It is known that compounds having phosphoryl choline groups and other zwitterionic groups, have useful biocompatibilising properties. Coatings of polymers with pendant phosphoryl choline groups have been shown to be useful as coatings to render blood contacting devices non-thrombogenic. Contact lenses formed from hydrogel polymers with pendant PC groups are less subject to protein deposition, lipid deposition and bacterial adhesion than contact lenses having similar water contents.

We have also described a variety ofreagents which are useful for derivatising pre- formed surfaces, for instance of polymeric substrates, to introduce PC groups. Such reagents are generally mono functional, that is each reagent molecule includes a single PC group and a single reactive group. Examples of some such reagents are described in EP-A-0157469, EP-A-0515895 and EP-A-0556216 (WO-A-9207858). In EP-A- 0515895 reagents which are capable of reacting with amino groups at surfaces to give amine linkages are described. In EP-A-0556216 compounds which react with surface amino, hydroxyl and carboxylic groups include activated amine groups.

In WO-A-9301221 we described copolymers of ethylenically unsaturated PC group containing monomers and copolymerisable comonomers selected so as to give suitable surface binding characteristics. One class of comonomers includes a reactive group by which covalent bonding to an underlying surface may be carried out. Examples of covalent reactive groups include an aldehyde group.

Several techniques have been described for synthesising phosphoryl choline derivatives and analogues thereof. The route we have used involves the reaction of an alcohol with 2-chioro-2-oxo-1,3,2-dioxaphospholane (CCP) followed by a ring opening amination of the phospholane. The ring opening amination was originally described by Nguyen Thuong and P. Chabrier in the early-mid 1970's, inter alia, FR-A-2270887.

Those two authors in C.R. Acad. Sci. Paris (1972) 275, C1125-1127 describe the reaction of CCP with various primary and secondary aliphatic and aromatic alcohol compounds including cyclohexanol and derivatives and cyclohexenol derivatives. The

cyclic phospholane product is reacted with sodium cyanate to form the disodium salt of the monoester (or amidite).

Sarma, R., Ramirez, F., et al in J.Am. Chem. Soc. (1978)100:14, 4453-4458 describe the synthesis of cyclopentyl phosphoryl-choline by PC-ylation of cyclopentanol using a multi-step synthetic route. In a first step the cyclopentanol is reacted with 1,2- dimethyl-ethylenylenepho sphorochloridate. The intermediate is then reacted with choline chloride, to form a phosphate triester and finally the ester linkage joining the 1-acetoethyl group hydrolysed to form the product.

It has been reported that PC may have significant benefits in extending the life and reducing calcification of tissue valves, although the means by which PC had been incorporated into such heart valve was not disclosed.

Monomers for use in forming condensation polymers, such as polyesters and polyurethanes have been described. For instance in EP-A-0 199790 and EP-A-0275293, monomers comprising two hydroxyl groups are used to react with di-isocyanates and dicarboxylic acids respectively to form polyurethanes and polyesters.

Biological tissues can be "fixed" by allowing them to soak for some minutes in a dilute solution of a dialdehyde, usually glutaraldehyde. The glutaraldehyde is used to cross link proteins by their amine groups. Other dialdehydes having even numbers of carbon atoms between the CHO groups have been disclosed in US-A-5429797. Lysine residues in the proteins are the most common source of these amine groups. The aldehyde and amine undergo a condensation reaction to form an imine with the subsequent loss of water. Further details of the reactions taking place are described by Cheung, D.T., et al in Connective Tissue Res. (1982) 10, 187-199.

The major constituent of bioprosthetic implants is the protein collagen. To increase the stability of such implants against biodegradation and to reduce the antigenicity, collagen is cross-linked with glutaraldehyde. The problem is that, after implantation, calcification onto the implant gradually occurs, rendering it necessary to replace the implant.

The present inventors have established that a PC derivative having two aldehyde groups or precursors to aldehyde groups, such as gem diols, hemiacetals and acetals, is useful to replace glutaraldehyde in tissue fixing. The present invention provides an intermediate used in the synthesis of such a compound. The intermediate has other uses

as a reagent for producing other difunctional PC derivatives and as a radical polymerisable compound. The invention also provides a process for producing the novel compound.

