WO2005003213A2

WO2005003213A2 - Substituted organopolysiloxanes, methods for the production and use thereof

Info

Publication number: WO2005003213A2
Application number: PCT/GB2004/002782
Authority: WO
Inventors: Alice Caroline Sullivan; John Robert Howe Wilson
Original assignee: Queen Mary & Westfield College
Priority date: 2003-06-28
Filing date: 2004-06-28
Publication date: 2005-01-13
Also published as: WO2005003213A3; GB0315201D0

Abstract

The invention relates to new compounds of Formula (2) as defined in claim 1. The compounds are useful as catalysts for a wide variety of reactions and as cation exchangers, organic and inorganic compound scavengers and solid phase purification or extraction materials and have the advantages that they can be prepared in a one-pot reaction and have functional group loading can be tailored to be at a required level. In addition, the compounds have high chemical and thermal stability, fixed and rigid structures, are insoluble in organic solvents, high resistance to ageing, and can easily be purified and reused.

Description

Substituted organopolysiloxanes, methods for the production and use thereof

The invention relates to two new substituted organopolysiloxane classes of compounds. The first contain phosphinic acid groups that can act as acid catalysts, cation exchangers, organic and inorganic compound scavengers, solid phase purification or extraction materials and possess in their characteristics a number of advantages over organic polymer systems and inorganic supporting materials. In addition the metal salts of the organopolysiloxane phosphinic acids can be used to catalyse a wide variety of chemical transformations. The second contain phosphonic amide groups that can act as base catalysts, cation exchangers and possess in their characteristics a number of advantages over organic polymer systems and inorganic supporting materials. In addition the metal salts of the organopolysiloxane phosphonic amides can be used to catalyse a wide variety of chemical transformations. Precursors of both these new products, processes for their production and their uses are also described.

As is known, acid, base and metal reagents as well as catalysts are utilised in the chemical and biochemical industry to conduct a wide range of chemical transformations. A range of homogenous and heterogeneous reagents and 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. This need has led to investigations into the design of new materials that can catalyse a variety of chemical transformations. Key requirements for such new catalysts are very good thermal stability, high insensitivity to chemical attack, high functional group loading, fixed and rigid structures, optimum functional groups so as to avoid rearrangements and side products, limited swelling capability, insolubility in organic solvents, ease of purification and high reusability, high ageing resistance and ease of access to the functional group which conducts the chemical transformation. In addition the processes to make such catalyst systems have to be flexible so as to enable the production of optimum structures and shapes for specific reactions. This could include tailoring the porosity from anywhere between macroporous to microporous structures, variable loading of the functional group, ease of making different metal derivatives and selective pH ranges. A range of metals and catalysts have been embedded within or adsorbed on to the surface of silica, and other materials. The state of this art, for silica and its derivatives, is described by M.A.Brook in Silicon in Organic, Organometallic and Polymer Chemistry, Chapter 10, page 318, John Wiley & Sons, Inc., 2000. One of the problems encountered with these systems is the loss of the active functional groups due to their often very weak attachment to the silica. New organo-silica materials are needed which whilst possessing the properties described above have functional groups which are strongly attached and which bind strongly to a range of metals and catalysts.

As a consequence of stricter environmental regulations there is a growing requirement for more effective systems for the removal and recovery of metals from a wide spectrum of metal contaminated solvents and aqueous based wastes and from contaminated waters. For example 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. Another major challenge is the removal of catalysts based on platinum, palladium and rhodium, which are extensively used to conduct a variety of chemical transformations, from both the reaction products as well as waste effluent. Cation exchangers have been used to remove metal ions from solution and the state of this art is described in Kirk - Othmer's Encyclopaedia of Chemical Technology, 4^th Edition, Nol.14, page 737. The type of cation exchangers that are employed consist primarily of an organic, partly cross-linked polystyrene backbone with sulfonate groups attached to some of the phenyl rings. The physical and chemical properties of these polystyrene sulfonic cation exchangers are strongly affected by the organic nature of the polymeric backbone so that a number of disadvantages affect their technical field of application. The chemical and physical properties of a variety of such polystyrene based systems are described in the Bio-Rad Life Science Research Products catalogue 1998/99, pages 56 - 64. These limitations include relatively low temperature resistance 90°-110°C, sensitivity to chemical attack that can result in complete breakdown of the polymer matrix, strong swelling capacity, non-usability in certain organic solvents and the need for swelling to make the functional groups accessible. Amine functionalised polystyrene beads have also been used but suffer in a similar fashion. Organophosphonic acid cation exchangers have also been reported in US 5,281,631. These systems are based on the products from the copolymerisation of the very expensive vinylidene disphosphonic acid with styrene, acrylonitrile and divinylbenzene. However the physical and chemical properties of these organophosphonic acid resins are very similar to the polystyrene sulfonic acid based systems and thus likewise their field of application is limited. Inorganic polymer systems such as silica, aluminium oxide and titanium oxide, which do not suffer some of these drawbacks, have been investigated as ion exchangers. Active functional groups or metals are attached by a variety of means to these systems. However these systems suffer from the fact that only a low level of functional groups can be bound onto these surfaces. One of the additional problems encountered with these systems is that the functional groups can be removed on use or on standing. This is due to the rather weak attachment between the functional group and the surface atoms on the support.

Strong acidic cation exchangers based on sulfonic acid groups attached to a organopolysiloxane backbone have been described in US 4,552,700 and US 5,354,831. The materials reported have a general formula of (0₃/₂Si — R¹ — S0₃ ^")_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 Si0_4/2, R'SiOaa, Ti0_4/2, A10_3/2j etc. Whilst these materials can act as cation exchangers it is generally recognised that sulfonic acid groups are limited in their effectiveness to complex with a range of metals and in comparison to other functional groups. In addition the sulfonate group is also limited by the fact that it is a mono anion and thus more of these functional groups are needed to bind to metals compared to other functional groups.

Functionalised solid materials are used in solution phase organic synthesis to aid rapid purification and workup. These functionalised solid materials, also known as scavengers, can remove excess reagents and side products. At the end of the reaction the scavenger is added to quench and selectively react with excess or unreacted reagents and reaction side products. The unwanted chemicals now attached to the functionalised materials are removed by simple filtration. This simple process circumvents the standard purification methodologies of liquid-liquid extraction, chromatography and crystallisation. Substituted polystyrene derivatives are the main class of materials being used as scavengers. However these materials suffer a number of significant limitations such as lack of thermal stability, swelling and shrinking in organic solvents and low functional group loading (0.6-2 mmol/g).

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 found that the metal invariably complexes to the desired API and metal contents in the range of 600-1000 ppm are not uncommon. The current target for palladium is less than 5 ppm. Various methods have been tried to reduce the residual palladium content, most unsuccessfully. Selective re-crystallisation leads to only a slight lowering of metal content. A lower yield of the API is a significant unwanted side effect of this process. Attempts to reposition the palladium catalysed reaction from the final to an earlier step leads also to a slight but not significant lowering of metal content. Attempts to pass a solution of the API through a medium containing a metal exchanger such as a functionalised polystyrene resin have also been largely unsuccessful. Alternative and more costly processes have been tried - washing with an aqueous solution of a suitable metal chelator. A number of such reagents have been used with only limited success.

In our earlier patent application PCT/GB 0200069 we reported compounds of General Formula 1:

wherein R and R¹ are each independently hydrogen, a linear or branched Cuo alkyl, C₂. o alkenyl or C₂.₄₀ alkynyl group, an aryl or Cι.₄o alkylaryl group or an optionally complex metal ion Mⁿ⁺/n; wherein n is an integer from 1 to 8; 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 .π alkyl group or by cross-linking bridge members R³ _qM'(OR²) _mQ_m or Al(OR²)₃._pO_p/2 or R³Al(OR²)₂._rO_{r 2}; where M¹ is Si or Ti; R² is a linear or branched C_\._\2 alkyl group; and R³ is a linear or branched .₆ alkyl 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; and p is an integer from 1 to 3; and r is an integer from 1 to 2; or other known oxo metal bridging systems; x, y and z are integers such that the ratio of x : y+z, varies from 0.00001 to 100,000 with the fragments [0₃/₂SiCH(CH₂PO(OR)(OR^I))CH₂CH₂Siθ3/2]_x and [0₃/2SiCH₂CH₂PO(OR)(OR¹)]_y always present whilst the integer z varies from 0 to 200y.

