Dental materials based on monomers having debonding-on-demand properties

Abstract

The invention relates to a dental restorative material which comprises a thermolabile or photolabile polymerizable compound of Formula I:
[(Z.sup.1).sub.m-Q.sup.1-X)].sub.k-T-[Y-Q.sup.2-(Z.sup.2).sub.n].sub.lFormula I,
in which T represents a thermolabile or photolabile group, Z.sup.1 and Z.sup.2 in each case independently represent a polymerizable group selected from vinyl groups, CH.sub.2CR.sup.1COO and CH.sub.2CR.sup.1CONR.sup.2 or an adhesive group selected from Si(OR).sub.3, COOH, OPO(OH).sub.2, PO(OH).sub.2, SO.sub.2OH and SH, wherein at least one Z.sup.1 or Z.sup.2 is a polymerizable group, Q.sup.1 in each case independently is missing or represents an (m+1)-valent linear or branched aliphatic C.sub.1-C.sub.20 radical which can be interrupted by O, S, COO, OCO, CONR.sup.3, NR.sup.3CO, OCONR.sup.3, NR.sup.3COO or NR.sup.3CONR.sup.3, Q.sup.2 in each case independently is missing or represents an (n+1)-valent linear or branched aliphatic C.sub.1-C.sub.20 radical which can be interrupted by O, S, COO, OCO, CONR.sup.3, NR.sup.3CO, OCONR.sup.3, NR.sup.3COO or NR.sup.3CONR.sup.3, X and Y in each case independently are missing or represent O, S, COO, OCO, CONR.sup.3, NR.sup.3CO, OCONR.sup.3, NR.sup.3COO or NR.sup.3CONR.sup.3, R, R.sup.1, R.sup.2 and R.sup.3 in each case independently represent H or a C.sub.1-C.sub.7 alkyl radical and k, l, m and n in each case independently are 1, 2 or 3.

Claims

1. Dental restorative material which comprises a thermolabile polymerizable compound of Formula II: ##STR00050## in which in each case independently of each other one of Z.sup.1 and Z.sup.2 in each case independently represents a polymerizable group selected from CH.sub.2CR.sup.1COO and CH.sub.2CR.sup.1CONR.sup.2 and the other of Z.sup.1 and Z.sup.2 in each case independently represents an adhesive group selected from Si(OR)3, COOH, OPO(OH)2, PO(OH)2, SO2OH and SH, Q.sup.1 in each case independently is missing or represents a C.sub.1-C.sub.10 radical, Q.sup.2 in each case independently is missing or represents a C.sub.1-C.sub.10 radical, R in each case independently is CH.sub.3 or C.sub.2H.sub.5, R.sup.1 in each case independently is H or CH.sub.3, R.sup.2 in each case independently is H, CH.sub.3 or C.sub.2H.sub.5, R.sup.3 in each case independently is H, CH.sub.3 or C.sub.2H.sub.5, R.sup.4 is H, CH.sub.3 or C.sub.2H.sub.5, R.sup.5 is H, R.sup.6 is H and/or m and n in each case independently are 1 or 2.

2. Dental restorative material according to claim 1, which comprises one or more additional radically polymerizable monomers.

3. Dental restorative material according to claim 2, which comprises methyl, ethyl, hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl (meth)acrylate, bisphenol-A-di(meth)acrylate, bis-GMA, UDMA, di-, tri- or tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra-(meth)acrylate, glycerol di(meth)acrylate, 1,4-butanediol di-(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecane-diol di(meth)acrylate, and/or one or more N-mono- or disubstituted acrylamides, N-ethyl-acrylamide, N,N-dimethacrylamide, N-(2-hydroxyethyl)acrylamide, N-methyl-N-(2-hydroxyethyl)acrylamide, one or more N-mono-substituted methacrylamides, N-ethylmethacrylamide, N-(2-hydroxyethyl)methacrylamide, N-vinylpyrrolidone, one or more cross-linking allyl ethers, and/or one or more cross-linking pyrrolidones, 1,6-bis(3-vinyl-2-pyrrolidonyl)-hexane, one or more cross-linking bisacryl-amides, methylene or ethylene bisacrylamide, one or more cross-linking bis(meth)acrylamides, N,N-diethyl-1,3-bis(acrylamido)-propane, 1,3-bis(methacrylamido)-propane, 1,4-bis(acrylamido)-butane, 1,4-bis(acryloyl)-piperazine, and/or one or more thermolabile cross-linking monomers or a mixture thereof.