In a new process according to the invention a cyclic phosphate triester compound of the Formula I in which either a) R1 is CR212 in which each R'2 is independently selected from hydrogen and a C1-4-alkyl groups, and R2 is CR3=CR122, in which each Rl2 is as defined above; or b) R' and R2 together are CR3; each R3 is independently selected from hydrogen and C1-6-alkyl groups; and in which R4 and R5 are each selected from a bond and a group (CR62)n, provided that at least one of the groups R4 or R5 is other than a bond where Rl and R2 together are CR3, each group R6 is independently selected from hydrogen hydroxyl, protected hydroxyl, C1-4-alkyl groups C1.4 hydroxyalkyl, or C1.4 protected hydroxyalkyl or a group of formula III or C1.4 alkyl substituted by a group of formula III or two groups R6 may together form a group selected from

C1-5 alkylene and C2.5 alkylidene groups in which the alkylene or alkylidene groups may be substituted by a hydroxy or a protected hydroxyl group or a group of formula III, R7 is selected from hydrogen and C1.4 alkyl groups; R8 is a bond or a C1-4 alkylene; R9 is a bond or a group C(R10)R11; each group R° is selected from hydrogen and C1-4 alkyl groups; each group R11 is selected from hydrogen and C1.4 alkyl groups or two groups R11 may form a C1-5 alkylene group; and nis 1-4; is reacted in an aprotic polar solvent with an amine of the formula II NR213R14(II) in which each Rl3 is H or Me, and Rl4 is selected from H and C1-24 alkyl, C1-24 hydroxyalkyl, C4.24-cycloalkyl, C7.24 aralkyl, C6.24 aryl (including alkaryl) to produce a compound of the Formula IV in which the groups Rl, R2, R3 and R8 are the same as in the compound of formula I; R4, R5' and R6' are the same as groups R4, R5 and R6, respectively, of the compound of the formula I or, where a group R6 included a group of formula III that group R6' is the same as the respective group R6 except that the group of formula III is replaced by a group of formula V

R9 to R11 are the same as in the compound of the formula I; and Rl3 and Rl4 are the same as in the amine compound of the formula II.

Although the ring opening amination reaction of 1,3,2-dioxaphospholanes by trialkylamines is known, it is believed to be novel to carry out the reaction on an unsaturated phosphate triester of the general formula I.

In the process of the invention the dioxaphospho ring of the compound of the formula I is preferably attached through a phosphate ester bound to the residue of a secondary alcohol, that is R8 is preferably a bond.

The process is of particular value for producing intermediates in which the ethylenically unsaturated bond(s) of the ammonium phosphate ester compound of the formula IV are further derivatised, for instance by oxidation to form a carbonyl- containing groups C(O)R3 Preferably such compounds are aldehydes, and hence the groups R3 are preferably hydrogen. In one embodiment the dioxaphospholane compound of the formula I is preferably symmetrical. Preferably therefore R4 is R5CR62 and both R5,s are the same. Preferably each R5 is a bond or CR62, that is a group (CR62)n in which n is 1 and the groups CR62 are the same. Where R4 and RS are other than a bond and/or where n is 2 or more, the dialdehyde end product formed from the product ofthe process of the present invention may be susceptible to an internal aldol condensation reaction, which is undesirable. For such compounds it is desirable for one group R6 attached to each of the carbon atoms joined to the group Rl and R2 together to represent a methylene group.

In another preferred embodiment the alcohol residue is cyclic, that is R' and R2 together are CR3 The compound of the formula I can be represented as the general formula VI Preferably the compound is achiral, that is R4 is R5CR62 and both groups R5 are identical and both groups CR62 are identical.

In another preferred embodiment the alcohol residue is a cyclic, that is the compound of the formula I is an alkadiene compound. Such compounds can be represented by the general formula VII Preferably the compound is achiral. Preferably R4 is R5CR62 and both groups R5 are the same. Preferably the two groups Cur122 are the same. More preferably each Rl2 is methyl or, most preferably, hydrogen.

