Crosslinking Monomers With at Least One Sulfur Atom

Abstract

The invention relates to a cross-linking monomer with at least one sulfur atom, representable by a structure of formula (I)

##STR00001## wherein the symbols have the following meaning: L.sup.1 is a linear, branched or cyclic, saturated or unsaturated, aliphatic or heteroaliphatic group with 2 to 10 carbon atoms; an aromatic or heteroaromatic group with 4 to 12 carbon atoms or a group with 6 to 14 carbon atoms, which comprises at least one saturated or unsaturated, aliphatic and/or heteroaliphatic residue and at least one aromatic and/or heteroaromatic residue, wherein the phosphorus atom is directly bonded with a carbon atom; V.sup.1 is a saturated or unsaturated, aliphatic or heteroaliphatic group with 2 to 50 carbon atoms; an aromatic or heteroaromatic group with 5 to 50 carbon atoms or a group with 6 to 50 carbon atoms, which comprises at least one saturated or unsaturated, aliphatic and/or heteroaliphatic residue and at least one aromatic and/or heteroaromatic residue; X.sup.1 is the same or different, O or NR.sup.3, each time it occurs; R.sup.1 is H or a hydrolyzable group; R.sup.2 is H or an alkyl residue with 1 to 4 carbon atoms; R.sup.3 is H or an aliphatic, heteroaliphatic, aromatic or heteroaromatic group with 1 to 6 carbon atoms, and n is 2, 3, 4, 5 or 6, wherein the sulfur atom in the structure according to formula (I) is separated from group X.sup.1 by a maximum of 12 bonds, which group is spaced from the sulfur atom by the lowest number of bonds, wherein double bonds or triple bonds are counted as a single bond.

Claims

1. A cross-linking monomer with at least one sulfur atom, represented by a structure of formula (I) ##STR00031## wherein the symbols have the following meaning: L.sup.1 is a linear, branched or cyclic, saturated or unsaturated, aliphatic or heteroaliphatic group with 2 to 10 carbon atoms; an aromatic or heteroaromatic group with 4 to 12 carbon atoms or a group with 6 to 14 carbon atoms, which comprises at least one saturated or unsaturated, aliphatic and/or heteroaliphatic residue and at least one aromatic and/or heteroaromatic residue, wherein the phosphorus atom of the group PO(OR.sup.1).sub.2 is directly bonded with a carbon atom; V.sup.1 is a saturated or unsaturated, aliphatic or heteroaliphatic group with 2 to 50 carbon atoms; an aromatic or heteroaromatic group with 5 to 50 carbon atoms or a group with 6 to 50 carbon atoms, which comprises at least one saturated or unsaturated, aliphatic and/or heteroaliphatic residue and at least one aromatic and/or heteroaromatic residue; X.sup.1 is the same or different each time it occurs, either O or NR.sup.3; R.sup.1 is H or a hydrolyzable group; R.sup.2 is H or an alkyl residue with 1 to 4 carbon atoms; R.sup.3 is H or an aliphatic, heteroaliphatic, aromatic or heteroaromatic group with 1 to 6 carbon atoms, and n is 2, 3, 4, 5 or 6, wherein the sulfur atom in the structure according to formula (I) is separated from group X.sup.1 by a maximum of 12 bonds, which group is spaced from the sulfur atom by the lowest number of bonds, wherein double bonds or triple bonds are counted as a single bond.

2. The monomer according to claim 1, wherein group V.sup.1 has at least one aromatic and/or heteroaromatic residue.

3. The monomer according to claim 2, wherein the aromatic and/or heteroaromatic residue of group V.sup.1 is a monocyclic residue.

4. The monomer according to claim 1, wherein L.sup.1 is a linear, branched, or cyclic alkylene group with 2 to 10 carbon atoms, in which one or more non-adjacent CH.sub.2 groups is/are not substituted or is/are substituted with R.sup.3CCR.sup.3, CC, (CO), (CS), (CNR.sup.3), C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), [CH(C.sub.xH.sub.2x)P(O)(OR.sup.1).sub.2], O, S, (SO), or (SO.sub.2), wherein x is an integer in a range of 0 to 6.

5. The monomer according to claim 1, wherein the hydrolyzable group R.sup.1 is an alkyl residue with 1 to 4, carbon atoms.

6. The monomer according to claim 1, wherein the monomer is represented by structure (II) ##STR00032## wherein V.sup.2 is a saturated or unsaturated, aliphatic and/or heteroaliphatic group with 2 to 10 carbon atoms; an aromatic or heteroaromatic group with 4 to 12 carbon atoms or a group with 6 to 14 carbon atoms, which comprises at least one saturated or unsaturated, aliphatic and/or heteroaliphatic residue and at least one aromatic and/or heteroaromatic residue; and L.sup.2 is a linear, branched or cyclic, saturated or unsaturated, aliphatic or heteroaliphatic ether or ester group with 2 to 30 carbon atoms; an aromatic and/or heteroaromatic ether or ester group with 5 to 30 carbon atoms or an ether or ester group with 6 to 30 carbon atoms, which comprises at least one saturated or unsaturated, aliphatic and/or heteroaliphatic residue and at least one aromatic and/or heteroaromatic residue.

7. The monomer according to claim 6, wherein group V.sup.2 is selected from the following structures (V.sup.2-1), (V.sup.2-2) and/or (V.sup.2-3) ##STR00033## wherein the broken lines represent the bonds to groups L.sup.2 or X.sup.1.

8. The monomer according to claim 6, wherein group L.sup.2 is represented by a structure of formula (L.sup.2-1) ##STR00034## wherein, each time it occurs, R.sup.4 is H, an alkyl group with 1 to 10 carbon atoms or an aromatic group with 6 to 8 carbon atoms; each time it occurs, R.sup.5 is independently H or an alkyl group with 1 to 10 carbon atoms; the index m is an integer in the range of 0 to 8, and the broken lines each represent the bond to the sulfur atom or group V.sup.2.

9. The monomer according to claim 1, wherein the monomer is represented by structure (III) ##STR00035## wherein V.sup.3 is a saturated or unsaturated, aliphatic and/or heteroaliphatic group with 2 to 10 carbon atoms; an aromatic and/or heteroaromatic group with 4 to 12 carbon atoms or a group with 6 to 14 carbon atoms, which comprises at least one saturated or unsaturated, aliphatic and/or heteroaliphatic residue and at least one aromatic and/or heteroaromatic residue, in which one or more non-adjacent CH.sub.2 groups is/are not substituted or is/are substituted with R.sup.3CCR.sup.3, CC, (CO), (CS), (CNR.sup.3), C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), [CH(C.sub.xH.sub.2x)P(O)(OR.sup.1).sub.2], O, S, (SO), or (SO.sub.2), wherein x is an integer in the range of 0 to 6; and L.sup.3 is a linear, branched, or cyclic, saturated or unsaturated, aliphatic and/or heteroaliphatic ether or ester group with 6 to 40 carbon atoms; an aromatic and/or heteroaromatic ether or ester group with 6 to 40 carbon atoms; or an ether or ester group with 6 to 40 carbon atoms, which comprises at least one saturated or unsaturated, aliphatic and/or heteroaliphatic residue and at least one aromatic and/or heteroaromatic residue, in which one or more non-adjacent CH.sub.2 groups is/are not substituted or is/are substituted with R.sup.3CCR.sup.3, CC, (CO), (CS), (CNR.sup.3), C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), [CH(C.sub.xH.sub.2x)P(O)(OR.sup.1).sub.2], O, S, (SO), or (SO.sub.2), wherein x is an integer in the range of 0 to 6.