4. Dental restorative material according to claim 1, which comprises one or more thermolabile cross-linking monomers.

5. Dental restorative material according to claim 1, which comprises one or more radically polymerizable, acid-group-containing monomers.

6. Dental restorative material according to claim 5, which comprises maleic acid, acrylic acid, methacrylic acid, 2-(hydroxymethyl)-acrylic acid, 4-(meth)acryloyloxyethyltrimellitic anhydride, 10-methacryloyloxydecylmalonic acid, N-(2-hydroxy-3-methacryl-oyloxypropyl)-N-phenylglycine, 4-vinylbenzoic acid, and/or vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinyl-benzylphosphonic acid, 2-methacryloyloxyethylphosphonic acid, 2-methacrylamidoethylphosphonic acid, 4-methacrylamido-4-methyl-pentyl-phosphonic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid, 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]-acrylic acid ethyl- or -2,4,6-trimethylphenyl ester and/or 2-methacryloyloxypropyl mono- or dihydrogen phosphate, 2meth-acryloyloxyethylphenyl hydrogen phosphate, dipentaerythritol-pentamethacryloyloxyphosphate, 10-methacryloyloxydecyl dihydrogen phosphate, phosphoric acid mono-(1-acryloyl-piperidin-4-yl)-ester, 6-(methacrylamido)hexyl dihydrogen phosphate, 1,3-bis-(N-acryloyl-N-propyl-amino)-propan-2-yl-dihydrogen phosphate, and/or vinylsulphonic acid, 4-vinylphenylsulphonic acid, 3-(methacryl-amido)propylsulphonic acid, or a mixture thereof.

7. Dental restorative material according to claim 1, which comprises an initiator for radical polymerization.

8. Dental restorative material according to claim 1, which comprises a thermally gas-releasing additive.

9. Dental restorative material according to claim 1, which comprises an additive which can convert radiated electromagnetic radiation into heat.

10. Dental restorative material according to claim 1, which comprises a) 0.1 to 50 wt.-% compound of Formula II, b) 0.01 to 10 wt.-% initiator, c) 0 to 80 wt.-% comonomer, d) 0 to 30 wt.-% adhesive monomer, e) up to 80 wt.-% filler, f) 0 to 70 wt.-% solvent.

11. Dental restorative material according to claim 1, which comprises a) 1 to 40 wt.-% compound of Formula II, b) 0.1 to 3.0 wt.-% initiator, c) 1 to 60 wt.-% comonomer, d) 0.5 to 15 wt.-% adhesive monomer, e) up to 80 wt.-% filler, f) 0 to 70 wt.-% solvent.

12. Dental restorative material according to claim 1, which comprises a) 2 to 30 wt.-% compound of Formula II, b) 0.2 to 2 wt.-% initiator, c) 5 to 50 wt.-% comonomer, d) 1 to 5 wt.-% adhesive monomer, e) up to 80 wt.-% filler, f) 0 to 70 wt.-% solvent.

13. Dental restorative material according to claim 1, which comprises a) 5 to 30 wt.-% compound of Formula II, b) 0.01 to 10 wt.-% initiator, c) 0 to 80 wt.-% comonomer, d) 0 to 30 wt.-% adhesive monomer, e) up to 80 wt.-% filler, f) 0 to 70 wt.-% solvent.

14. Dental restorative material according to claim 1, in which in each case independently of each other Q.sup.1 in each case independently is missing or represents a C.sub.1-C.sub.8 radical, and/or Q.sup.2 in each case independently is missing or represents C.sub.1-C.sub.8 radical.

15. Dental restorative material according to claim 1, in which in each case independently of each other Q.sup.1 in each case independently is missing or represents a C.sub.2-C.sub.6 radical, and/or Q.sup.2 in each case independently is missing or represents a C.sub.2-C.sub.6 radical.