Compounds of General Formula 1 are capable of acting as catalysts, catalyst immobilisation supports and ion exchanger materials.

The present invention relates to novel variants of General Formula 1 which are capable of acting as catalysts, catalyst immobilisation supports, ion exchanger materials, organic and inorganic compound scavengers and solid phase purification or extraction materials, or which are precursors for these.

Therefore, in a first aspect of the present invention, there is provided a compound of General Formula 2:

wherein; the free valences of the silicate oxygen atoms are saturated by one or more of: silicon atoms of other groups of Formula 2, hydrogen, or by cross-linking bridge members or polymer chains R^M^OR²) _mO_m or Al(OR²)_3-pO_{p 2} or R³Al(OR²)_2-rO_r2; where M is Si or Ti; R² is a linear or branched -π alkyl group; and R³ is a linear or branched Cι_ ₀ alkyl group, C2- o alkenyl or C_2- o alkynyl group, an aryl or C₁.₄0 alkylaryl group, or substituted linear or branched C].₄o alkyl group, C₂- o alkenyl or C₂.₄o alkynyl group, an aryl or Cι_₄₀ alkylaryl group with one or more halogens, amines and alkyl amines, hydroxyl groups, sulfide and sulfonic acids, nitriles, alkyl and aryl phosphines, carboxylate acids and esters; k is an integer from 1 to 4 and q and m are integers from 0 to 2; such that m + k + q = 4; and p is an integer from 1 to 3; and r is an integer from 1 to 2; or other known oxo metal bridging systems; and wherein either:

A. A¹ is hydrogen; g is equal to zero; and A is a hydroxyl group or 0(Mⁿ⁺/n);

M is an optionally complex metal ion; and n is an integer from 1 to 8; e, f, and h are integers such that the ratio of e : f+h, varies from 0.00001 to 100,000 with the fragments [03/₂SiCH(CH2P0(A)(A¹))CH₂CH₂Si03/2]e and [0₃/₂SiCH₂CH2PO(A)(A¹)]f always present whilst the integer h varies from 0 to 200f; or

B. A is NR⁴R⁵

R⁴ and R⁵ are each independently hydrogen, a linear or branched Cι.₄₀ alkyl, C₂. o alkenyl or C₂.₄o alkynyl group, an aryl or C₁.₄0 alkylaryl group, or ((CH₂)_sNR⁶) (CH₂)_NHR⁷ where R⁶ is hydrogen, a linear or branched Cι. ₀ alkyl or ((CH₂)_SNR⁶)_W(CH₂)_SNHR⁷ and each s, t and w is independently an integer from 1 to 12, and R⁷ is hydrogen or a linear or branched Cι_₄₀ alkyl;

A s NR or OR⁸; R⁴ and R⁵ are as defined above; R⁸ is hydrogen, a linear or branched C _O alkyl, C₂- o alkenyl or C₂. o alkynyl group, an aryl or C].₄o alkylaryl group or an optionally complex metal ion Mⁿ⁺/n and n is an integer from 1 to 8; h is equal to zero; and e, f and g are integers such that the ratio of e : f+g, varies from 0.00001 to 100,000 with the fragments [0₃/₂SiCH(CH₂P(0)AA¹)CH₂CH₂Si0₃/₂]e and [0_{3 2} SiCH₂CH₂P(0)AA¹]_f always present whilst the integer g varies from 0 to 200f.

or a metal complex M_v(T)_j of a polyalkyl amine compound as defined in B above, where Mⁿ⁺ are ions derived from lanthanide, actinide, main group or transition metals, T is a counter ion and v and j are integers which balance the overall charge;

One advantage of the new catalysts, catalyst immobilisation supports, cation exchangers, organic and inorganic compound scavengers and solid phase purification or extraction materials based on compounds of Formula 2 is that the functional group can be selected to have either a high or a low value according to the requirements of the user. 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, ease of purification and high reusability. In addition the processes for the preparation of compounds of Formula 2 are very flexible, enabling the porosity to be varied from micro to macro porous, the loading of the phosphonic or phosphinic groups to be varied as required, different amines can be readily incorporated via common intermediates and a wide range of metal derivatives can be made with the added advantage of a high metal incorporation. Furthermore compounds of Formula 2 have the added advantages of a more effective cation exchange group compared to sulfonate, of strong metal to phosphinic or phosphonate amide binding and thus little or no leaching on operation.

The phosphinic acid derivatives of Formula 2 act as a mild and selective acid catalyst. The substituted phosphonic amides act as basic catalysts.

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 2 do not require these cross linking agents to possess the desired physical and chemical properties. The bridging unit [0₃/₂SiCH(CH₂PO(A)(A¹))CH2CH₂Siθ3/2] in Formula 2 provides the necessary cross-linking. In the context of the present invention, Cι_-40 alkyl refers to a straight, branched or cyclic hydrocarbon chain having from one to forty carbon atoms. The Cι_-4o alkyl group may be substituted with one or more substituents selected from nitro, chloro, fluoro, bromo, nitrile, Cι_₆ alkoxy, a Cι- o alkyl or aryl di substituted phosphine, amino, amino Cι.₄₀ alkyl or amino di (Cι_₄₀ alkyl), C_1-4o alkyl phosphinic or phosphonic group or carboxylate acids or esters. Examples include methyl, ethyl, isopropyl, n-propyl, butyl, tert-butyl, n-hexyl, n-decyl, 72-dodecyl, cyclohexyl, octyl, ώo-octyl, hexadecyl, octadecyl, iso- octadecyl and docosyl. A Cι_ι₂ alkyl group has from one to twelve carbon atoms.

In the context of the present invention, C₂--₁0 alkenyl refers to a straight, branched or cyclic hydrocarbon chain having from one to forty carbon atoms and including at least one carbon-carbon double bond. The C₂- o alkenyl group may be substituted with one or more substituents selected from nitro, chloro, fluoro, bromo, nitrile,

alkoxy, a Cι_₄o alkyl or aryl di substituted phosphine, amino, amino Cι.₄₀ alkyl or amino di (C₁.₄0 alkyl), 0 alkyl phosphinic or phosphonic group or carboxylate acids or esters. Examples include ethenyl, 2-propenyl, cyclohexenyl, octenyl, zso-octenyl, hexadecenyl, octadecenyl, ώooctadβcenyl and docosenyl.

In the context of the present invention, C₂.₄o alkynyl refers to a straight, branched or cyclic hydrocarbon chain having from one to forty carbon atoms and including at least one carbon-carbon triple bond. The C₂.₄o alkynyl group may be substituted with one or more substituents selected from nitro, chloro, fluoro, bromo, nitrile, Q-β alkoxy, a .₄0 alkyl or aryl di substituted phosphine, amino, amino C₁.₄0 alkyl or amino di (C^o alkyl), ^o alkyl phosphinic or phosphonic group or carboxylate acids or esters. Examples include ethynyl, 2-propynyl octynyl, ώø-octynyl, hexadecynyl, octadecynyl, -so-octadecynyl and docosynyl.

C_.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. The aryl group may be substituted with one or more substituents selected from nitro, chloro, fluoro, bromo, nitrile,

alkyl or aryl di substituted phosphine, amino, amino Cι.₄₀ alkyl or amino di (Ci^o alkyl), C^o alkyl phosphinic or phosphonic group or carboxylate acids or esters. Examples include phenyl, pyridinyl and furanyl.

The term Cι_{- 0} alkylaryl group refers to a straight or branched hydrocarbon chain having from one to forty carbon atoms linked to an aryl group. The Cι. o alkylaryl group may be substituted with one or more substituents selected from nitro, chloro, fluoro, bromo, nitrile, -β alkoxy, a Cι_-4o alkyl or aryl di substituted phosphine, amino, amino Cι_« alkyl or amino di (Cι_₄₀ alkyl), C_MO alkyl phosphinic or phosphonic group or carboxylate acids or esters. Examples include benzyl, phenylethyl and pyridylmethyl. In a Cι_-8 alkylaryl group, the alkyl chain has from one to eight carbon atoms.

Compounds in which A¹ is hydrogen and A is either hydroxyl or 0(Mⁿ⁺/n) where M is an optionally complex metal ion and n is an integer from 1 to 8 and g is zero are designated below as compounds of Formula 2A. The metal ion M^"1"" is derived from a lanthanide, actinide, main group or transition metal.