10. The monomer according to claim 9, wherein group L.sup.3 is represented by a structure of formula (L.sup.3-1) ##STR00036## wherein, each time they occur, L.sup.4 and L.sup.5 independently are a linear, branched, or cyclical alkylene group with 2 to 20 carbon atoms, in which one or more non-adjacent CH.sub.2 groups is/are not substituted or is/are substituted with R.sup.3CCR.sup.3, CC, CO, CS, CNR.sup.3, C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), [CH(C.sub.xH.sub.2x)P(O)(OR.sup.1).sub.2], O, S, SO, or SO.sub.2, wherein x is an integer in the range of 0 to 6, or an aryl or heteroaryl group with 5 to 20 carbon atoms, which is not substituted or is substituted with one or more substituents R.sup.3; or a group with 6 to 40 carbon atoms, which comprises at least one saturated or unsaturated, aliphatic, and/or heteroaliphatic residue and at least one aromatic and/or heteroaromatic residue; and the broken lines each represent the bond to group V.sup.3 or group X.sup.1.

11. The monomer according to claim 10, wherein group L.sup.4 is represented by a structure of formula (L.sup.4-1) or (L.sup.4-2) ##STR00037## wherein Ar.sup.1 is an aryl or heteroaryl group with 4 to 12 carbon atoms which is not substituted or is substituted with one or more substituents R.sup.3; L.sup.6 is selected from CO, CS, CNR.sup.3, C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), O, S, SO, or SO.sub.2 or a linear, branched, or cyclic alkylene group with 1 to 6 carbon atoms, in which one or more non-adjacent CH.sub.2-groups is not substituted or is substituted with R.sup.3CCR.sup.3, CC, CO, CS, CNR.sup.3, C(O)O, C(O)NR.sup.3, NR.sup.3, P(O)(R.sup.3), [CH(C.sub.xH.sub.2x)P(O)(OR.sup.1).sub.2], O, S, SO, or SO.sub.2, wherein x is an integer in the range of 0 to 6 and the broken lines each represent the bond to group V.sup.3 or the oxygen atom.

12. The monomer according to claim 10, wherein group L.sup.5 is represented by a structure of formula (L.sup.5-1) ##STR00038## wherein, each time it occurs, R.sup.6 is independently H, an alkyl group with 1 to 10 carbon atoms or an aromatic group with 6 to 8 carbon atoms; R.sup.7 is H or an alkyl group with 1 to 10 carbon atoms; and the index m is an integer in the range of 0 to 8 and the broken lines represent bonds to the oxygen atom or the group X.sup.1.

13. The monomer according to claim 9, wherein group V.sup.3 is represented by a structure of formulae (V.sup.3-1), (V.sup.3-2), (V.sup.3-3), (V.sup.3-4), (V.sup.3-5), or (V.sup.3-6) ##STR00039## wherein the broken lines represent bonds to S or groups L.sup.3.

14. A curable composition for use in dental medicine, comprising at least one monomer according to claim 1.

15. A method for producing a monomer according claim 1, comprising reacting an unsaturated compound with a sulfurous compound in accordance with formula (E-I) ##STR00040##

16. (canceled)

17. The monomer according to claim 2, wherein group V.sup.1 has at least one aromatic residue.

18. The monomer according to claim 3, wherein the aromatic and/or heteroaromatic residue of group V.sup.1 is a phenyl or phenylene residue.

19. The monomer according to claim 4, x is an integer in a range of 1 to 5.

20. The monomer according to claim 5, wherein the hydrolyzable group R.sup.1 is an alkyl residue with 2, carbon atoms.

21. The monomer according to claim 6, wherein V.sup.2 is a saturated or unsaturated, aliphatic and/or heteroaliphatic group with 3 to 6 carbon atoms; an aromatic or heteroaromatic group with 4 to 12 carbon atoms or a group with 6 to 14 carbon atoms, which comprises at least one hydrocarbon residue with 3 to 5 carbon atoms.

22. The monomer according to claim 8, wherein, each time it occurs, R.sup.4 is H or a phenyl group; each time it occurs, R.sup.5 is independently H; and the index m is an integer in the range of 0 to 7.

23. The monomer according to claim 22, wherein the index m is an integer in the range of 0 to 5.

24. The monomer according to claim 9, wherein: V.sup.3 is a saturated or unsaturated, aliphatic and/or heteroaliphatic group with 3 to 6 carbon atoms or an aliphatic group with 2 to 10 carbon atoms wherein and x is an integer in the range of 1 to 5; and L.sup.3 is a linear, branched, or cyclic, saturated or unsaturated, aliphatic and/or heteroaliphatic ether or ester group with 10 to 25 carbon atoms; an aromatic and/or heteroaromatic ether or ester group with 10 to 25 carbon atoms; or an ether or ester group with 10 to 25 carbon atoms, which comprises at least one aliphatic and/or aromatic ether or ester group with 6 to 40, carbon atoms, wherein x is an integer in the range of 1 to 5.

25. The monomer according to claim 24, wherein: V.sup.3 is a saturated or unsaturated, aliphatic and/or heteroaliphatic group with 3 to 6, carbon atoms; an aliphatic group with 3 to 6 carbon atoms; and L.sup.3 is an ether or ester group with 10 to 25 carbon atoms, which comprises at least one aliphatic and/or aromatic ether or ester group with 10 to 25 carbon atoms.

26. The monomer according to claim 10, wherein, each time they occur, L.sup.4 and L.sup.5 independently are a linear, branched, or cyclical alkylene group with 3 to 15 carbon atoms, x is an integer in the range of 1 to 5, or a group with 10 to 25 carbon atoms, which comprises at least one saturated or unsaturated, aliphatic, and/or heteroaliphatic residue and at least one aromatic and/or heteroaromatic residue.

27. The monomer according to claim 11, wherein Ar.sup.1 is an aryl or heteroaryl group with 6 carbon atoms and x is an integer in the range of 1 to 5.

28. The monomer according to claim 12, wherein, each time it occurs, R.sup.6 is independently H, R.sup.7 is H, and the index m is an integer in the range of 0 to 7.

29. The monomer according to claim 28, wherein the index m is an integer in the range of 0 to 5.

Description

EXAMPLE 1

Step 1

Synthesis of 9-((3-diethoxyphosphoryl)thio)octadecane acid

[0132] ##STR00018##

[0133] 6.5 g (23 mmol) oleic acid, 5.1 g (24 mmol) diethyl(3-mercaptopropyl) phosphonate and 295.8 mg (1.15 mmol) 2,2-dimethoxy-2-phenylacetophenone were mixed. The mixture was stirred for 6.5 hours under UV light. Educts that did not react were extracted through a 1-molar hydrochloric acid solution (3). The raw product obtained was purified using column chromatography (ethyl acetate/methanol 95/5). A yellow liquid was obtained.

