynyl, aryl or C_{1 40}-alkylaryl in acid conditions

31 A process for treating a feedstock comprising contacting a compound as claimed in any one of claims 1 to 27 with a feed stream ι) to effect a chemical reaction by catalytic transformation of a component of the feed stream to produce a desired product,

M) to remove a component of the feed stream from the stream, or in) to remove an ionic species in the feed stream in an ion exchange process

32 A process as claimed in claim 31 for conducting an oxidation, reduction, alkylation, polymerisation, hydroformylation, arylation, acylation, isomerisation, alkylation, carboxylation, carbonylation, esterification, trans-esteπfication or rearrangement reaction

33 Use of a compound as claimed in any one of claims 1 to 27 as a catalyst

34. Use as claimed in claim 33 in which the compound is used as a heterogenous acid catalyst

35 Use as claimed in claim 34 of a compound as claimed in any one of claims 1 to 27 as a heterogeneous catalyst for an oxidation, reduction, alkylation, polymerisation, hydroformylation, arylation, acylation, isomerisation, alkylation, carboxylation, carbonylation, esteπfication, trans-esterification or rearrangement reaction

Use of a compound as claimed in any one of claims 1 to 27 for ion exchange

Use of a compound as claimed in any one of claims 1 to 27 as a scavenger for the removal of an unwanted organic or inorganic compound from a liquid substrate

Use as claimed in claim 37 in which the liquid substrate is selected from a reaction mixture, waste stream and waste water

Use of a compound as claimed in any one of claims 1 to 27 for the immobilisation of a biological molecule such as enzymes, peptides, proteins and nucleic acids

An anti-microbial composition comprising a compound as claimed in any one of claims 1 to 27 and a carrier

Use of a compound as claimed in any one of claims 1 to 27 and a composition as claimed in claim 40 as an anti-microbial agent

Use of a compound as claimed in any one of claims 1 to 27 as a hydrophilicity modifier, a flameproofing agent, an antistatic agent, a coating for biomedical devices, a water repellent film and as a coating

Use of a compound as claimed in any one of claims 1 to 27 for solid phase synthesis or for solid phase extraction and purification

Use of a compound as claimed in any one of claims 1 to 27 as a heterogeneous catalyst support

Use of a compound as claimed in any one of claims 1 to 27 for the separation or purification of organic, biological or inorganic molecules from gaseous, liquid and solid environments

Use of a compound as claimed in any one of claims 1 to 27 for chiral separation Use of a compound as claimed in any one of claims 1 to 27 as a gel filtration, size- exclusion or chromatography medium.

Use as claimed in claim 47 for the purification and/or identification of an organic or biological compound