Compounds of Formula 2A in which A¹ is hydrogen and A is hydroxyl have been found to be useful for catalysing a wide range of reactions, particularly reactions which are conventionally acid catalysed such as condensation reactions of aldehydes and ketones, ketalisation and acetalisation, polymerisations, condensations, hydrations, acylations, amidations, additions, dehydration of olefins, a wide range of rearrangement and fragmentation reactions, isomerisations, glycohsations, esterifϊcations and the trans-esterification of carboxylate esters.

Compounds of Formula 2A in which A¹ is hydrogen and A is 0(Mⁿ⁺/n) are particularly useful 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, additions, carboxylations, glycohsations, carbonylations, esterifications, trans-esterifications and rearrangements.

Preferred Mⁿ⁺ are ions derived from lanthanide, actinide, main group or transition metals and more preferred Mⁿ⁺ ions are derived from lanthanide, main group or transition metals.

The metal salts of Formula 2A, where A¹ is hydrogen and A is 0(Mⁿ⁺/n), are also useful as cation exchangers and preferred A¹, A and Mⁿ⁺ are as specified above. Compounds in which A is NR R , where R and R are as defined above, are designated compounds of Fonnula 2B.

Compounds of Formula 2B in which A¹ is NR⁴R⁵ or OR⁸ where R⁴ and R⁵ are independently hydrogen or Cj.₁₂ alkyl, and ((CH₂)_sNR⁶)_t(CH₂)_sNHR⁷ where R⁶ is hydrogen, a linear or branched Cμ₀ alkyl or ((CH₂)sNR⁶)_w(CH₂)_sNHR⁷ and s, t and w are integers from 1 to 6, and R⁷ is hydrogen or a linear or branched C .n alkyl are preferred. Compounds where A and A¹ are based on commercially available polyalkyl amines are particularly preferred.

Metal salt complexes M_v(T)_j of these polyamine compounds of Formula 2B where M are ions derived from lanthanide, actinide, main group or transition metals and T are counter ions, for example well known anions such as halides, nitrates, sulphates, phosphates, acetates are especially preferred.

Compounds of Formula 2B in which A is NR⁴R⁵ and A¹ is either NR⁴R⁵ or OR⁸ have been found to be useful for catalysing a range of reactions which are conventionally based catalysed such as condensation reactions, hydrolysis, additions, eliminations, alkylations, substitutions, a wide range of rearrangement and fragmentation reactions and isomerisations.

The metal salt complexes M_v(T)_j of the polyamine compounds of Formula 2B have been found to be useful as solid immobilisation supports for metal catalysts and complexes and as heterogeneous catalysts for a wide range of reactions, for example oxidations, reductions, hydrogenations, alkylations, polymerisations, hydroformylations, arylations, acylations, isomerisations, additions, carboxylations, glycolisations, carbonylations, esterifications, trans-esterifications and rearrangements.

The compounds of Formula 2B where A is NR⁴R⁵ and A¹ is either NR⁴R⁵ or OR⁸ are also useful as cation exchangers and preferred A¹, A and Mⁿ⁺ are as specified above.

Compounds of Formula 2B in which A is NR⁴R⁵ and A¹ is either NR⁴R⁵ or OR⁸ where either or both A and A¹ contain a chiral group can be used for applications such as asymmetric synthesis. Where a cross linker is used, it is preferred that the ratio of cross linker to e+f+g+h varies from 0 to 99:1. Particularly suitable cross linkers are derived from orthosilicates, titanium alkoxides and aluminium trialkoxides. Examples include tetraethyl orthosilicate, aluminium triethoxide, aluminium tributoxide and titanium isopropoxide. The cross linking bridge member is preferably Si0_4/2 or R³Si0_3/2 or (R³)₂Si0₂/₂ or Ti0₄₂ or R³Ti0₃/₂ or (R³)₂Tiθ2₂ or A10_{3 2} or R³Alθ2/₂. R³ is preferably C_M2 alkyl, C₂-ιo alkenyl, aryl or substituted derivatives thereof.

It is particularly preferred that the ratio of e : f varies from 1:1000 to 1000:1 and more usually from 1:500 to 500:1.

The preparation of compounds of Formula 2 will now be discussed in greater detail.

The general procedure used for the production of the organopolysiloxane phosphinic compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl consists of a free radical catalysed reaction between hypophosphorous acid and vinyl trialkoxy silane. The state of the art of the addition of phosphorus radicals to double bonds is described in Org. Reactions. NolJ3, 218-222. It is known that in general the free radical reaction between hypophosphorous acid and an alkene does not proceed in high yield. Depending on the particular starting materials dimers and higher tellomers can be produced. It was decided to use this general observation to produce organopolysiloxane comprising phosphinic groups with the desired physical and chemical properties.

Hypophosphorous acid, commercially available as a solution in water, is first heated at 40°C under reduced pressure such as 0.01 mm of Hg to remove excess water. The amount of water left in the hypophosphorous acid has a direct impact on the ratios of e, f and h as well as the speed with which the reaction mixture starts to solidify.

Depending on the ratios of starting materials and temperature, varying ratios of [0₃/2SiCH(CH2PO(H)(OH))CH₂CH2Siθ3/2]e and [03/2SiCH₂CH2PO(H)(OH)]_f and

[0₃2SiCH2CH2PO(OH)(CH2CH₂Siθ32)]h are produced via a free radical addition of hypophosphorous acid to vinyl trialkoxy vinyl silane in the presence of a free radical initiator under an atmosphere of nitrogen.

alkoxy groups are preferred with methoxy and ethoxy especially preferred. 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 60°C and 170°C can be used, though a reaction temperature of between 100°C and 140°C 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. Reaction times of between 15 minutes to 48 hours have been used with 3 to 18 hours preferred. The reaction mixture is stirred rapidly and starts to solidify after a couple of hours. On completion the reaction mixture is concentrated under reduced pressure and the resultant glass is then crushed and washed with water.

The presence of the fragments [θ3/2SiCH(CH2PO(H)(OH))CH₂CH2Siθ32]_e and [0₃/2SiCH₂CH₂PO(H)(OH)]_f and [θ3/2SiCH2CH₂PO(OH)(CH2CH₂Siθ3/₂)]h in compounds of Formula 2A was evident from a detailed analysis of a series of Η, ¹³C and ³¹P nmr experiments performed on the sodium salt of the compound from Example 1 conducted on a Bruker AMX 600™. For the fragment e the signals due to the methine proton occurs at δπ 0.73, the methylene protons next to phosphorus at δπ 1.55 and 1.34, the phosphorus at δ_p at 33.69 and the hydrogen attached to phosphorus at δπ 6.89 and the Jp._H 500 Hz. For the fragment f the signals due to the methylene protons next to phosphorus occur at δπ 1J8 and 0J4, the methylene protons next to silicon occur at δπ 1J8 and 0J4, the phosphorus at δ_p at 37.86 and the hydrogen attached to phosphorus at δu 6.68 and the Jp._H 500 Hz. For the fragment h the phosphorus signal occurs at δ_p 53.05.

The monovalent to octavalent optionally complex metal ion salts of Formula 2A, where A¹ is hydrogen and A is 0 h/t^Ω/ ), are prepared by first reacting the corresponding phosphinic acid derivatives of Formula 2A with dilute base to a pH of approximately 6. A solution containing the desired metal ion and/or complex is then added and the metal derivatives of Formula 2A are subsequently filtered off. A wide range of bases and solvents, well known to those skilled in the art of chemistry, can 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 2 can also be prepared in a range of non-aqueous solvents 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 2A were prepared. Thus an important application of compounds of Formula 2 A is their use as solid immobilisation supports for metal catalysts/complexes. The general procedure used for the production of the organopolysiloxane phosphonic amides of Formula 2B, where A is NR⁴R⁵ and A¹ is NR⁴R⁵ or OR⁸, involves reacting an amine with the phosphoryl acid chloride derivative of Formula 1 described above where both R and R¹ are -π alkyl groups or hydrogen. The preparation of compounds of Formula 1 is described in our earlier patent application PCT/GB 0200069.