[0134] The .sup.1H NMR spectrum obtained of 9-((3-diethoxyphosphoryl)thio)octadecane acid is shown in FIG. 1.

[0135] Yield: 72%;

[0136] R.sub.f-value: 0.35 (ethyl acetate/methanol 95/5);

[0137] FT-IR (diamond, cm.sup.1): {tilde over (v)}=3457 (b, v.sub.OH), 2924/2853 (m, v.sub.CH), 1724 (w, v.sub.COOR), 1456 (w, .sub.P C), 1393, 1205 (m, v.sub.PO), 1097, 1055 (m, .sub.POC), 1024 (s, .sub.POC), 962, 784 (m, v.sub.POC), 723, 540, 494;

[0138] .sup.1H-NMR (300 MHz, CDCl.sub.3, [ppm]): 4.12-3.97 (m, 4H, b), 2.58-2.42 (m, 3H, e and f), 2.25 (t, .sup.3J.sub.HH=7.39 Hz, 2H, v), 1.91-1.71 (m, 5H, c, d and p), 1.61-1.16 (m, 34H, g to n, q to u, p and a), 0.85-0.79 (m, 3H, o);

[0139] .sup.13C-NMR (75 MHz, CDCl.sub.3, [ppm]): 176.68 (s, w), 60.79 (d, .sup.2J.sub.PC=6.56 Hz, b), 44.86 (s, f), 33.96-33.71 (d, p and g), 33.11 (s, v), 30.88 (s, m), 29.86 (d, .sup.3J.sub.PC=18.19 Hz, e), 28.65-27.92 (m, i to l and r to t), 25.83-25.57 (m, h and q), 23.79 (s, u), 23.67 (d, .sup.1J.sub.PC=141.57 Hz, c), 21.82 (d, .sup.2J.sub.PC=4.57 Hz, d), 21.66 (s, n), 15.42 (s, .sup.3J.sub.PC=6.08 Hz, a), 13.09 (s, o);

[0140] .sup.31P-NMR (121 MHz, CDCl.sub.3, [ppm]): 32.09 and 32.03 (2s, Markownikow and anti-Markownikow product);

[0141] MS (ESI) m/z: 495 [M+H.sup.+]; EAcalc. (%): C, 60.70. H, 10.39. S, 6.48; EAfound (%): C, 60.37. H: 10.14. S: 6.11.

Step 2

Synthesis of 2-((9-((3-(diethoxyphosphoryl)propyl)thio)octadecanoyl)oxy)propane-1,3-diyl-bis (2-methyl acrylate)

[0142] ##STR00019##

[0143] In a 50 ml flask, 2 g (4 mmol) 9-((3-diethoxyphosphoryl)thio) octadecane acid were dissolved in 20 ml dry dichloromethane and cooled in an ice bath to 0 C. 0.83 (4 mmol) DCC and 50 mg (0.4 mmol) DMAP were suspended in 5 ml dry dichloromethane. The suspension was added drop by drop. After 2 hours, 0.9 ml (1 g, 4.4 mmol) glycerine-1,3-dimethacrylate were added; the mixture was brought to room temperature and stirred for 24 hours. Precipitated DCU was filtered and the filtrate was cooled with a dry ice-acetone mixture for 45 minutes (3). The organic solution was concentrated under reduced pressure. The raw product was purified using column chromatography (silica gel) with ethyl acetate. A yellow liquid with a honey-like consistency was obtained.

[0144] The obtained .sup.1H NMR spectrum of 2-((9-((3-(diethoxyphosphoryl)propyl)thio)-octadecanoyl)oxy)propane-1,3-diyl-bis(2-methyl acrylate) is shown in FIG. 2.

[0145] Yield: 39%;

[0146] R.sub.f-value: 0.66 (ethyl acetate);

[0147] FT-IR (diamond, cm.sup.1): {tilde over (v)}=2926/2854 (w, v.sub.CH), 1723 (s, v.sub.COOR), 1638, 1454 (w, .sub.PC), 1321, 1294, 1235 (m, v.sub.P O), 1154 (s, .sub.POC), 1097, 1057, 1027 (s, .sub.POC), 942, 812 (m, v.sub.POC), 723, 653, 541, 491;

[0148] .sup.1H-NMR (300 MHz, CDCl.sub.3, [ppm])=6.06-6.03 (m, 2H, B), 5.55-5.51 (m, 2H, B), 5.38-5.26 (m, 1H, x), 4.35-4.14 (m, 4H, y), 4.10-3.95 (m, 4H, b), 2.53-2.44 (m, 3H, e and f), 2.26 (td, .sup.2J.sub.HH=1.99 Hz, .sup.3J.sub.HH=7.51 Hz, 2H, v), 1.88-1.75 (m, 10H, c, d and C), 1.60-1.20 (m, 34H, a, g to n and p to u), 0.85-0.77 (m, 3H, o);

[0149] .sup.13C-NMR (75 MHz, CDCl.sub.3, [ppm])=172.72 (s, w), 166.66 (s, z), 135.61 (s, A), 126.25 (s, B), 68.73 (s, x), 62.55 (s, y), 60.51 (d, .sup.2J.sub.PC=6.64 Hz, b), 45.79 (s, f), 34.79 (s, p and g), 34.04 (s, v), 31.82 (s, m), 30.82 (d, .sup.3J.sub.PC=17.94 Hz, e), 29.59-28.97 (m, i to l and r to t), 26.72 (s, h and q), 24.83 (s, u), 24.70 (d, .sup.1J.sub.PC=141.55 Hz, c), 22.84 (d, .sup.2J.sub.PC=4.61 Hz, d), 22.60 (s, n), 18.17 (s, C), 16.40 (s, .sup.3J.sub.PC=6.05 Hz, a), 14.05 (s, o);

[0150] .sup.31P-NMR (121 MHz, CDCl.sub.3, [ppm])=31.68 (s, 1P);

[0151] MS (ESI) m/z: 495 [C.sub.25H.sub.51O.sub.5PS+H.sup.+], 706 [M+H.sup.+]; EA.sub.calc. (%): C, 61, 34, H, 9.29, S, 4.55; EA.sub.found (%): C, 61.17, H, 9.26, S, 4.12.

EXAMPLE 2

Synthesis of 3-((1-((1,3-bis(methacryloyloxy)propane-2-yl)oxy)-1-oxooctadecane-9-yl(thio)propyl)phosphonic acid

[0152] ##STR00020##

[0153] The hydrolysis of 2-((9-((3-(diethoxyphosphoryl)propyl)thio)octadecanoyl)oxy)-propane-1,3-diyl-bis(2-methyl acrylate) was conducted using the known method.