R7 is preferably a methyl group or, more preferably hydrogen.

The process of the present invention may be of value for producing products having more than one group of formula V, but is of most use where the product has only one such group. Accordingly it is preferred that no group R6 contains a group of formula III. It is also preferred that R6 not include a hydroxyl or protected hydroxyl group. Each R6 is thus preferably C, 4-alkyl, for instance methyl, or more preferably, hydrogen, or alternatively that two groups R6 together form a C15 alkylene group, preferably whereby the two groups R6 and the carbon atoms to which they are attached and any carbon atom to which those carbon atoms are in turn both attached (i.e. where the two groups R6 are attached to next adjacent carbon atoms) form a 5- or 6- membered ring. Such compounds, also where R1 and R2 together are CR3, are polycycloalkyl compounds.

In the groups of the formula III and V it is preferred that the ring be a five membered ring, since the ring opening step proceeds relatively slowly for 6-membered rings. R9 is thus preferably a bond. Although the process may be of interest where two

groups R11 together represent an alkylene group, preferably each group R'l is selected from hydrogen and C1.4 alkyl, more preferable methyl, most preferably hydrogen.

A preferred embodiment of process includes a first step for producing a compound of the formula I, in which an alcohol of the general formula VIII in which Rl to R3, R7 and R8 are the same as in the compound of the formula I and R4" to R6" are the same as the groups R4 to R6, respectively, of the compound of the formula I, provided that where any groups R6 comprises a group of formula III, the corresponding group R6 comprises a hydroxyl group in place ofthe group offormula III, is reacted with a halophospholane of the general formula IX in which R9 to R" are the same as the groups R9 to R11 of the compound ofthe formula I; and Hal is a halogen atom.

Hal is preferably chlorine, but may alternatively represent bromine or iodine.

The product of the process of the first aspect of the invention is believed to be novel and compounds of the general formula IV forms a further (second) aspect of the invention.

Some of the compounds of the general formula I are also believed to be novel compounds and form the third aspect of the present invention.

According to the third aspect of the present invention there is provided a novel compound of the general formula X in which either a) R21 is CR242 in which each R24 is independently selected from hydrogen and C1-4 alkyl groups; and R22 is CR23 = CR242 in which each R24 is as defined above; or b) R21 and R22 together are CR23; and in which each R23 is independently selected from hydrogen and C, 6 alkyl groups; each group R26 is independently selected from hydrogen, hydroxyl, protected hydroxy, C1-4 alkyl, C1-4 ihydroxy alkyl or C1-4 protected hydroxyalkyl, a group of formual III or a C1.4 alkyl substituted by a group of formula III; and R7 to Rll are as defined in relation to the compound ofthe formula I.

Preferably the groups R23 are hydrogen.

Preferably both groups CR262 are identical. Preferably in each group CR262 the groups R26 are identical. More preferably all groups R26 are hydrogen. In another embodiment two groups R26 together are C1.5 alkylene, preferably whereby a 5 or 6 membered ring is formed with the carbon atoms to which they are attached and with the carbon atom to which those two carbon atoms are in turn attached (ie where the two R26 groups forming the alkylene are attached to different carbon atoms).

Preferred groups R24 are methyl, or more preferably hydrogen. Preferably in a compound having two groups CR242, the groups CR242 are identical.

One embodiment of this aspect of the invention is a cyclopentene compound of the general formula XI Another embodiment is a 1,6-heptadiene compound of the general formula MI In this third aspect of the invention the same preferences for the definitions of groups R7 to R11 apply as have been mentioned above in relation to the first aspect ofthe invention.

Alternatively the compounds of the Formula IV may be used as monomers in polymerisation, either alone, or, preferably, along with copolymerisable unsaturated comonomers. The comonomer may be an ethylenically unsaturated comonomer for instance any ofthose mentioned in our publicationWO-A-9301221, especially the acrylic comonomers. Cycloalkene compounds of the formula VI may alternatively be polymerised by ring opening metathesis polymerisation usually with cyclic alkene comonomers, which may be cyclopentene, cyclohexene or norbornene derivatives. Such polymerisations are described in J. Molecular Catalysis A. Chemical, 115(1997) 85-94.