An additional method to prepare compounds of Formula 1, where R and R¹ are hydrogen, involves the reaction of mixtures of (RO)3SiCH(CH2PO(OR)(OR¹))CH₂CH₂Si(OR)3,

(RO)₃SiCH₂CH₂PO(OR)(OR¹) and (RO)₃SiCH₂CH₂CH₂PO(OR)(OR¹), where R and R¹ are C_M2 linear or branched alkyls, with concentrated hydrochloric acid. A ten-fold excess by volume or weight of concentrated hydrochloric acid to the organopolysiloxane phosphonate ester is used and the mixture is stirred under reflux for between 1-24 hours. After cooling the organopolysiloxane phosphonic acids of Formula 1 are filtered off and washed with de-ionised water till the washings are pH 7. The solid is washed with ethanol and then ether and dried at between 20°C-100°C under reduced pressure 0.001- 5mm of Hg. This method has the added advantage of producing the organopolysiloxane phosphonic acids of Formula las a fine powder thereby avoiding the need to crush the glass.

Refluxing a mixture of compounds of Formula 1 where R, R¹ = H with an excess of an acid chloride for between l-12h followed by removal of the excess reagent under reduced pressure and then reaction with an amine in a solvent gave the phosphonic amides of Formula 2. The phosphonic amides were filtered off from the reaction mixture, washed with first a small amount of dilute base, water and then with ethanol and finally with ether and dried under reduced pressure, temperatures between 20-100°C and pressures between 0.001-5mm of Hg can be used. A range of acid chlorides, well known to the practitioners of organic chemistry can be used with phosphorous pentachloride preferred. A range of solvents well known to the practitioners of organic chemistry can be used with aromatic and chloro alkanes preferred. Using chiral amines optically active compounds of Formula 2 were prepared which can find application in asymmetric synthesis.

Compounds of Formula 2B where A is NR⁴R⁵ and A¹ is OH were prepared by using 1J-1.5 equivalents of the acid chloride. Compounds of Formula 2B where A is NR⁴R⁵ and A¹ is OR⁸, where R⁸ is Ci_₂o alkyl, were prepared by using 1.5 equivalents of phosphorus pentachloride on the corresponding mono esters of Formula 1. Solid state MAS Cι₃ NMR was used to demonstrate the presence of phosphonic amides in the samples. The solid state cpmas spectrum at 9.4kHz of the product from Example 3 using tris (2-aminoethyl) amine shows peaks at 64.14, 52.28, 38.52, 21.92, 12.37 and 7.02.

Differential Scanning Calorimetry (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 2, 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 2 possess very good thermal stability.

Compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl were found to catalyse a wide range of acid promoted reactions. In addition these compounds of Formula 2A possess good thermal and chemical stability. One of the advantages of these catalysts is that on completion of the reaction they can be simply filtered off and reused, without apparent loss of activity, in the same reaction without need for purification. 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 art of organic chemistry and drying at temperatures ranging from 20°C-120°C under reduced pressure the compounds of Formula 2 can be used to catalyse other reaction types without apparent loss of activity. These catalytic reactions can be conducted with or without solvent. The range of solvents which 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 2A, where A¹ is hydrogen and A is hydroxyl, but is not intended to limit the scope of their capability to catalyse a wide range of reactions.

Compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, 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. An advantage of this procedure is that the catalyst can simply be filtered off and reused without any apparent reduction in activity. The use of protecting groups, particularly for hydroxyl and carbonyl groups, is very important for the preparation of a wide range of complex organic and biological compounds. Compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, readily catalyse a range of these transformations for the protection of the hydroxyl and carbonyl groups. Again the catalyst can simply be filtered off and reused without any apparent reduction in activity.

Utilising known reaction conditions compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, readily catalyse the ketahsation of ketones. 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 2 A where A¹ is hydrogen and A is hydroxyl, gave the desired product 2-methyl - 2-phenyl-lJ-dioxolane in quantitative yield.

Utilising known reaction conditions compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, 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 compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, gave the desired product lJ-dimethoxy-1-phenyl methane in quantitative yield.

An advantage is that for both reactions, ketahsation and acetalisation, the catalyst can simply be filtered off and reused without any apparent reduction in activity. An additional advantage is that phosphinic acids are milder acids compared to the commonly used sulfonic acids for these reactions and are thus less likely to cause any rearrangements in the reactants or products.

The deketalisation and deacetalisation reactions are known to occur in the presence of aqueous acid. Compounds of Fonnula 2A, where A¹ is hydrogen and A is hydroxyl, catalyse these transformations. For example stirring the ketal of acetophenone in the presence of compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, in an aqueous solvent mixture gave acetophenone 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. Compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, readily catalyse the protection of primary and secondary alcohols as tetrahydropyran (THP) derivatives. For example stirring a mixture of 4-methyl benzyl alcohol in the presence of compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, in an anhydrous solvent gave the THP protected product in quantitative yield. A range of solvents can be used well known to those skilled in organic and inorganic chemistry.

Compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, readily catalyse the dehydration of olefins. Standard conditions were used to conduct these reactions. For example heating 1-phenyl- 1-propanol in toluene with catalysts of Formula 2A, where A¹ is hydrogen and A is hydroxyl, at 90°C gave β-methyl styrene. Prolonged heating leads to the production of a polymer, poly-β-methyl styrene.

Acids are widely used to catalyse a wide range of rearrangements and fragmentations. Likewise compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, readily catalyse a wide range of such reactions. For example heating 2,3-dimethyl butan-2, 3-diol at between 130°C to 180°C without solvent in the presence of compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, gave 3,3 -dimethyl 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. Again the catalyst can simply be filtered off and reused without any apparent reduction in activity.

Heating 2, 3-butanedione mono oxime at between 90 -180°C, without solvent, in the presence of compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, gave acetic acid and acetonitrile in high yield. The reaction can also be conducted in a variety of solvents, well known to practitioners in the art of chemistry. Again the catalyst can simply be filtered off and reused without any apparent reduction in activity.

Compounds of Formula 2 can catalyse the esterification of carboxylic acids. For example treatment of oleic acid in refluxing ethanol with compounds of Formula 2, where A¹ is hydrogen and A is hydroxyl, gave the ester ethyl oleate 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. Compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, catalyse the trans-esterification of carboxylate esters. For example treatment of ethyl oleate in pentanol at temperatures between 60- 140°C with compounds of Formula 2 A, where A¹ is hydrogen and A is hydroxyl, gave the ester pentyl oleate 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.

Alkyl glycosides are a particularly important class of compounds because they are based on renewable raw materials and are highly biodegradable. Depending on the substituents they find uses as surfactants, wetting agents and anti foams. Compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, catalyse the glycosylation of glucose with 1-butanol to give varying mixtures, depending on the reaction conditions, of both the butyl pyranoside and furanoside derivatives.

The monovalent to octavalent optionally complex metal ion salts of Formula 2A, where A¹ is hydrogen and A is hydroxyl, are prepared by first reacting the corresponding phosphinic acid derivatives of Formula 2 with dilute base to a pH of approximately 6. A solution containing the desired metal ion and/or complex is then added and the metal derivatives of Formula 2A are subsequently filtered off. A wide range of bases and solvents, well known to those skilled in the art of chemistry, can 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 2A 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 2A, where A¹ is hydrogen and A is 0(M⁺ⁿ/n), were prepared. Thus an important application of compounds of Formula 2A, where A¹ is hydrogen and A is hydroxyl, is their use as solid immobilisation supports for metal catalysts/complexes.

Metal salt/complexes of Formula 2A, where A¹ is hydrogen and A is 0(M⁺ⁿ/n), 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, additions, carboxylations, glycolisations, carbonylations, esterifications, trans-esterifications and rearrangements. These organopolysiloxane phosphonic systems of Formula 2A, where A¹ is hydrogen and A is OζM^/n), 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. In addition these can be filtered off and reused. Thus an important application of the metal derivatives of Formula 2A, where A¹ is hydrogen and A is OOVT^/n), is their use as heterogeneous catalysts.

Cobalt salts of compounds of Formula 2, where A¹ is hydrogen and A is OζM^l ), can be used for allylic and benzylic oxidation. For example, treatment of fluorene with a cobalt salt of Formula 2A, that is A¹ is hydrogen and A is 0(Co⁺²/2), with an alkyl hydroperoxide in solvents such as acetonitrile and benzene gave 9-fluorenone in 70% yield. The catalyst can simply be filtered off and reused without any apparent reduction in activity.