16. Dental restorative material according to claim 1, in which in each case independently of each other Q.sup.1 in each case independently is missing or represents C.sub.1-C.sub.2 radical, which can be interrupted by O, COO, OCO, CONR3-, NR3-CO, OCONR3-, NR3-COO or NR3-CONR3-, and/or Q.sup.2 in each case independently is missing or represents a C.sub.2-C.sub.3 radical, which can be interrupted by O, COO, OCO, CONR.sup.3, NR.sup.3CO, OCONR.sup.3, NR.sup.3COO or NR.sup.3CONR.sup.3.

Description

EXAMPLES

Example 1

Synthesis of methacrylic acid-3,5-dioxo-4-(3-phosphonooxypropyl)-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-1-ylmethyl ester (MATPA)

Step 1: 4,10-Dioxa-tricyclo[5.2.1.02,6]dec-8-ene-3,5-dione

(1) ##STR00020##

(2) A solution of maleic anhydride (98.06 g, 1.0 mol) and furan (102.12 g, 1.5 mol) in acetonitrile (200 ml) was stirred for 96 h at room temperature. The precipitate formed was filtered off, washed with acetonitrile (100 ml) and dried in a vacuum drying oven (125 mbar, 50 C.). 123.30 g (740 mmol, 74% yield) of a white solid was obtained.

(3) .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): =3.31 (s, 2H), 5.35 (s, 2H), 6.58 (s, 2H).

(4) .sup.13C-NMR (DMSO-d.sub.6, 100 MHz): =49.0, 81.6, 136.8, 171.5.

Step 2: 4-(3-Hydroxy-propyl)-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-ene-3,5-dione

(5) ##STR00021##

(6) A solution of 3-amino-1-propanol (15.02 g, 200 mmol) in methanol (30 ml) was added dropwise to a suspension of 4,10-dioxa-tricyclo[5.2.1.0.sup.2,6]dec-8-ene-3,5-dione (33.23 g, 200 mmol) in methanol (70 ml). The reaction mixture was then heated under reflux. After 24 h, the solution was concentrated on a rotary evaporator. The yellowish solid was dissolved in water (100 ml) and extracted with dichloromethane (3200 ml). The combined organic phases were dried over Na.sub.2SO.sub.4, filtered, concentrated on the rotary evaporator and dried under fine vacuum. 25.40 g (114 mmol, 57% yield) of a white solid was obtained.

(7) .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): =1.59 (m, 2H), 2.91 (s, 2H), 3.38 (m, 4H), 4.45 (br s, 1H), 5.12 (s, 2H), 6.55 (s, 2H). .sup.13C-NMR (DMSO-d.sub.6, 100 MHz): =30.5, 35.5, 47.0, 58.3, 80.3, 136.4, 176.4.

Step 3: 1-(3-Hydroxy-propyl)-pyrrole-2,5-dione

(8) ##STR00022##

(9) A solution of 4-(3-hydroxy-propyl)-10-oxa-4-aza-tricyclo[5.2.1.0.sup.2,6]dec-8-ene-3,5-dione (17.80 g, 79.8 mmol) in toluene (300 ml) was heated under reflux for 16 h. The solution was concentrated on the rotary evaporator and the residue dried under fine vacuum. 11.92 g (76.8 mmol, 96% yield) of a white solid was obtained.

(10) .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): =1.65 (m, 2H), 3.40 (t, 2H; J=6.2 Hz), 3.47 (t, 2H; J=7.4 Hz), 4.48 (br s, 1H), 6.99 (s, 2H).

(11) .sup.13C-NMR (DMSO-d.sub.6, 100 MHz): =31.2, 34.7, 58.4, 134.4, 171.0.

Step 4: Methacrylic acid-4-(3-hydroxypropyl)-3,5-dioxo-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-1-ylmethyl ester

(12) ##STR00023##

(13) 1-(3-Hydroxy-propyl)-pyrrole-2,5-dione (5.17 g, 33.3 mmol), furfuryl methacrylate (5.65 g, 34.0 mmol) and BHT (10 mg) were dissolved in benzene (60 ml). The solution was heated under reflux accompanied by the introduction of a light air stream. The solvent was distilled off after 20 h. The brownish oil was purified by means of column chromatography (SiO.sub.2, ethyl acetate). 2.84 g (8.8 mmol, 27% yield, mixture of exo and endo isomer) of a yellowish oil was obtained.