The suitability of such comonomers or copolymerisation with the compound of the formula IV may be established by a person skilled in the art based upon the reactivity ratios of the respective compounds.

The reaction ofthe alcohol compound ofthe Formula VIII with the phospholane compound of the Formula IX must be carried out under anhydrous conditions, in a suitable solvent. Suitable solvents are benzene and ethers or nitriles. It is preferred for the phospholane reagent ofthe Formula II to be extremely pure. Purity can be accessed using the 31P-NMR as described in our earlier publication WO-A-9514702.

The ring opening reaction ofthe compound ofthe formula I with the amine ofthe formula II is preferably carried out under anhydrous conditions, to avoid production of hydrolytically ring opened by-product. The solvent may be selected from the same solvents as that used for the first step. For a two step process, preferably the solvents used in the two steps are the same and the compound ofthe formula I is not isolated from the solvent used for the first step before the step of reacting with the amine is carried out.

The solvent is preferably a nitrile, most preferably acetonitrile.

The reaction ofthe alcohol compounds VII with the phospholane IX is preferably carried out in the presence of a tertiary amine base to assist removal of hydrogen halide co-product from the reaction mixture as a precipitate. Suitably the tertiary amine is triethylamine.

The compound of the Formula IV may be recovered from the product mixture by removal of the solvents and may be purified by known techniques.

The alcohols ofthe formula VIII are generally known compounds. The two step process ofthe present invention may consequently use as starting materials commercially available alcohols of the formula VIII. Where the alcohol is not readily available it may be synthesised in one or more preliminary steps. The process ofthe present may include such preliminary steps.

In one embodiment of a multistep process for producing a cyclopentenol compound having the general formula VIII in which Rl and R2 together are CR3, and R5" is a bond, R4" is (CR6 2)n and n is 1 and R8 is a bond, preliminary steps involve reaction of cyclopentadiene to form an epoxy group across one of the C=C bonds and reducing the epoxy group to form the corresponding mono-ol.

In another embodiment of a multistep process for producing a 1,6-hexadiene compound having the general formula VIII in which R1 is CH2 and R2 is CH=CH2, R5 is a bond, R8 is a bond and n is 1, a Grignard reagent is formed by reacting magnesium with

allyl bromide and is reacted with an ester R7COOR15 where Rl5 is C1-6 alkyl, preferably ethyl, in the following reaction scheme.

The invention is illustrated in the following examples: Example 1 - Synthesis of 3-Cyclopenten-1-oxyethyl-2'- (trimethylammonium ethyl) phosphate The steps prior to step 1.3 are described by Crandal, JK et al in J. Org. Chem.

(1968) 33, 423.

1.1-1.2: Synthesis of 3-Cyclopenten-1-ol 1.1 To a stirred solution ofcyclopentadiene (57.8g, 0.87mole), and sodium carbonate (400g) in dichloromethane (1000ml) at 0°C, peracetic acid (168ml, 40% in acetic acid), pre-treated with sodium acetate (0.2g) was added slowly, and the reaction allowed to stir for 4 h. The reaction mixture was filtered, and the solvent distilled off.

[1H NMR (199.5MHz, CDCl3) 2.0-3.0(m, CH-O-CH), 3.8(d, CH2), 6.1(m, CH=CH)] 1.2 The residue was slowly added to a slurry of lithium aluminium hydride (13 .0g, 0.36mole) in diethyl ether (400ml) at 0°C, and stirred overnight. The reaction was quenched by slow addition of water (50ml), and then after 10 min dried magnesium sulphate was added (50-70g). The solids were filtered off, and then washed with diethyl ether (2x200ml). The organic layers were combined, and the solvent was removed carefully in vacuo (no heating). 3-Cyclopenten-1-ol (20.38g, 0.243mole) was isolated from the mixture by distillation (27°C, ca 754 mmHg).