The metal salt complexes M_v(T)_j of the polyamine compounds of Formula 2B have been found to be useful as solid immobilisation supports for metal catalysts and complexes and as heterogeneous catalysts for a wide range of reactions, for example oxidations, reductions, hydrogenations, alkylations, polymerisations, hydroformylations, arylations, acylations, isomerisations, additions, carboxylations, glycolisations, carbonylations, estβrifications, trans-esterifications and rearrangements.

In addition these compounds of Formula 2B, where A is NR⁴R⁵ and A¹ is either NR R⁵ or OR⁸ possess good thermal and chemical stability. One of the advantages of these catalysts is that on completion of the reaction they can be simply filtered off and reused, without apparent loss of activity, in the same reaction without need for purification. 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 art of organic chemistry and drying at temperatures ranging from 20°C-120°C under reduced pressure the compounds of Formula 2B can be used to catalyse other reaction types without apparent loss of activity. These catalytic reactions can be conducted with or without solvent. The range of solvents which 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 2B, where A is NR⁴R⁵ and A¹ is either NR⁴R⁵ or OR⁸, but are not intended to limit the scope of their capability to catalyse a wide range of reactions.

Condensations such as the Aldol and the Knoevenagel reactions are some of the most important C-C bond forming reactions and are widely used in the synthesis of important intermediates or products for pharmaceuticals, perfumes, and polymers. For example treatment of a mixture of benzaldehyde and ethyl cyano acetate with compounds of Formula 2B, where A is NR⁴R⁵ and A¹ is either NR⁴R⁵ or OR⁸, gave ethyl 2-cyano-3-phenyl propenoate in 70% yield.

Metals salts and complexes of Formula 2B, where A is NR⁴R⁵ and A¹ is either NR⁴R⁵ or OR⁸, can also catalyse a wide range of reactions such as oxidations, reductions, hydrogenations, alkylations, polymerisations, hydroformylations, arylations, acylations, isomerisations, additions, carboxylations, glycolisations, carbonylations, esterifications, trans-esterifications and rearrangements. For example the cupric nitrate complex of Formula 2B, where A is NR⁴R⁵ and A¹ is either NR⁴R⁵ or OR⁸, can catalyse the hydrolysis of bis (4-nitrophenoxy) phosphate to the mono phosphate.

An important application of these new products is based on the ability of the polymeric organopolysiloxanes carrying phosphinic and phosphonate amide groups to exchange ions, that is to say, their application as a cation 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 phosphinic and phosphonate amide 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 phosphinic and phosphonate amide groups as cation exchangers.

The new cation exchangers described herein can also be characterized with the aid of elementary analyses and their decomposition point exceeds 400°C. under protective gas atmosphere. The latter is evident from DSC analysis where no thermal events are seen below 400°C. Compounds of Formula 2 act as very effective cation exchangers for a wide range of metals of known oxidations state. These include the lanthanides, actinides, main group and transition metals.

The phosphinic derivatives of Formula 2 are prepared by treatment with dilute base to pH 6. The mono phosphonic amides of Formula 2B, where A is NR⁴R⁵ and A¹ is OH, are prepared by treatment with dilute base to pH 8. 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 hydroxide are the preferred bases for aqueous reactions. Fast and very effective cation exchange or complexation occurs following treatment of these derivatives, including compounds of Formula 2B, where A is NR⁴R⁵ and A¹ is NR⁴R⁵, 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 or complexation.

For example one gram of a sodium salt of Formula 2 A, where A¹ is hydrogen and A is hydroxyl can abstract 0J1 grams of Co⁺² or 0J9 g of Ni⁺²from an aqueous environment. Treatment of this cobalt salt with acid regenerates the material that can be reused without apparent loss of activity. In comparison a commercially available sulphonic acid resin, sold for use as a cation exchange resin, abstracts 0.015 grams of Co⁺² and 0.028 grams of Ni⁺² in a similar experiment.

For example one gram of the lJ-diaminopropyl or the tetraethylene pentamine derivatives of Formula 2B, where A is NR⁴R⁵ and A¹ is either NR⁴R⁵ or OR⁸, can abstract 0.07 grams or 0J3 grams of Co⁺² respectively or 0J9 g or 0J7 grams of Ni⁺² respectively from an aqueous environment. In comparison a commercially available sulphonic acid resin, sold for use as a cation exchange resin, abstracts 0.015 grams of Co⁺² and 0.028 grams of Ni⁺² in a similar experiment.

A major environmental and product quality challenge is the removal of catalysts based on platinum, palladium and rhodium, extensively used for a variety of chemical transformations, from reaction products as well as waste material and washings. Treatment of either an aqueous or alcohol solution of palladium chloride (6 mg in 5 ml of solvent) with the tetraethylene pentamine derivative (80 mg) of Formula 2B, where A is NR⁴R⁵ and A¹ is either NR⁴R⁵ or OR⁸, resulted in complete removal of the palladium chloride from the solution. Similar results were obtained for other polyalkyl amine derivatives of Formula 2B where A is NR⁴R⁵ and A¹ is either NR⁴R⁵ or OR⁸.

Compounds of Formula 2 can also be used to remove excess reagents and side products from organic reactions. Compounds prepared in Examples 1-2 can readily remove all types of basic organic compounds such as amines, hydrazines and heteroaromatic amines. Compounds prepared in Examples 3 to 9 can remove metal ions and complexes, Lewis acid reagents and catalysts such as aluminium chloride, boron trifluoride and tin halides, inorganic and organic acids and acylating reagents.

Further applications of compounds of Formula 2 include the separation of amines, including optically active amines, the immobilisation of biological molecules such as enzymes and use as anti-microbial agents.

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 Hypophosphorous acid (10 g of a 50% w by w solution in water) was concentrated under reduced pressure to remove water (3 g). Vinyl trimethoxy silane (11.2 g, 76 mmol) was added and the mixture was warmed slowly to 120°C with rapid stirring. Once the mixture reached circa 75°C di-tertbutyl peroxide (6 drops) was added and the same quantity was added every 20 min. The methanol was collected in a Dean and Stark apparatus. After 3h at 120°C the reaction mixture started to solidify and after a further 2h the reaction mixture was cooled to room temperature. Water (50 ml) was added and the mixture was stirred under reflux for lh and then cooled to room temperature. The solid was filtered, washed very well with water, ethanol and finally with ether. The white solid was crushed to a very fine powder (8.5 g). Catalyst A

NMR data - Bruker AMX 600™ For the fragment e the signals due to the methine proton occurs at δ_H 0.73, the methylene protons next to phosphorus at δπ 1.55 and 1J4, the phosphorus at δ_p at 33.69 and the hydrogen attached to phosphorus at δπ 6.89 and the 'jp.n 500 Hz. For the fragment f the signals due to the methylene protons next to phosphorus occur at δe 1J8 and 0J4, the methylene protons next to silicon occur at δπ 1J8 and 0J4, the phosphorus at δ_p at 37.86 and the hydrogen attached to phosphorus at δπ 6.68 and the 'jp_-H 500 Hz. For the fragment h the phosphorus signal occurs at δ_p 53.05. The ratio of e:f:h is approximately 5.5:1:0.1

Example 2

Hypophosphorous acid (10 g of a 50% w.w solution in water) was concentrated under reduced pressure to remove water (2 g). Vinyl trimethoxy silane (11.2 g, 76 mmol) was added and the mixture was warmed to 120°C with rapid stirring. Once the mixture reached circa 70°C di-tertbutyl peroxide (6 drops) was added and the same quantity was added every 20 min. The methanol was collected in a Dean and Stark apparatus. After 4h at 120°C the reaction mixture started to solidify and after a further 2h the reaction mixture was cooled to room temperature. Water (50 ml) was added and the mixture was stirred under reflux for lh and then cooled to room temperature. The solid was filtered, washed very well with water, ethanol and finally with ether. The white solid was crushed to a very fine powder (8J g). Catalyst B.