[0154] 570 mg (0.81 mmol) 2-((9-((3-(diethoxyphosphoryl)propyl)thio)octadecanoyl)oxy)-propane-1,3-diyl bis 2-methyl acrylate was dissolved in 8.2 ml dry dichloromethane. The solution was de-gassed through the introduction of nitrogen for 10 minutes. Then, 1.07 l (8.1 mmol) bromtrimethyl silane were added, and the solution was stirred for 9 hours with a bath temperature of 23 C. The organic solvent was removed under reduced pressure and dried under vacuum. The interim product was treated with 15 ml methanol and stirred for 1 hour at room temperature. Then, the solvent was removed at reduced pressure. After drying the product under vacuum, a yellow, highly viscous liquid was obtained.

[0155] The obtained .sup.1H NMR spectrum of 3-((1-((1,3-bis(methacryloyloxy)propane-2-yl)oxy)-1-oxooctadecane-9-yl(thio)propyl)phosphonic acid is shown in FIG. 3.

[0156] Yield: 79% (0.64 mmol);

[0157] FT-IR (diamond, cm.sup.1): {tilde over (v)}=3386 (b, v.sub.OH), 2925/2854 (m, v.sub.CH), 1724 (s, v.sub.COOH), 1638 (w, v.sub.COC), 1455 (w, .sub.PC), 1378, 1294 (m, v.sub.P O), 1154 (s, .sub.POC), 1007 (s, .sub.POC), 942, 813 (m, v.sub.POC), 723, 654, 520, 461;

[0158] .sup.1H-NMR (300 MHz, CDCl.sub.3, [pm])=6.56 (s, a), 6.07-6.04 (m, 2H, A), 5.56-5.52 (m, 2H, A), 5.36-5.22 (m, 1H, w), 4.41-4.11 (m, 4H, x), 2.53-2.44 (m, 3H, d and e), 2.26 (t, .sup.2J.sub.HH=7.22 Hz, 2H, u), 1.90-1.79 (m, 10H, b, c and B), 1.54-1.14 (m, 28H, f to m and o to t), 0.83-0.79 (m, 3H, n);

[0159] .sup.13C-NMR (75 MHz, CDCl.sub.3, [ppm])=172.97 (s, v), 166.79 (s, y), 135.64 (s, z), 126.40 (s, A), 68.82 (s, w), 62.62 (s, x), 45.91 (s, e), 34.76 (s, o and f), 34.19 (s, u), 31.88 (s, l), 30.81 (d, .sup.3J.sub.PC=19.21 Hz, d), 29.68-29.03 (m, h to k and q to s), 26.74 (s, g and p), 24.90 (s, t), 24.89 (d, .sup.1J.sub.PC=143.37 Hz, b), 22.67 (s, m), 22.53 (d, .sup.2J.sub.PC=4.17 Hz, c), 18.24 (s, B), 14.12 (s, n);

[0160] .sup.31P-NMR (121 MHz, CDCl.sub.3, [ppm])=36.68 (s, 1P);

[0161] MS (ESI) m/z: 650 [M+H.sup.+], 678 [single saponified educt+H.sup.+], 729 [educt+Na.sup.+].

EXAMPLE 3

Step 1

Synthesis of 3-((3-(diethoxyphosphoryl)propyl)thio)-3-phenyl propane acid

[0162] ##STR00021##

[0163] 2 g (13.5 mmol) cinnamic acid and 2.56 g (12.1 mmol) diethyl (3-mercaptopropyl) phosphonate were dissolved in 6 ml THF. The solution was de-gassed through the introduction of nitrogen for 15 minutes. Following the addition of 0.4 ml (2.64 mmol) DBU (1,8-diazabicyclo[5.4.0]-7-undecene), the mixture was heated for approx. 48 hours under return flow. Following a cooling of the reaction mixture to room temperature, dichloromethane was added, and the mixture was washed twice with 1-molar, once with 0.1-molar hydrochloric acid, and with water. The solvent was removed under reduced pressure.

[0164] The obtained .sup.1H NMR spectrum of 3-((3-(diethoxyphosphoryl)propyl)thio)-3-phenyl propane acid is shown in FIG. 4. Raw yield: 2.09 g;

[0165] FT-IR (diamond, cm.sup.1): {tilde over (v)}=3465 (b, v.sub.OH), 2981/2933/2905/2867 (w, v.sub.CH), 1707 (m, v.sub.COOH), 1638 (w, v.sub.CC), 1575, 1494, 1451, 1393, 1366, 1306, 1261, 1190 (m, v.sub.COH), 1097, 1020 (s, .sub.POC), 958 (s), 834, 796, 770/700 (m, .sub.benzyl), 748, 699, 581, 530, 485;

[0166] .sup.1H-NMR (300 MHz, DMSO-d6, [ppm]): 7.42-7.39 (m, 2H, i and k), 7.35-7.31 (m, 3H, h, j and l), 4.19 (t, .sup.3J.sub.HH=7.67 Hz, 1H, f), 4.02-3.87 (m, 4H, b), 3.36 (s, n), 2.81 (dd, .sup.3J.sub.HH=7.75 Hz, 2H, m), 2.47-2.33 (m, 2H, e), 1.89-1.50 (m, 4H, c and d), 1.20 (t, .sup.3J.sub.HH=7.07 Hz, 6H, a);

[0167] .sup.31P-NMR (121 MHz, DMSO-d6, [ppm]): 31.29 (s, 1P Edukt]), 31.10 (s, 1P, product);

[0168] MS (ESI) m/z: 361 [C.sub.16H.sub.25O.sub.5PS+H.sup.+].

Step 2

Synthesis of 2-((3-((3-(diethoxyphosphoryl)propyl)thio-3-phenylpropanoyl)oxy)-propane-1,3-diyl bis (2-methyl acrylate)

[0169] ##STR00022##

[0170] In a 100 ml flask, 1 g (approx. 2.3 mmol) 3-((3-(diethoxyphosphoryl)propyl)thio)-3-phenyl propane acid was dissolved in 11 ml dry dichloromethane and cooled in an ice bath to 00 C. 711.8 mg (3.5 mmol) DCC and 42 mg (0.35 mmol) DMAP were suspended in 2 ml dry dichloromethane. The suspension was added drop by drop via a syringe. After 1.5 hours, 774 l (3.8 mmol) glycerine-1,3-dimethacrylate were added; the mixture was brought to room temperature and stirred for 48 hours. Precipitated DCU was filtered, and the filtrate was cooled with a dry ice-acetone mixture for 60 minutes (3). The organic solution was concentrated under reduced pressure. The raw product was purified using column chromotography (silica gel) with ethyl acetate and light petroleum (v:v 1:1). A light yellow liquid with a honey-like consistency was obtained.

[0171] The obtained .sup.1H NMR spectrum of 2-((3-((3-(diethoxyphosphoryl)propyl)thio-3-phenylpropanoyl)oxy)propane-1,3-diyl bis (2-methyl acrylate) is shown in FIG. 5.