(14) .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): (endo isomer)=1.55-1.64 (m, 2H), 1.88 (s, 3H), 3.01-3.05 (d, 1H; J=6.4 Hz), 3.09 (d, 1H; J=6.4 Hz), 3.32-3.49 (m, 4H), 4.41 (d, 1H; J=12.8 Hz), 4.45-4.48 (m, 1H), 4.78-4.84 (m, 1H), 5.15 (d, 1H; J=1.5 Hz), 5.68-5.70 (m, 1H), 6.00-6.03 (m, 1H), 6.47-6.52 (m, 1H), 6.58-6.64 (m, 1H).

(15) .sup.13C-NMR (DMSO-d.sub.6, 100 MHz): (endo isomer)=17.8, 30.5, 35.6, 48.1, 49.6, 58.2, 61.7, 80.5, 88.8, 126.2, 135.4, 136.7, 137.3, 166.1, 174.7, 176.0.

Step 5: Methacrylic acid-3,5-dioxo-4-(3-phosphonooxypropyl)-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-1-ylmethyl ester (MATPA)

(16) ##STR00024##

(17) A solution of methacrylic acid-4-(3-hydroxypropyl)-3,5-dioxo-10-oxa-4-aza-tricyclo[5.2.1.0.sup.2,6]dec-8-en-1-ylmethyl ester (2.6 g, 8.2 mmol), BHT (10 mg) and triethylamine (910 mg, 9.0 mmol) in tetrahydrofuran (20 ml) was added dropwise to a solution of phosphoroxychloride (1.39 g, 9.0 mmol) in tetrahydrofuran (30 ml) at 5 C. After addition was complete, the suspension was stirred for 3 h at 5 C. and then water (2 ml) was added dropwise. The suspension was stirred for a further 30 min at 5 C. and the precipitate was then filtered off cold. The yellowish filtrate was washed with saturated aqueous NaCl solution (330 ml). The combined aqueous phases were re-extracted with tetrahydrofuran (230 ml). The combined organic phases were dried over Na.sub.2SO.sub.4, filtered and concentrated on the rotary evaporator. The brownish oil had acetonitrile (250 ml) added to it to remove water and was concentrated on the rotary evaporator. The residue had diethyl ether (50 ml) added to it and was stirred at room temperature. The solvent was decanted off after 1 h. The brown oil was dried on the rotary evaporator and under fine vacuum. 2.46 g (6.1 mmol, 75% yield, mixture of exo and endo isomer) of a brownish resin was obtained.

(18) .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): (endo isomer)=1.73-1.82 (m, 2H), 1.87 (s, 3H), 3.03 (d, 1H; J=6.5 Hz), 3.10 (d, 1H; J=6.5 Hz), 3.42-3.48 (m, 2H), 3.76-3.84 (m, 2H), 4.41 (d, 1H; J=12.5 Hz), 4.84 (d, 1H; J=12.5 Hz), 5.15 (s, 1H), 5.69 (s, 1H), 6.01 (s, 1H), 6.50 (d, 1H; J=5.7 Hz), 6.59-6.63 (m, 1H), 6.94 (br, 2H).

(19) .sup.13C-NMR (DMSO-d.sub.6, 100 MHz): (endo isomer)=17.8, 28.2 (d, J=7 Hz), 35.2, 48.2, 49.7, 61.6, 63.0 (d, J=5 Hz), 80.4, 88.8, 126.2, 135.4, 136.7, 137.3, 166.1, 174.7, 176.0.

(20) .sup.31P-NMR (DMSO-d.sub.6, 162 MHz): =1.3.