1H NMR 199.5MHz, CDCl3) 1.9(1H, br.s, OH), 2.2-2.8(4H, qd, CH2CHCH2), 4.5(1H, br.m, CHOH), 5.7(2H, s, CH=CH).

13C NMR (50.1MHz, CDCl3) 42.0 (CH2), 10.8 (CHOH), 122.4 (C=C).

1.3: Synthesis of 3-Cyclopenten-1-oxyethyl-2'-(trimethylammonium ethyl) phosphate To a solution of 3-cyclopenten-1-ol (8.04g, 0.091mole) made as in 1.1-1.2, and N,N,N,N-tetramethyl ethylene diamine (6.33g, 0.055mole) in acetonitrile (160mol) at - 10°C, a solution of 2-chloro-2-oxo-1,3,2-dioxaphospholane (15.6g, 0.073mole) in acetonitrile (50ml) was added, and the reaction allowed to warm to RT over 1.5 h. The reaction mixture was filtered, and then trimethylamine (12.68g, 0.2lmole) was added.

The reaction was heated at 50°C in a closed system for 18 h. The reaction was cooled, and solvents removed in vacuo. The reaction mixture was taken up into water, and washed with chloroform (2x1 00ml). The aqueous layer was concentrated to yield 3- cyclopenten- 1 -oxyethyl-2' -(trimethylammonium ethyl) phosphate (15.3 g, 0.061 mole) as an oil.

1H NMR (199.5MHz, D2O) 2.1-2.4(4H, m, 2x-CH2-), 3.0(9H, s, NMe3), 3.3-4.1(5H, m, CHOP, OCH2CH2N), 5.5(2H, s, CH=CH).

13C NMR (50.1MHz, D2O) 39.5(CH2), 53(ref NMe3), 58.5&60.0, 65.0&66.5(OCH2CH2N), 75.5(CHOP), 127.2(C=C). m/s (FAB+) 336(M+#NMe3#H2O), 250(M+), 185 Ir (KBr smear) 3401, 2959, 2510, 1653, 1483, 1220, 991, 769, 668, 510.

Example 2 <BR> <BR> <BR> <BR> Svnthesis of 5-[(oxy)-( 1.1,1 trimethvl ammonium) oho sphoranate methvll-bicvclo r2.2. 11 hept-2-ene.

To a solution of 5-norbornene-2-methanol (1.00 g, 0.0079 mol) and N,N,N',N'- tetramethylethylenediamine (0.46 g, 0.0038 mol) in acetonitrile (30 ml) at 0 °C, a solution of2-chloro- 1,3 ,2-dioxaphospholane-2-oxide (1.13 g, 0.0079 mol) in MeCN (10

ml) was slowly added over 20 minutes under N2. The solution was stirred for 4h. The solution was filtered and cooled to O °C Trimethylamine (1.17 g, 0.0198 mol) was added and the solution heated at 50 °C overnight in a closed system. The solution was cooled, degassed, and the solution decanted. The solvent was evaporated and the residue partitioned between H20 (20 ml) and Et2O (20 ml). The aqueous layer was washed with Et2O (20 ml), separated and evaporated. The yellow oil was identified as the product: lH NMR (400 MHz, D2O) 6 complex spectra.

13C NMR (50.1 MHz, D2O) 6 27.0 (CH2CH(CH2O)), 38.0 (CHCH2OP), 41.8 (C(CH2)CH), 43.5 (C(CH2)CH2), 47.8 (CH2 bridge), 54.0 (Me3N), 58.1 (CH2NMe3), 64.8 (CH2OP), 68.5 (CHCH2OP), 131. 1 (CHCH, trans), 135.4 (CHCH, cis), 136.2 (CHCH cis) 136.7 (CHCH trans).

The NMR results are consistent with the reaction taking place being by the following reaction scheme where OPC is a group of formula V in which R9 is a bond, each R10 and each R11 is hydrogen and each Rl3 and R'4 are methyl.