Example 3

Phosphorus pentachloride (2 g) was added to dried phosphonic acid (0.68 g) of Formula 1 where R and R¹ are hydrogen and x:y is 1 : 10 in toluene (20 ml). The mixture was stirred and refluxed under an atmosphere of nitrogen for 12h. After cooling to room temperature the mixture was filtered and the white solid was washed with dry benzene. Tris (2-aminoethyl) amine (0.6 g) and triethyl amine (1 ml) in ether (10 ml) was added dropwise over 15 min to a mixture containing the di chloride in ether (20 ml). The mixture was stirred overnight and then filtered. The solid was washed with dilute sodium hydroxide solution (0JM), water and then with ethanol and dried under reduced pressure at 100°C to give a white solid (0.51 g). C¹³ MAS δ_c 64.14, 52.28, 38.52, 21.92, 12.37 and 7.02.

Example 4

Phosphorus pentachloride (3 g) was added to dried phosphonic acid (1 g) of Formula 1 where R and R¹ are hydrogen and x:y is 1:5 in toluene (40 ml). The mixture was stirred and refluxed under an atmosphere of nitrogen for 12h. After cooling to room temperature the mixture was filtered and the white solid was washed with dry benzene or toluene. Tris (2-aminoethyl) amine (1 g) and triethyl amine (1 ml) in ether (20 ml) was added dropwise over 15 min to a mixture containing the di chloride in ether (30 ml). The mixture was stirred overnight at room temperature and then filtered. The solid was washed with dilute sodium hydroxide solution (0JM), water and then with ethanol and dried under reduced pressure at 100°C to give a white solid (0.87 g).

Example 5

Phosphorus pentachloride (3 g) was added to dried phosphonic acid (1 g) of Formula 1 where R and R¹ are hydrogen and x:y is 1:8 in toluene (40 ml). The mixture was stirred and refluxed under an atmosphere of nitrogen for 12h. After cooling to room temperature the mixture was filtered and the white solid was washed with dry benzene or toluene. Tris (2-aminoethyl) amine (1.6 g) and triethyl amine (1 ml) in ether (20 ml) was added dropwise over 15 min to a mixture containing the di chloride in ether (20 ml). The mixture was stirred overnight at room temperature and then filtered. The solid was washed with dilute sodium hydroxide solution (0JM), water and then with ethanol and dried under reduced pressure at 100°C to give a white solid (0.92 g).

Example 6

Phosphorus pentachloride (3 g) was added to dried phosphonic acid (1 g) of Formula 1 where R and R¹ are hydrogen and x:y is 1:8 in toluene (40 ml). The mixture was stirred and refluxed under an atmosphere of nitrogen for 12h. After cooling to room temperature the mixture was filtered and the white solid was washed with dry benzene or toluene. Triethylene tetramine (1.6 g) and triethyl amine (1 ml) in ether (5 ml) was added dropwise over 15 min to a mixture containing the di chloride in ether (20 ml). The mixture was stirred overnight at room temperature and then filtered. The solid was washed with dilute sodium hydroxide solution (0JM), water and then with ethanol and dried under reduced pressure at 100°C to give a white solid (1.4 g).

Example ?

Phosphorus pentachloride (3 g) was added to dried phosphonic acid (1 g) of Formula 1 where R and R¹ are hydrogen and x:y is 1:8 in toluene (40 ml). The mixture was stirred and refluxed under an atmosphere of nitrogen for 12h. After cooling to room temperature the mixture was filtered and the white solid was washed with dry benzene or toluene. Pentaethylene hexamine (2.0 g) and triethyl amine (1 ml) in ether (5 ml) was added dropwise over 15 min to a mixture containing the di chloride in ether (20 ml). The mixture was stirred overnight at room temperature and then filtered. The solid was washed with dilute sodium hydroxide solution (OJM), water and then with ethanol and dried under reduced pressure at 100°C to give a white solid (1.22 g).

Example 8 Phosphorus pentachloride (3 g) was added to dried phosphonic acid (1 g) of Formula 1 where R and R¹ are hydrogen and x:y is 1:8 in toluene (40 ml). The mixture was stirred and refluxed under an atmosphere of nitrogen for 12h. After cooling to room temperature the mixture was filtered and the white solid was washed with dry benzene or toluene. lJ-Diaminopropane (1J g) and triethyl amine (1 ml) in ether (5 ml) was added dropwise over 15 min to a mixture containing the di chloride in ether (20 ml). The mixture was stirred overnight at room temperature and then filtered. The solid was washed with dilute sodium hydroxide solution (OJM), water and then with ethanol and dried under reduced pressure at 100°C to give a white solid (1.24 g).

Example 9 Phosphorus pentachloride (3 g) was added to dried phosphonic acid (1.0 g) of Formula 1 where R and R¹ are hydrogen and x:y:z is 1:8:1 in toluene (40 ml). The mixture was stirred and refluxed under an atmosphere of nitrogen for 12h. After cooling to room temperature the mixture was filtered and the white solid was washed with dry benzene or toluene. Triethylene tetramine (1.6 g) and triethyl amine (1 ml) in ether (5 ml) was added dropwise over 15 min to this residue in ether (20 ml). The mixture was stirred overnight at room temperature and then filtered. The solid was washed with dilute sodium hydroxide solution (OJM), water and then with ethanol and dried under reduced pressure at 100°C to give a white solid (1.45 g).

Example 10 A solution of cupric nitrate hydrate (1.3 g) in water (30 ml) was stirred with a sample of the phosphonic amide from Example 3 for 12h. The solid was filtered and washed well with water, then ethanol and finally ether to afford a light green blue solid (0J g)

Example 11 A mixture of 2,3-dimethyl 2J-butanediol (4.0 g) and catalyst A (0.05 g) was warmed with stirring to 150°C for 12h under a reflux condenser. The reaction flask was then set for distillation and 3,3 dimethyl 2-butanone (2.9 g) was obtained as a colourless liquid. B.p. 106 °C, Lit. b.p. 106 °C Example 12

A mixture of 2,3-dimethyl 2,3-butanediol (4.0 g) and catalyst B (0.05 g) was warmed with stirring to 150°C for 12h under a reflux condenser. The reaction flask was then set for distillation and 3,3 dimethyl 2-butanone (2.1 g) was obtained as a colourless liquid.

Example 13

A mixture of 2,3-butandione mono oxime (2.0 g) and catalyst A (0.06 g) was heated at 140°C under a reflux condenser for lOh to give acetic acid and acetonitrile in quantitative yield.

Example 14

A mixture of 1-phenyl ethanone (4.8 g, 40 mmol), ethylene glycol (6 ml) and catalyst A or B (0.4 g) in toluene (30 ml) was refluxed under a Dean and Stark condenser for 4h. The reaction mixture was cooled, filtered and washed with water (3 x 50 ml) and then dried over magnesium sulphate. On concentration 1 -methyl- 1-phenyl 1,3 dioxolane was obtained as a solid (6.0 g) in 93% yield.

Example 15

A mixture of 1-phenyl- 1-propanol (0J6 g, 1.17mmol) and catalyst A or B (30 mg) in toluene (1 ml) was stirred and heated at 75°C for lOh under nitrogen. Ether (20 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 (0J3 g, 92%). δπ (CDC1₃, 270 MHz) 7.4-7.1 (5H, m), 6.4 (1H, d, J 12Hz), 6.25 (1H, dq, J, 12Hz, J₂ 6Hz) and 1.87 (3H, d, J6Hz).

Example 16

A mixture of 1-phenyl- 1-propanol (0J6 g, lJ7mmol) and catalyst A or B (30 mg) in toluene (1 ml) was stirred and heated under reflux for 40h under nitrogen to give poly (β-methylstyrene).

Example 17

A mixture containing catalyst A (0.05 g), oleic acid (2.8 g, 10 mmol) and ethanol (15 ml) was refluxed with stirring for 40h. On cooling ether (40 ml) was added and the catalyst was filtered off. The organic washings were concentrated to give ethyl oleate as an oil (2.01 g, 65% yield). δ_H (CDC1₃, 270 MHz) 5.33 (2H, m, olefin hydrogens), 4.11 (2H, q, J8Hz, OCH_?). 2.29 (2H, t, J9Hz, CH₂CO) Example 18

A mixture of acetophenone ketal (1.64 g, 10 mmol) and catalyst A (0.07 g) was stirred in acetonitrile: water (1:1, 16 ml) at 80°C for 2h. On cooling to room temperature, the catalyst was filtered and washed with ethyl acetate (50 ml). The combined organic washings were washed with water, dried over magnesium sulphate, concentrated to give 1-phenyl ethanone as an oil (1.11 g, 92%). δ_H (CDC1₃, 270 MHz) 2.58 (3H, COCH₃, s)

Example 19

A mixture of 4-methylbenzyl alcohol (0.49g, 4 mmol), dihydropyran (4 fold molar excess) and catalyst (50 mg) was stirred in dry ether (15 ml) for 12h. The reaction was followed by TLC - 95 pet. ether- 5% ethyl acetate and on completion the catalyst was filtered off and washed with dry ether (20 ml). The organic layer was concentrate under reduced pressure to give the THP derivative as an oil (0.8 g)

Example 20 A mixture of the THP derivative (0.8 g) from Example 19 dissolved in aqueous methanol (1:2-15 ml) and catalyst (50 mg) was stirred for 12h. The catalyst was filtered off and washed with ethyl acetate

(25ml). The combined organic solutions were concentrated under reduced pressure. The residue was dissolved in ethyl acetate (60ml) washed with water (20 ml), dried over magnesium sulphate, filtered, and then concentrated under reduced pressure to give 4-methyl benzyl alcohol in quantitative yield.