[0172] Yield: 53% (1.2 mmol);

[0173] R.sub.f-value: 0.3 (ethyl acetate:light petroleum 1:1);

[0174] FT-IR (diamond, cm.sup.1): {tilde over (v)}=2961/2957/2928/2902 (w, v.sub.CH), 1720 (m, v.sub.CO), 1636 (w, v.sub.CC), 1453, 1377, 1321, 1294, 1234, (m, v.sub.PO), 1144, 1096, 1055, 1025 (s, .sub.POC), 950, 812/700 (m, (monosubstituted ring), 653, 532 cm.sup.1;

[0175] .sup.1H-NMR (300 MHz, DMSO-d6, [ppm]): 7.36-7.18 (m, 5H, h to l), 6.03-5.95 (m, 2H, s), 5.71-5.65 (m, 2H, s), 5.32-5.20 (m, 1H, o), 4.37-4.14 (m, 5H, f and p), 4.06-3.87 (m, 4H, b), 2.95 (dd, .sup.3J.sub.HH=7.45 Hz, 2H, m), 2.46-2.32 (m, 2H, e), 1.88-1.82 (m, 6H, t), 1.79-1.52 (m, 4H, c and d), 1.20 (t, .sup.3J.sub.HH=7.08 Hz, 6H, a); 13C-NMR (75 MHz, DMSO-d6, [ppm]): 169.30 (s, n), 165.97 (s, q), 141.11 (s, g), 135.25 (s, r), 128.33-126.32 (quintet, h to l), 127.17 (s, s), 69.05 (s, o), 62.19 (d, .sup.2J.sub.PC=28.03 Hz, b), 60.79 (s, p), 44.25 (s, m), 40.36 (s, f), 30.74 (d, .sup.3J.sub.PC=17.55 Hz, e), 23.52 (d, .sup.1J.sub.PC=138.96 Hz, c), 22.15 (d, .sup.2J.sub.PC=4.16 Hz, d), 17.18 (s, t), 16.19 (d, .sup.3J.sub.PC=5.8 Hz, a);

[0176] .sup.31P-NMR (121 MHz, DMSO-d6, [ppm]): 30.97 (s, 1P);

[0177] MS (ESI) m/z: 572 [C.sub.27H.sub.39O.sub.9PS+H.sup.+]; EA.sub.calc. (%): C, 56.83, H, 6.89, S, 5.62; EA.sub.found (%): C, 56.43, H, 6.95, S, 5.54.

EXAMPLE 4

Synthesis of (3-((3-1,3-bis(methacryloyloxy)propane-2-yl)oxy-1-phenylpropyl)thio)propyl)-phosphonic acid

[0178] ##STR00023##

[0179] According to the method described in example 2, 3-((3-1,3-bis(methacryloyloxy)propane-2-yl)oxy-1-phenylpropyl)thio)propyl)phosphonic acid was produced from 2-((3-((3-(diethoxyphosphoryl)propyl)thio-3-phenylpropanoyl)oxy)propane-1,3-diyl-bis-(2-methyl acrylate).

EXAMPLE 5

Step 1

Synthesis of 2-(acryloyloxy)propane-1,3-diyl bis(2-methyl acrylate)

[0180] ##STR00024##

[0181] 2-(acryloyloxy)propane-1,3-diyl bis(2-methyl acrylate) was obtained through the addition of 9.2 ml (10.3 g, 45 mmol) glycerine-1,3-dimethacrylate and 7.3 ml (5.3 g, 53 mmol) triethylamine to 100 ml dry dichloromethane in a 250-ml flask. The solution was cooled in an ice bath to 00 C. Then, 4.3 ml (4.8 g, 53 mmol) acrylic acide chloride, dissolved in 30 ml dry dichloromethane, were added drop by drop for 30 minutes. The solution was brought to room temperature and stirred for over 72 hours. The organic solution was washed three times with water, dried over MgSO.sub.4 and filtered. Following the addition of phenothiazine, the solvent was removed under reduced pressure. A brown liquid was obtained.

[0182] The obtained .sup.1H NMR spectrum of 2-(acryloyloxy)propane-1,3-diyl bis(2-methyl acrylate) is shown in FIG. 6.

[0183] Yield: 83% (37.6 mmol);

[0184] FT-IR (diamond, cm.sup.1): {tilde over (v)}=2980/2960/2929 (w, v.sub.CH), 1719 (s, v.sub.COOR), 1680, 1637 (w, v.sub.CC), 1453, 1406, 1321, 1293, 1264, 1149, 1050, 1066, 1043, 1012, 984 (m, .sub.CC), 943, 862, 809, 657, 598, 460;

[0185] .sup.1H-NMR (300 MHz, CDCl.sub.3, [ppm]): 6.35 (ddd, .sup.2J.sub.HH=5.10 Hz, .sup.3J.sub.HH=17.08 Hz, 1H, i), 6.16-5.98 (m, 3H, h and c), 5.80 (ddd, .sup.2J.sub.HH=3.92 Hz, .sup.3J.sub.HH=10.4 Hz, 1H, i), 5.52 (s, 1H, c), 5.44-5.31 (m, 1H, f), 4.40-4.19 (m, 4H, e), 1.85 (s, 6H, a);

[0186] .sup.13C-NMR (75 MHz, CDCl.sub.3, [ppm]): 165.68 (s, d), 164.03 (s, g), 134.66 (s, b), 130.77 (s, i), 126.80 (s, h), 125.29 (s, c), 68.16 (s, f), 61.53 (s, e), 17.18 (s, a);

[0187] MS (ESI) m/z: 99 [C.sub.5H.sub.7O.sub.2.sup.], 197 [C.sub.10H.sub.13O.sub.4.sup.], 211 [C.sub.11H.sub.15O.sub.4.sup.], 214 [C.sub.10H.sub.14O.sub.5], 283 [M+H.sup.+], 300 [M+NH.sub.4.sup.+], 305 [M+Na.sup.+].

Step 2

Synthesis of 2-((3-((3-(diethoxyphosphoryl)propyl)thio)propanoyl)oxy)propane-1,3-diyl bis(2-methyl acrylate)

[0188] ##STR00025##

[0189] In a round flask, 5.1 g (18 mmol) 2-(acryloyloxy)propane-1,3-diyl bis(2-methyl acrylate), 3.1 g (14 mmol) diethyl (3-mercaptopropyl)phosphonate and 123 l triethylamine were stirred for 6 days at room temperature. Then, 132 l concentrated hydrochloric acid were added. The suspension was dissolved in dichloromethane and washed three times with water. The organic phase was dried over MgSO.sub.4, filtered, and following the addition of phenothiazine, was concentrated under reduced pressure. The raw product was purified using column chromatography (silica gel) with ethyl acetate. A yellow-orange liquid with a honey-like consistency was obtained.

[0190] The obtained .sup.1H NMR spectrum of 2-((3-((3-(diethoxyphosphoryl)propyl)thio)-propanoyl)oxy)propane-1,3-diyl bis(2-methyl acrylate) is shown in FIG. 7.