Example 3 3.1 Synthesis of 1 6-heptadien-4-ol: To a suspension of activated magnesium ribbon [activated overnight by stirring in an inert atmosphere] (19.6 g, 0.82 mol) and anhydrous diethyl ether (307 ml), an initiating solution of allyl bromide (10%, 9.0 g, 0.074 mol) in Et2O (13 ml) was added. Once the reaction had started to reflux gently, the remainder of the allyl bromide (81.0 g, 0.646mol) in Et2O(1 19 ml) was slowly added maintaining a gentle reflux. The reaction was left refluxing for 2h. The mixture was cooled in an ice bath

and a solution of ethyl formate (24.77 g, 0.33 mol) in Et2O (53 ml) was slowly added to the stirred mixture over 1h. The reaction was left to warm to room temperature overnight. The reaction was quenched with saturated ammonium chloride solution (260 ml), and H2O then added (250 ml). The aqueous layer was acidified with dilute (0. 1 M) hydrochloric acid and the organic layer separated. The organic layer was washed with NaHCO3 (300 ml), H2O (200 ml), and NaCI (200 ml). The organic layer was dried with anhydrous sodium sulphate and the solvent removed. The resulting pale yellow oil was identified as a mixture of the alcohol and the formate ester (approximately 5:2 ratio): 1H NMR (400 MHz, CDCl3) # 1.90 (1H, m, CHOH), 2.20 (2H,m, CHCH2), 2.35 (2H, m, CHCH2), 3.70 (1H, m, CHOH), 5.15 (4H, m, 2xCHCH2), 5.75 (2H, m, 2xCHCH2), 8.05 (1 H, s, OC(H)-O-CH).

3C NMR (50. 1 MHz, CDCl3) 6 37.8 (CH2), 41.2 (CH2), 69.7 (CHOH), 72.4 (CHO- COH), 118.1 (CHCH2) 118.3 (CHCH2), 133.0 (CHCH2), 134.6 (CHCH2), 160.7 (CO(H)-O-CH).

3.2 Synthesis of 4-[(oxy)(1,1,1 trimethyl ammonium) phosphoranate]-1,6- heptadiene.

To a solution of 1,6-heptadien-4-ol (10.00 g, 0.089 mol) and N,N,N',N'- tetramethylethylenediamine (5.18 g, 0.045 mol) in acetonitrile [MeCN] (100 ml) at 0 °C, a solution of 2-chloro-1,3,2-dioxaphospholane-2-oxide (12.72 g, 0.089 mol) in MeCN (60 ml) was slowly added over 20 minutes under N2. The solution was stirred for 4h. The solution was filtered and cooled to 0 OC. Trimethylamine (13.17 g, 0.223 mol) was added and the solution heated at 50 °C overnight in a closed system. The solution was cooled, degassed, and the solution decanted. The solvent was evaporated and the residue partitioned between H2O (150 ml) and dichloromethane [DCM] (150 ml). The aqueous layer was washed with DCM (150 ml), separated and evaporated. The residue was washed with acetone (2x 150 ml) and stored in acetone (100 ml) overnight. The acetone layer was evaporated to leave a solid residue. The solid residue was identified as the product: 'H NMR (400 MHz, D2O) 6 complex spectra.

13C NMR (50.1 MHz, D2O) 6 43.5 (CH2), 54.0 (Me3NCH2), 55.5 (CH2NMQ), 59.8 (CH2OPO), 65.7 (CHOP), 118. 1 (CHCH2), 134.2 (CHCH2).

The example is represented by the following reaction The reaction allows synthesis of pure product in a satisfactory yield.