Example 21

A mixture of glucose (1.0 g), butanol (10 ml) and catalyst A (0J g) was stirred under reflux for 30h.

The catalyst was filtered off and washed with methanol (30 ml). The combined organic solutions were concentrated under reduced pressure to afford a mixture of and β butyl glucopyranoside and glucofuranoside (0.9 lg). Example 22

An organopolysiloxane phosphinic acid - catalyst A - (1.0 g) was suspended in de-ionised water (50 ml) and the pH of the mixture was adjusted to pH 6 with dilute sodium hydroxide. A clear solution was obtained and the solution was made up to 70 ml with distilled and de-ionised water. To a sample of this solution (35 ml) was added cobalt nitrate hexahydrate (0.4 g) dissolved in de-ionised water (8 ml). The mixture was stirred overnight at room temperature and then concentrated under reduced pressure. Water (30 ml) was added and the mixture again concentrated under reduced pressure. This was repeated three times. Water (50 ml) was then added to the residue and stirred for 3h. The solid was filtered off to give the cobalt derivative of a organopolysiloxane phosphinic acid as a blue-purple solid (0.5 g). The above was repeated using cobalt acetate tetrahydrate in place of cobalt nitrate and afforded a blue solid (0.48g). Example 23 To a mixture under nitrogen containing fluorene (0J3 g, 2 mmol) and the cobalt catalyst from Example 22 (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 24h. 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 ether-pet. ether to give 9-fluorenone in 70% yield.

Example 24 A mixture of benzaldehyde (2J2 g, 20 mmol), ethyl cyano acetate (2.26 g, 20 mmol) and catalyst from Example 3 (50 mg) in toluene 920 ml) was heated at reflux under a Dean and Stark apparatus for 12h. The catalyst was filtered and the filtrate was concentrated under reduced pressure. The mixture was eluted from a flash silica gel column with ethyl acetate-pet. ether (1:8) to give ethyl 2- cyano-3-phenyl propenoate in 69% yield. Using a sample of the catalyst from Example 5 (50 mg) and identical reaction conditions afforded ethyl 2-cyano-3-phenyl propenoate in 63% yield.

Example 25 An organopolysiloxane phosphonic acid - Catalyst A or B - (0.8 g) was suspended in de-ionised water (20 ml) and the pH of the mixture was adjusted to pH 6 with dilute sodium hydroxide. A clear solution was obtained and the solution was made up to 80ml with distilled and de-ionised water. To a sample of this solution (2 ml) was added de-ionised water (2 ml) and a known concentration of a solution (2 ml) of a metal salt. The resultant mixtures were centrifuged to remove the precipitate and known spectroscopic and/or analytical methods were used to analyse the concentration of the metal remaining in the solution.

A sample of cobalt nitrate hexahydrate (0.31 M, 2 ml) or nickel chloride hexahydrate (0.4964 M, 2 ml) was added to a sample of the organopolysiloxane phosphinic acid solution (2 ml), above, and de- ionised water (2 ml). The resultant mixtures were centrifuged to remove the precipitate and UV spectra were run on the remaining liquids. Comparison of the intensity of the peaks with known standard solutions of cobalt nitrate hexahydrate and nickel chloride hexahydrate indicated that 1.0 g of this organopolysiloxane phosphinic acid can abstract 0J 1 grams of Co⁺² or 0J9 g of Ni⁺² metals.

Example 26

To a known weight (0.04 g) of compounds of Formula 2B, where A is NR⁴R⁵ and A¹ is either NR⁴R⁵ or OR⁸, is added de-ionised water (4 ml) and a known concentration of a solution (2 ml) of a metal salt. After standing for 12h the resultant mixtures were centrifuged to remove the solid and known specttoscopic and/or analytical methods were used to analyse the concentration of the metal remaining in the solution. A sample of cobalt nitrate hexahydrate (0J 1 M, 2 ml) or nickel chloride hexahydrate (0.4964 M, 2 ml) was added to a sample of the lJ-diaminopropyl (0.04 g) or the tetraethylene pentamine (0.04 g) derivatives of Formula 2, where A is NR⁴R⁵ and A¹ is either NR⁴R⁵ or OR⁸, and de-ionised water (4 ml). After standing for 12h the resultant mixtures were centrifuged to remove the solid and UV spectra were run on the remaining liquids. Comparison of the intensity of the peaks with known standard solutions of cobalt nitrate hexahydrate and nickel chloride hexahydrate indicated that 1.0 g of these organopolysiloxane phosphonic amides can abstract 0.07 grams or 0J3 grams of Co⁺² metal respectively or 0J9 g or 0J7 grams of Ni⁺² metal respectively from an aqueous environment.

Example 27

A solution of palladium chloride (6 mg) in ethanol (5 ml) was added to a sample (80 mg) of the product from Example 3. After standing for 12h the resultant mixture was centrifuged to remove the solid and the remaining colourless liquid was treated with excess dimethyl glyoxime. No colour change or precipitate was observed indicating removal of the palladium cation from solution.

Example 28

The product from Example 1 (2.5 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.

Claims

CLAIMS 1. A compound of General Formula 2:

wherein the free valences of the silicate oxygen atoms are saturated by one or more of: silicon atoms of other groups of Formula 2, hydrogen, or by cross-linking bridge members or polymer chains R³ _<,M¹(OR )_mO_{k 2} or Al(OR²)₃-pO_p/₂ or R³Al(OR²)₂._rO_{r 2}; where M¹ is Si or Ti; R² is a linear or branched Cι_ι₂ alkyl group; and R³ is a linear or branched C₁.₄0 alkyl group, C₂.₄o alkenyl or C₂.₄o alkynyl group, an aryl or Cι- o alkylaryl group, or substituted linear or branched Cι.₄o alkyl group, C_2-4o alkenyl or C_2-4o alkynyl group, an aryl or Cι_-4o alkylaryl group with one or more halogens, amines and alkyl amines, hydroxyl groups, sulfide and sulfonic acids, nitriles, alkyl and aryl phosphines, carboxylate acids and esters; k is an integer from 1 to 4 and q and m are integers from 0 to 2; such that m + k + q = 4; and p is an integer from 1 to 3; and r is an integer from 1 to 2; or other known oxo metal bridging systems; and wherein either:

A. A¹ is hydrogen; g is equal to zero; and A is a hydroxyl group or 0(Mⁿ⁺/n); M is an optionally complex metal ion; and n is an integer from 1 to 8;

e, f, and h are integers such that the ratio of e : f+h, varies from 0.00001 to 100,000 with the fragments [θ3/₂SiCH(CH₂PO(A)(A¹))CH₂CH₂Siθ3/₂]_e and [0_3/2SiCH₂CH₂PO(A)(AJ]_f always present whilst the integer h varies from 0 to 200f; or

B. A is NR⁴R⁵

R⁴ and R⁵ are each independently hydrogen, a linear or branched Cι_-4o alkyl, C₂.₄o alkenyl or C2-40 alkynyl group, an aryl or Cι.₄₀ alkylaryl group, or ((CH₂)_sNR⁶)_t(CH₂)_sNHR⁷; where R⁶ is hydrogen, a linear or branched Cι.₄₀ alkyl or ((CH₂)_SNR⁶)_W(CH₂)_SNHR⁷; each s, t and w is independently an integer from 1 to 12, and R⁷ is hydrogen or a linear or branched Cι_₄o alkyl;

A¹ is NR⁴R⁵ or OR⁸;

R⁴ and R⁵ are as defined above; R⁸ is hydrogen, a linear or branched Cι.₄₀ alkyl, C₂.₄o alkenyl or C_2-4o alkynyl group, an aryl or C]. o alkylaryl group or an optionally complex metal ion Mⁿ⁺/n and n is an integer from 1 to 8;

h is equal to zero; and

e, f and g are integers such that the ratio of e : f+g, varies from 0.00001 to 100,000 with the fragments [0₃2SiCH(CH2P(0)AA¹)CH2CH₂Siθ3/2]e and [O3/2

always present whilst the integer g varies from 0 to 200f. or a metal complex M_v (T)_j of a polyamine compound as defined in B above, where Mⁿ⁺ are ions derived from lanthanide, actinide, main group or transition metals and T is a counter ion and v and j are integers which balance the overall charge.