[0191] Yield: 35% (5.1 mmol);

[0192] R.sub.f-value: 0.39 (ethyl acetate);

[0193] FT-IR (diamond, cm.sup.1): {tilde over (v)}=2962/2929/2907 (w, v.sub.CH), 1722 (s, v.sub.COOR), 1637 (w, v.sub.CC), 1452 (w, .sub.P C), 1407, 1321, 1295, 1258, 1235 (w, v.sub.PO), 1156 (m, .sub.POC), 1022 (m, .sub.POC), 962, 863, 792 (m, v.sub.POC), 701, 661, 539, 480;

[0194] .sup.1H-NMR (300 MHz, CDCl.sub.3, [ppm]): 6.13-6.11 (m, 2H, n), 5.63-5.60 (m, 2H, n), 5.45-5.35 (m, 1H, i), 4.44-4.25 (m, 4H, j), 4.16-4.04 (m, 4H, b), 2.77 (t, .sup.3J.sub.HH=6.99 Hz, 2H, g), 2.63 (dd, .sup.3J.sub.HH=6.99 Hz, 4H, e and f), 1.95-1.79 (m, 10H, c, d and m), 1.33 (t, .sup.3J.sub.HH=7.13 Hz, 6H, a);

[0195] .sup.13C-NMR (75 MHz, CDCl3, [ppm]): 169.85 (s, h), 165.68 (s, k), 134.63 (s, l), 125.4 (s, n), 68.42 (s, i), 61.46 (s, j), 60.55 (d, .sup.2J.sub.PC=6.40 Hz, b), 33.68 (s, g), 31.52 (d, .sup.3J.sub.PC=18.56 Hz, e), 25.59 (s, f), 23.53 (d, .sup.1J.sub.PC=141.68 Hz, c), 21.47 (d, .sup.2J.sub.PC=4.57 Hz, d), 17.24 (s, m), 15.47 (d, .sup.3J.sub.PC=6 Hz, a);

[0196] .sup.31P-NMR (121 MHz, CDCl.sub.3, [ppm]): 31.23 (s, 1P);

[0197] MS (ESI) m/z: 495 [M+H.sup.+], 517 [M+Na.sup.+], 533 [C.sub.21H.sub.35O.sub.9PS+K.sup.+]; EA.sub.calc. (%): C, 51.00, H, 7.13, S, 6.48; EA.sub.found (%): C, 50.43, H, 7.22, S, 6.65.

EXAMPLE 5

Synthesis of (3-((3-((1,3-bis(methacryloyloxy)propane-2-yl)oxy)-3-oxopropyl)thio)-propyl) phosphonic acid

[0198] ##STR00026##

[0199] In a 100 ml double-neck flask, 2 g (4 mmol) 2-((3-((3-(diethoxy-phosphoryl)propyl)thio)propanoyl)oxy)propane-1,3-diyl bis(2-methyl acrylate) were dissolved in 5.3 ml dry dichloromethane. The solution was de-gassed through the introduction of nitrogen for 1 hour.

[0200] Then, 5.3 ml (40 mmol) bromtrimethyl silane were added, and the solution was stirred for 24 hours at a bath temperature of 23 C. The organic solvents were removed at reduced pressure and dried under vacuum. The interim product was treated with 5 ml methanol and stirred for 1 hour at room temperature. Then, the solvent was removed under reduced pressure. After the product was dried under vacuum, an olive-green, clear, highly viscous liquid was obtained.

[0201] The obtained .sup.1H NMR spectrum of (3-((3-((1,3-bis(methacryloyloxy)propane-2-yl)oxy)-3-oxopropyl)thio)propyl) phosphonic acid is shown in FIG. 8.

[0202] Yield: 90% (3.6 mmol);

[0203] FT-IR (diamond, cm.sup.1): {tilde over (v)}=3498 (b, v.sub.OH), 2957/2921 (w, v.sub.CH), 1718 (m, v.sub.COOH), 1637 (w, v.sub.CC), 1452 (w, .sub.PC), 1409, 1321, 1294, 1258, 1238 (w, v.sub.PO), 1151 (m, .sub.POC), 1006 (m, .sub.POC), 941, 813, 719, 651, 519, 456;

[0204] .sup.1H-NMR (300 MHz, CDCl.sub.3, [ppm]): 9.83 (s, a), 6.06-6.04 (m, 2H, l), 5.56-5.52 (m, 2H, l), 5.37-5.28 (m, 1H, h), 4.36-4.18 (m, 4H, i), 2.69 (t, .sup.3J.sub.HH=6.80 Hz, 2H, f), 2.58-2.52 (q, 4H, d and e), 1.89-1.71 (m, 10H, b, c and m);

[0205] .sup.13C-NMR (75 MHz, CDCl3, [ppm]): 171.14 (s, g), 166.83 (s, j), 135.56 (s, k), 126.59 (s, l), 69.46 (s, h), 62.47 (s, i), 34.66 (s, f), 32.31 (d, .sup.3J.sub.PC=18.72 Hz, d), 26.54 (s, e), 24.67 (d, .sup.1J.sub.PC=144.55 Hz, b), 22.14 (d, .sup.2J.sub.PC=3.64 Hz, c), 18.23 (s, m);

[0206] .sup.31P-NMR (121 MHz, CDCl.sub.3, [ppm]): 35.33 (s, 1P);

[0207] MS (ESI) m/z: 439 [M+H.sup.+], 462 [M+Na.sup.+].

EXAMPLE 6

Step 1

Synthesis of 1,3-bis(4-(3-hydroxypropoxy)phenyl)prop-2-en-1-on

[0208] ##STR00027##

[0209] The chalcone 1,3-bis(4-hydroxyphenyl)prop-2-en-1-on was produced using a method known from the literature using a base-catalysed Claisen-Schmidt condensation of 4 hydroxybenzaldehyde and 4-hydroxyacetophenone (cf. N. Garg, T. Chandra, A. B. Jain and A. Kumar, European journal of medicinal chemistry 45:1529-1535 (2010)).

[0210] 3.6 g (15 mmol) 1,3-bis(4-hydroxyphenyl)prop-2-en-1-on and 4.2 g (30 mmol) potassium carbonate were dissolved in 125 ml anhydrous acetone. Following the addition of a spatula tip of potassium iodide, 3.4 ml (5.28 g, 38 mmol) 3-brompropan-1-ol were added drop by drop via a dropping funnel. The mixture was heated for approx. 23 hours under return flow. The precipitation was filtered and washed with acetone. The clear, yellow filtrate was concentrated under reduced pressure and precipitated in water. The solid obtained was dissolved in acetone and again precipitated in water. Following filtration, the yellow solid was dried under vacuum.

[0211] The obtained .sup.1H NMR spectrum of 1,3-bis(4-(3-hydroxypropoxy)phenyl)prop-2-en-1-on is shown in FIG. 9.