Example 4 4.1 Synthesis of 3,5-dimethyl-1,6-heptadien-4-ol: To a suspension of activated magnesium ribbon [activated overnight by stirring in an inert atmosphere] (6.22 g, 0.26 mol) and anhydrous tetrahydrofuran [THF] (110 ml), an initiating solution of 3 chloro-l-butene (10%, 2.0 g, 0.02 mol) in THF (6 ml) and a crystal of iodine were added. Once the reaction had started to reflux gently, the remainder ofthe 3 chloro- 1 -butene (18.0 g, 0.199 mol) in THIF (51 ml) was slowly added maintaining a gentle reflux. The reaction was left refluxing for 2h and heated further at 70 °C for 1 h. The mixture was cooled to room temperature and a solution of ethyl formate (7.38 g, 0. 10 mol) in T11F (20 ml) was slowly added to the stirred mixture over 1h. The reaction was left overnight. The reaction was quenched with saturated ammonium chloride solution (270 ml). The organic layer was separated and washed with NaHCO3 (275 ml) and brine solution (250 ml). Ethyl acetate (300 ml) was added and organic layer separated. The organic layer was treated with charcoal, filtered with celite and the solvent removed. The resulting yellow oil was believed to be a mixture of the three types of alcohol and their ester derivatives:

'H NMR (400 MHz, CDCl3) complex spectra. 6 0.9 - 1.10 (3H, m, CliMe), 1.60 (3H, d, MeCH=), 2.20 (2H,m, CHCH2), 2.35 - 2.55 (2H, m, CHCH2), 3.25 - 3.70 (1H, M, CHOH), 5.00 - 5.15 (4H, m, 2xCHCH2), 5.65 - 5.85 (2H, m, 2xCHCH2 and MeCHCH), 8.05 - 8.15 (1H, s, OC(HJ-O-CH).

13C NMR (50. 1 MHz, CDCl3) complex spectra. 6 15 - 20 (CH3), 38.0 - 41.5 (CH2 and CHMe), 75 - 80 (CHOH and CHO-COH), 114 - 118 (CHCH2 and CHCHMe), 138 - 141 (CHCH2 and CHCHMe), 160.7 (OC(H)-O-CH).

4.2 Synthesis of 4-[(oxy)-(1,1,1 trimethyl ammonium) phosphoranate]-3,5- dimethyl-1,6-heptadiene.

To a solution of 3, 5-dimethyl-1,6-heptadien-4-ol (2.00 g, 0.014 mol) and N,N,N',N'- tetramethylethylenediamine (0.83 g, 0.007 mol) in acetonitrile [MeCN] (20 ml) at 0 °C, a solution of 2-chloror-1,3,2-dioxaphospholane-2-oxide (2.04 g, 0. 14 mol) in MeCN (25 ml) was slowly added over 20 minutes under N2. The solution was stirred for 4h. The solution was filtered and cooled to 0 OC. Trimethylamine (3.10 g, 0.053 mol) was added and the solution heated at 50 °C overnight in a closed system. The solution was cooled, degassed and the solution decanted. The solvent was evaporated and the residue partitioned between H2O (125 ml) and ether [Et2O] (130 ml). The aqueous layer washed with Et2O (130 ml), separated and evaporated. The residue was identified as a phosphorous species, but without the dialkene.

1H NMR (400 MHz, D2O) 6 complex spectra.

13C NMR (50. 1 MHz, D2O) 5 54.0 (Me3NCH2). 55.0 (CH2NMe3), 62.2 (CH2OPO).

The methyl substituents lead to the formation of a variety of isomers. Where a pure product is desired this route may not be satisfactory.

Example 5 5.1 Copolvmerisation of cyclopentene and norbornene: To a solution of ruthenium trichloride (59. 5 mg, 0.0002 mol) in ethanol (4ml), a solution of cyclopentene (8ml, 0. 1080 mol) and norbornene (0.56 g, 0.0060 mol) in chlorobenzene (4 ml) was added. The Parr tube was sealed and heated at 60 °C for 72

hr. The solvent was decanted off and the solid residue was dissolved in chloroform (20 ml). The polymer was reprecipitated in methanol (200 ml) to yield a grey/black solid. The polymer was dried with filter paper.

1H NMR (400 MHz, CDCl3) complex spectra. 1.0 - 2.9 (m, CH and CH2 of alkyl backbone), 5.17 - 5.42 [CH of polyalkene units (cyclopentene copolymer unit, M1; and norbornene copolymer unit, M2) in polymer].