2. A compound as claimed in claim 1 which includes a cross linking bridge member and wherein the ratio of cross linker to e+f+g+h varies from 0 to 99:1.

3 A compound as claimed claim 1 or claim 2 that includes a cross linking bridge member or polymer chain derived from an orthosilicate, a titanium alkoxide or a aluminium trialkoxide.

4. A compound as claimed in claim 3 wherein the cross linking bridge or polymer chain is Si0_4/2 or R³Si0₃.₂ or (R³)₂Si0_{2 2} or Ti0₄₂ or R³Ti0_{3 2} or (R³ )₂Ti0₂₂ or A10_{3 2} or R³A10_2/2, wherein R³ is as defined in claim 1.

5. A compound as claimed in claim 4 wherein R³ is C e alkyl, C_2-6 alkenyl, or aryl.

6. A compound as claimed in any one of claims 1 to 5 wherein when A¹ is hydrogen, A is a hydroxyl group or 0(Mⁿ⁺/n), M is an optionally complex metal ion derived from a lanthanide, actinide, main group or transition metal, n is an integer from 1 to 8 and g is equal to zero.

7. A compound as claimed in any one of claims 1 to 5 wherein: A is NR⁴R⁵

R⁴ and R⁵ are each independently hydrogen, a linear or branched Cι_ι₂ alkyl, C_2-4o alkenyl or C_2-4o alkynyl group, an aryl or Cι_₄o alkylaryl or ((CH₂)_sNR⁶)_t(CH₂)_sNHR⁷; R⁶ is hydrogen, a linear or branched Cι_₄o alkyl or ((CH₂)_sNR⁶)_w(CH₂)sNHR⁷; each s, t and w is independently an integer from 1 to 12, and R⁷ is hydrogen or a linear or branched Cι.₄₀ alkyl;

A¹ is NR⁴R⁵ or OR⁸

R⁴ and R⁵ are as defined above; R⁸ is hydrogen, a linear or branched Cι_-4o alkyl, C_{2 0} alkenyl or C_{2 0} alkynyl group, an aryl or Cι_₄o alkylaryl group or an optionally complex metal ion Mⁿ⁺/n, and n is an integer from 1 to 8;

h is equal to zero; and

e, f and g are integers such that the ratio of e : f+g, varies from 0.00001 to 100,000 with the fragments [0₃/2SiCH(CH2P(0)AA¹)CH2CH₂Siθ3/2]e and [0_3/2 SiCH₂CH₂P(0)AA¹]_f always present whilst the integer g varies from 0 to 200f.

8. A compound as claimed in claim 6 wherein: R⁴ and R⁵ are each independently hydrogen, a linear or branched Cι_-i2 alkyl, C₂.ιo alkenyl or C_2-ιo alkynyl group, an aryl or Cι.ι₂ alkylaryl or ((CH₂)_sNR⁶)_t(CH2)_NHR⁷ where R⁶ is hydrogen, a linear or branched C_]-I2 alkyl or ((CH₂)sNR⁶)_w(CH₂)sNHR⁷; each s, t and w is independently an integer from 1 to 6; and R⁷ is hydrogen or a linear or branched Cι.ι₂ alkyl; R⁸ is hydrogen, a linear or branched Cι_-I2 alkyl, or an optionally complex metal ion Mⁿ⁺/n derived from a lanthanide, actinide, main group or transition metal, and n is an integer from 1 to 8.

5 9. A compound as claimed in claim 7 or claim 8 wherein: R⁴ and R⁵ are each independently hydrogen, a linear or branched Cμ alkyl or ((CH₂)sNR⁶)t(CH₂)_sNHR⁷; R⁶ is hydrogen, a linear or branched C_1-4 alkyl or ((CH )_SNR⁶)_W(CH₂)_SNHR⁷; each s, t and w is independently an integer from 1 to 6; and R⁷ is hydrogen or a linear or branched Cμ alkyl; R⁸ is hydrogen, a linear or branched Cι_₄ alkyl, or an optionally 10 complex metal ion Mⁿ⁺/n derived from a lanthanide, actinide, main group or transition metal, and n is an integer from 1 to 8.

10. A compound as claimed in any one of claims 7 to 9 which is complexed to metal salts M_v(T)_j wherein M is a metal ion derived from a lanthanide, actinide, main group or transition metal, T is a

15 mono, di or tri anion and v and j are integers to balance the overall charge.

11. A process for the preparation of a compound of Formula 2 as defined in claim 1, the process comprising: a. for a compound of Formula 2 in which A is hydroxyl and A¹ is hydrogen and g is 20 zero, the free radical addition of hypophosphorous acid to trialkoxy vinyl silane in the presence of a free radical initiator and under an atmosphere of nitrogen; b. for a compound of Formula 2 in which A is 0(M⁺7n) and A¹ is hydrogen and g is zero, reacting a compound of Formula 2 in which A is hydroxyl and A¹ is hydrogen with base and then adding a solution containing the desired metal ion and/or complex;

25 c. for a compound of Formula 2 in which A is NR⁴R⁵and A¹ is NR⁴R⁵ or OR⁸ and h is zero and where R⁴, R⁵, R⁶, R⁷and R⁸ are as defined in claim 1 by treating a compound of Formula 2 in which both A and A¹ are hydroxyl and h is zero with an acid chloride, filtering and then reacting with the required amine.

30 12. A process for the preparation of a compound of Formula 1, which is a variant of Formula 2 in which both A and A¹ are hydroxyl and h is zero, the process comprising reacting mixtures of (RO)₃SiCH(CH₂PO(OR)(OR¹))CH₂CH₂Si(OR)₃, (RO)₃SiCH₂CH₂PO(OR)(OR¹) and (RO)₃SiCH₂CH₂CH₂PO(OR)(OR¹), where R and R¹ are C ₂ linear or branched alkyls, with concentrated hydrochloric acid.

13 A process as claimed in claim 11 wherein in step (a) a precursor to a cross linking bridge member is combined with the trialkoxy vinyl silane and hypophosphorous acid.

14 A process as claimed in claim 13 wherein the cross-linking bridge member or polymer chain is Si0_4/2 or R³ Si0₃/2 or (R³)₂Si0₂/₂ or Ti0₄₂ or R³Ti0₃/₂ or (R³ )₂Ti0₂/₂ or A10₃/₂ or R³A10_{2 2}, where R³ is as defined in claim 1.

15. A process for conducting an acid catalysed reaction, the process comprising employing as a catalyst a compound as claimed in claim 6.

16. A process for conducting a base catalysed reaction, the process comprising employing as a catalyst a compound as claimed in claim 7 to 10.

17. The use of a compound as claimed in claim 6 as an acid catalyst.

18. The use of a compound as claimed in claim 7 to 10 as a base catalyst.

19. The use of a compound as claimed in any one of claims 6 to 10 as a heterogeneous catalyst for oxidations, reductions, alkylations, polymerisations, hydroformylations, arylations, acylations, isomerisations, additions, carboxylations, glycolisations, carbonylations, esterifications, trans- esterifications and rearrangements.

20. The use of a compound as claimed in any one of claims 6 to 10 as a cation exchanger.

21. The use of a compound as claimed in any one of claims 6 to 10 in the separation of amines, including optically active amines, and the immobilisation of biological molecules such as enzymes.

22.The use of a compound as claimed in any one of claims 1 to 9 as a scavenger for the removal of unwanted organic or inorganic compounds from reaction mixtures.