[0212] Yield: 37% (5.5 mmol);

[0213] FT-IR (diamond, cm.sup.1): {tilde over (v)}=3269 (b, v.sub.OH), 2952/2935/2874 (w, v.sub.CH), 1661, 1627 (m, v.sub.CO), 1600/1572/1509 (m, v.sub.Benzyl), 1470, 1421, 1388, 1334, 1305, 1293, 1233, 1174 (s, v.sub.COH), 1116, 1079, 1033, 992, 944, 875, 862, 845, 833, 817 (s, (disubstituted ring), 756, 670, 648, 621, 597, 554, 527, 517;

[0214] .sup.1H-NMR (300 MHz, DMSO-d6, [ppm]): 8.15 (d, .sup.3J.sub.HH=8.92 Hz, 2H, g and i), 7.85-7.78 (m, 3H, m, o and s), 7.68 (d, .sup.3J.sub.HH=15.53 Hz, 1H, l), 7.08 (d, 2H, p and r), 7.01 (d, 2H, f and j), 4.59 (q, .sup.3J.sub.HH=4.91 Hz, 2H, a and w), 4.18-4.09 (2t, .sup.3J.sub.HH=6.47 Hz, 4H, d and t), 3.61-3.54 (m, 4H, b and v), 1.94-1.84 (m, 4H, c and u);

[0215] .sup.13C-NMR (75 MHz, DMSO-d6, [ppm]): 178.16 (s, k), 162.51 (s, e), 160.63 (s, q), 143.07 (s, m), 130.74 (s, g and i), 130.61 (s, o and s), 130.48 (s, h), 127.27 (s, n), 119.34 (s, l), 114.76 (s, f and j), 114.31 (s, p and r), 64.87 (d, J=14.58 Hz, d and t), 57.14 (d, J=3.51 Hz, b and v), 31.96 (d, J=4.10 Hz, c and u);

[0216] MS (ESI) m/z: 357 [M+H.sup.+], 379 [M+K+].

Step 2

Synthesis of diethyl(3-((1,3-bis(4-(3-hydroxypropoxy)phenyl)-3-oxopropyl)thio)-propyl) phosphonate

[0217] ##STR00028##

[0218] 1 g (2.8 mmol) 1,3-bis(4-(3-hydroxypropoxy)phenyl)prop-2-en-1-on, 0.48 g (2.3 mmol) diethyl(3-mercaptopropyl) phosphonate and 38.8 l (28.1 mg, 0.3 mmol) triethylamine were dissolved in 7 ml THF. The reaction mixture was purified through the introduction of nitrogen for 20 minutes, and was heated for 20 hours under return flow. Following a cooling of the reaction mixture to room temperature, 30 ml of dichloromethane were added and the mixture was washed twice with 1-molar, once with 0.1-molar hydrochloric acid and with water. The organic solvent was removed under reduced pressure. Non-converted educt was separated using column chromatography (silica gel) with ethyl acetate. The product was purified using column chromatography (silica gel) with chloroform:methanol (v:v 2:1).

[0219] The obtained .sup.1H NMR spectrum of diethyl(3-((1,3-bis(4-(3-hydroxypropoxy)phenyl)-3-oxopropyl)thio)propyl) phosphonate is shown in FIG. 10.

[0220] Yield: 75% (1.8 mmol);

[0221] R.sub.f-value: 0.91 (chloroform:methanol 2:1);

[0222] FT-IR (diamond, cm.sup.1): {tilde over (v)}=3389 (b, v.sub.OH), 2980/2932/2875 (w, v.sub.CH), 1737, 1672 (m, v.sub.CO), 1598/1574/1510 (m, v.sub.Benzyl), 1472, 1421 (w, .sub.PC), 1392, 1334, 1304, 1248 (m, v.sub.P O), 1226, 1169 (s, v.sub.COH), 1097, 1053, 1023 (s, .sub.POC), 956, 831 (m, (disubstituted ring), 734, 699, 623, 543;

[0223] .sup.1H-NMR (300 MHz, CDCl.sub.3, [ppm]): 7.80 (d, .sup.3J.sub.HH=8.88 Hz, 2H, g and i), 7.23 (d, .sup.3J.sub.HH=8.72 Hz, 2H, o and s), 6.83 (d, .sup.3J.sub.HH=8.88 Hz, 2H, f and j), 6.76 (d, .sup.3J.sub.HH=8.72 Hz, 2H, p and r), 4.41 (t, .sup.3J.sub.HH=7.13 Hz, 1H, m), 4.09 (t, .sup.3J.sub.HH=6.09 Hz, 4H, d and t), 4.06-3.90 (m, 4H, A), 3.79-3.73 (2t, .sup.3J.sub.HH=5.76 Hz, 4H, b and v), 3.35 (dd, .sup.3J.sub.HH=7.08 Hz, 2H, l), 2.40-2.24 (m, 2H, x), 2.21 (s, 2H, a and w), 2.02-1.90 (m, 4H, c and u), 1.76-1.51 (m, 4H, y and z), 1.22 (t, .sup.3J.sub.HH=7.06 Hz, 6H, B);

[0224] .sup.13C-NMR (75 MHz, CDCl.sub.3, [ppm]): 195.49 (s, k), 162.95 (s, e), 157.95 (s, q), 134.08 (s, n), 130.41 (s, g and i), 129.82 (s, h), 128.87 (s, o and s), 114.49 (s, f and j), 114.21 (s, p and r), 65.47 (d, J=3.56 Hz, d and t), 61.59 (d, J=6.47 Hz, b and v), 59.76 (d, .sup.2J.sub.PC=41.30 Hz, A), 45.02 (s, l), 44.01 (s, m), 32.02 (s, J=9.39 Hz, c and u), 31.77 (s, x), 24.53 (d, .sup.1J.sub.PC=141.09 Hz, z), 22.19 (d, .sup.2J.sub.PC=4.23 Hz, y), 16.43 (d, .sup.3J.sub.PC=6.12 Hz, B);

[0225] .sup.31P-NMR (121 MHz, CDCl.sub.3, [ppm]): 31.61 (s, 1P);

[0226] MS (ESI) m/z: 570 [M+H.sup.+]; EA.sub.calc. (%): C, 59.14, H, 7.27, S, 5.64; EA.sub.found (%): C, 59.28, H, 7.20, S, 5.29.

Step 3

Synthesis of methacrylated diethyl(3-((1,3-bis(4-(3-hydroxypropoxy)phenyl)-3-oxopropyl)thio)-propyl) phosphonate

[0227] ##STR00029##

[0228] 0.9 g (1.58 mmol) diethyl(3-((1,3-bis(4-(3-hydroxypropoxy)phenyl)-3-oxopropyl)thio)-propyl) phosphonate and 0.5 ml (0.37 g, 3.66 mmol) triethylamine were dissolved in 3.5 ml dry dichloromethane and cooled in an ice bath to 0 C. After an hour, 0.36 ml (0.38 g, 3.64 mmol) methacryl acid chloride, dissolved in 1 ml dry dichloromethane, were added drop by drop. The solution was brought to room temperature and stirred for 20 hours. The precipitation formed was filtered and the filtrate was washed three times with 50 ml water. The solvent was removed under reduced pressure. The raw product was purified using column chromatography (silica gel) with ethyl acetate. A light yellow liquid with a honey-like consistency was obtained.

[0229] The obtained .sup.1H NMR spectrum of methacrylated diethyl(3-((1,3-bis(4-(3-hydroxypropoxy)phenyl)-3-oxopropyl)thio)-propyl) phosphonate is shown in FIG. 11.