13C NMR (50.1 MHz CDCl3) complex spectra. 26.5 - 27.1 (m, CH2), 29.2 - 30.1 (m, CH2), 31.8 - 33.4 (m, CH2), 37.8 - 38.7 (m, CH2), 40.8 - 42.3 (m, CH), 42.5 - 43.8 (m, CH2), 50.8 (s, MeOH), 128.0 - 128.2 (m, M1M2), 129.7 - 130.0 (m, M1M1 cis), 130.2 (m, M1M1 trans), 132.7 - 133.4 (m, M2M2 trans0, 133.7 - 134.1 (m, M2m2 cis), 135.0 - 135.5 (m, M2Ml).

5.2 Terpolvmerisation of cyclopentene norbornene and 5-[(xoy)-(1,1,1 trimethyl ammonium) phosphoranate methvll-bicvclo [2.2. 1 hept-2-ene.

To a solution of ruthenium trichloride (124 mg, 0.0005 mol) in ethanol (3ml), a solution of cyclopentene (8ml, 0. 1080 mol) and norbornene (0.54 g, 0.0057 mol) in chlorobenzene (3.5 ml) was added. A solution of 5-[(oxy)-(1,1,1 trimethyl ammonium) phosphoranate methyl]-bicyclo [2.2.1] hept-2-ene (0.34 g, 0.0012 mol) in EtOH (0.5 ml) and chlorobenzene (0.5 ml) was also added. The Parr tube was sealed and heated at 60 °C for 48 hr. The solution was decanted off and evaporated.

1H NMR (400 MHz, DMSO) complex spectra.

13C NMR (50. 1 MHz, DMSO) complex spectra. 28.0 - 28.9, 39.2, 39.5, 41.2, 41.8, 43.0, 43.3, 44.7, 49.0, 54.0 (Me3N), 59.5 (CH2N), 60.5, 60.6, 65.5 - 65.8, 66.8 (CH2OP), 67.7, 68.8 (CH2OP) (alkyl unit of polymer backbone), 128.6, 130.5, 132.5, 136.5, 136.9, 137.3 (vinyl units of polymer).

5.3 Terpolymerisation of 3-[(oxy)(1,1,1 trimethyl ammonium) phosphoranate]- cvclopentene. cvclopentene and norbornene: To a solution of ruthenium trichloride hydrate (59.7 mg, 0.00023 mol) in ethanol (4 ml), a solution of 3-[(oxy)(1,1,1 trimethyl ammonium) phosphoranate]- cyclopentene (1.99 g, 0.0080 mol) in ethanol (2 ml) and chlorobenzene (1 ml); and a solution of norbornene (0.52 g, 0.0055 mol) and cyclopentene (8 ml, 0.1080 mol) in

chlorobenzene (3 ml) was added. The Parr tube was sealed and heated at 60 °C for 72 hr. The solvent was decanted off and the precipitate was redissolved in methanol (15 ml) and chloroform (20 ml). The polymer solution was reprecipitated in acetone (350 ml). The polymer was identified as: 1H NMR (400 MHz, CD3OD/CDCl3) complex spectra.

13C NMR (50.1 MHz, CD3OD/CDCl3) complex spectra. 44.5 - 45, 45.8, 52.9 (Me3N), 53.5, 61.3, 62.5 (CH2N), 62.7, 67.0 (CH2OP), 68.7 (CHOP), 68.8, 77.5, 77.7 (alkyl backbone of polymer), 117.1, 119.9, 121.5, 125.4, 131.1, 136.4, 142.5 (vinyl units of polymer).

In this series of experiments, without optimisation, a standard ROMP was carried out (Journal of Molecular Catalysis A: Chemical 115 (1997) 85-94) (Example 5.1). This was then carried out with doping ofthis reaction mixture 5-[(oxy)-(l,1,l trimethyl ammonium) phosphoranate methyl]-bicyclo [2.2.1] hept-2-ene (Example 5.2), and then 1-[(oxy)-(1,1,1 trimethyl ammonium) phosphoranate]cyclopent-3-ene (Example 5.3). The carbon NMR spectra of the two reactions were consistent with inclusion of the PC derivative in the polymer according to the Scheme below.