[0230] Yield: 81% (1.3 mmol);

[0231] R.sub.f-value: 0.47 (ethyl acetate);

[0232] FT-IR (diamond, cm.sup.1): {tilde over (v)}=2979/2930/2899/2872 (w, v.sub.CH), 1716 (m, v.sub.CO), 1676 (m, v.sub.CC), 1636, 1599/1575/1510 (m, v.sub.Benzyl), 1472, 1452, 1421 (w, .sub.PC), 1319, 1296, 1232 (m, v.sub.P O), 1162 (s, v.sub.COH), 1114, 1047, 1026 (s, .sub.POC), 954, 831 (m, (disubstituted ring), 814, 650, 624, 543;

[0233] .sup.1H-NMR (300 MHz, CDCl.sub.3, [ppm]): 7.81 (d, .sup.3J.sub.HH=8.88 Hz, 2H, j and l), 7.24 (d, .sup.3J.sub.HH=8.65 Hz, 2H, r and v), 6.83 (d, .sup.3J.sub.HH=8.88 Hz, 2H, i and m), 6.75 (d, .sup.3J.sub.HH=8.65 Hz, 2H, s and u), 6.04-6.02 (m, 2H, b and B), 5.50-5.47 (m, 2H, b and B), 4.43 (t, .sup.3J.sub.HH=7.08 Hz, 1H; p), 4.26 (2t, .sup.3J.sub.HH=6.10 Hz, 4H, e and y), 4.08-3.94 (m, 8H, g, w, G), 3.35 (d, .sup.3J.sub.HH=7.08 Hz, 2H, o), 2.40-2.22 (m, 2H, D), 2.16-2.03 (m, 4H, f and x), 1.86 (s, 6H, a and A), 1.78-1.63 (m, 4H, E and F), 1.22 (t, .sup.3J.sub.HH=7.02 Hz, 6H, H);

[0234] .sup.13C-NMR (75 MHz, CDCl.sub.3, [ppm]): 195.29 (s, n), 167.32 (s, d), 167.28 (s, z), 162.77 (s, h), 157.85 (s, t), 136.26 (s, c), 136.19 (s, C), 134.11 (s, q), 130.39 (s, j and l), 129.95 (s, k), 128.88 (s, r and v), 125.62 (s, b), 125.51 (s, B), 114.42 (s, i and m), 114.17 (s, s and u), 64.69 (s, g), 64.33 (s, w), 61.55 (s, e), 61.46 (s, y), 61.38 (d, .sup.2J.sub.PC=17.10 Hz, G), 45.08 (s, p), 43.75 (s, o), 31.90 (d, .sup.3J.sub.PC=18.02 Hz, D), 28.67 (s, f), 28.51 (s, x), 24.65 (d, .sup.1J.sub.PC=141.03 Hz, F), 22.22 (d, .sup.2J.sub.PC=4.24 Hz, E), 18.31 (s, a and A), 16.45 (d, .sup.3J.sub.PC=5.81 Hz, H);

[0235] .sup.31P-NMR (121 MHz, CDCl.sub.3, [ppm]): 31.46 (s, 1P);

[0236] MS (ESI) m/z: 705 [M+H.sup.+], EA.sub.calc. (%): C, 61.35, H, 7.01, S, 4.55; EA.sub.found (%): C, 60.65, H, 6.94, S, 4.63.

EXAMPLE 7

Synthesis of (3-((1,3-bis(4-3-8methacryloyloxy)propoxy)phenyl)-3-oxopropyl)thio)-propyl-phosphonic acid

[0237] ##STR00030##

[0238] 430 mg (0.61 mmol) methacrylated diethyl(3-((1,3-bis(4-(3-hydroxypropoxy)phenyl)-3-oxopropyl)thio)-propyl) phosphonate were dissolved in a 50 ml double-neck round flask in 6.2 ml dry dichloromethane. The solution was de-gassed through the introduction of nitrogen for 1 hour. Then, 805 l (6.1 mmol) bromtrimethyl silane were added, and the solution was stirred for 9 hours at a bath temperature of 23 C. The organic solvent was removed under reduced pressure and dried under vacuum. The interim product was treated with 5 ml methanol and stirred for 30 minutes at room temperature. Then, the solvent was removed under reduced pressure. After drying the product under vacuum, a dark red, highly viscous liquid was obtained.

[0239] The obtained .sup.1H NMR spectrum of (3-((1,3-bis(4-3-8methacryloyloxy)-propoxy)phenyl)-3-oxopropyl)thio)propyl-phosphonic acid is shown in FIG. 12.

[0240] Yield: 89% (0-54 mmol);

[0241] FT-IR (diamond, cm.sup.1): {tilde over (v)}=3417 (b, v.sub.OH), 2961/2924/2867 (w, v.sub.CH), 1714 (m, v.sub.CO), 1676 (m, v.sub.CC), 1635, 1598/1572/1510 (m, v.sub.Benzyl), 1471, 1451, 1422 (w, .sub.PC), 1356, 1298, 1257 (s, v.sub.P O), 1166 (s, v.sub.COH), 1112, 1043, 1011 (s, .sub.POC), 986, 827, 813 (s, (disubstituted ring), 734, 702, 648, 624, 621, 552, 543;

[0242] .sup.1H-NMR (300 MHz, CDCl.sub.3, [ppm]): 7.91-7.81 (m, 4H, j, l and G), 7.30 (d, .sup.3J.sub.HH=8.59 Hz, 2H, r and v), 6.8 (d, .sup.3J.sub.HH=8.93 Hz, 2H, i and m), 6.11-6.07 (m, 2H, s and u), 6.04-6.02 (m, 2H, b and B), 5.57-5.53 (m, 2H, b and B), 4.45 (t, .sup.3J.sub.HH=7.03 Hz, 1H, p), 4.38-4.29 (m, 4H, e and y), 4.17-4.00 (m, 4H, g and w), 3.42-3.40 (m, 2H, o), 2.45-2.32 (m, 2H, D), 2.22-2.08 (m, 4H, f and x), 1.94-1.89 (m, 6H, a and A), 1.85-1.68 (m, 4H, E and F);

[0243] .sup.13C-NMR (75 MHz, CDCl.sub.3, [ppm]): 196.91 (s, n), 167.65 (s, d), 167.51 (s, z), 163.25 (s, h), 158.03 (s, t), 136.30 (s, c), 136.26 (s, C), 133.89 (s, q), 130.38 (s, j and l), 129.74 (s, k), 128.99 (s, r and v), 125.87 (s, b), 125.84 (s, B), 114.69 (s, i and m), 114.45 (s, s and u), 64.91 (s, g), 64.54 (s, w), 61.76 (s, e), 61.46 (s, y), 45.04 (s, p), 43.55 (s, o), 31.53 (d, .sup.3J.sub.PC=19.14 Hz, D), 28.74 (s, f), 28.60 (s, x), 24.55 (d, .sup.1J.sub.PC=141.63 Hz, F), 21.61 (d, .sup.2J.sub.PC=2.80 Hz, E), 18.42 (s, a and A);

[0244] .sup.31P-NMR (121 MHz, CDCl.sub.3, [ppm]): 35.46 (s, 1P);

[0245] MS (ESI) m/z: 581 [mono-methacrylated M+H.sup.+]; 649 [M+H.sup.+].