Example 2

Synthesis of methacrylic acid-3-(3,5-dioxo-1-phosphonooxymethyl-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-4-yl)-propyl ester

Step 1: Methacrylic acid-3-(2,5-dioxo-2,5-dihydro-pyrrol-1-yl)-propyl ester

(21) ##STR00025##

(22) 1-(3-Hydroxypropyl)-pyrrole-2,5-dione (5.36 g, 34.5 mmol), triethylamine (3.85 g, 38.0 mmol) and N,N-dimethylaminopyridine (120 mg, 1.0 mmol) were dissolved in dichloromethane (80 ml). A solution of methacrylic anhydride (5.86 g, 38.0 mmol) and BHT (10 mg) in dichloromethane (20 ml) was added dropwise at 0 C., and the reaction mixture was then stirred for 2 h at 0 C. and 22 h at room temperature. The reaction solution was washed with water (350 ml). The combined aqueous phases were re-extracted with dichloromethane (50 ml). The combined organic phases were dried over Na.sub.2SO.sub.4, filtered and concentrated on the rotary evaporator. The crude product was purified by means of column chromatography (SiO.sub.2, n-hexane/ethyl acetate 1:1). 2.81 g (12.5 mmol, 35% yield) of a yellowish oil was obtained.

(23) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.95 (2, 3H), 1.97-2.04 (m, 2H), 3.66 (t, 2H; J=6.9 Hz), 4.15 (t, 2H; J=6.2 Hz), 5.57 (m, 1H), 6.12 (s, 1H), 6.72 (s, 2H).

(24) .sup.13C-NMR (CDCl.sub.3, 100 MHz): =18.3, 27.6, 34.9, 61.8, 125.6, 134.2, 126.2, 167.2, 170.6.

Step 2: Methacrylic acid-3-(1-hydroxymethyl-3,5-dioxo-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-4-yl)-propyl ester

(25) ##STR00026##

(26) Methacrylic acid-3-(2,5-dioxo-2,5-dihydro-pyrrol-1-yl)-propyl ester (2.71 g, 12.1 mmol), furfuryl alcohol (1.28 g, 13.0 mmol) and BHT (10 mg) were dissolved in benzene (40 ml). The solution was heated under reflux accompanied by the introduction of a light air stream. The solvent was distilled off after 20 h. The brownish oil obtained as crude product was purified by means of column chromatography (SiO.sub.2, ethyl acetate). 3.10 g (9.6 mmol, 80% yield, mixture of exo and endo isomer) of a yellow oil was obtained.

(27) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.78-1.89 (m, 0.4H; exo), 1.93-2.02 (m, 5.8H; exo/endo), 2.94-3.02 (m, 3H; endo), 3.43-3.48 (m, 0.6H; exo), 3.55-3.69 (m, 2.2H; exo/endo), 4.05-4.14 (m, 4.4H; exo/endo), 4.15-4.22 (m, 0.2H; exo), 4.25-4.31 (m, 0.2H; exo), 5.25 (m, 1H; endo), 5.28-5.32 (m, 0.2H; exo), 5.57-5.60 (m, 1.2H; exo/endo), 6.10-6.12 (m, 0.2H; endo), 6.12-6.14 (m, 1H; endo), 6.35-6.38 (m, 0.2H; exo), 6.46-6.49 (m, 0.2H; exo), 6.52-6.56 (m, 1H; endo), 6.59-6.62 (m, 1H; endo).

(28) .sup.13C-NMR (CDCl.sub.3, 100 MHz): =18.3, 26.6 (endo), 26.7 (exo), 35.5 (exo), 35.8 (endo), 46.0 (exo), 48.1 (endo), 49.9, 60.7 (endo), 61.3 (exo), 61.4 (endo), 61.6 (exo), 79.5 (exo), 80.9 (endo), 91.5 (endo), 92.1 (exo), 125.7 (endo), 125.8 (exo), 134.9 (exo), 135.7 (exo), 136.1 (exo), 136.2 (endo), 137.0 (endo), 138.3 (endo), 167.2 (exo), 167.3 (endo), 174.7 (exo), 175.1 (exo), 175.8 (endo), 175.9 (endo).

Step 3: Methacrylic acid-3-(3,5-dioxo-1-phosphonooxymethyl-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-4-yl)-propyl ester

(29) ##STR00027##

(30) A solution of methacrylic acid-3-(1-hydroxymethyl-3,5-dioxo-10-oxa-4-aza-tricyclo[5.2.1.0.sup.2,6]dec-8-en-4-yl)-propyl ester (3.00 g, 9.3 mmol), BHT (10 mg) and triethylamine (1.04 g, 10.3 mmol) in tetrahydrofuran (20 ml) was added dropwise to a solution of phosphoroxychloride (1.57 g, 10.3 mmol) in tetrahydrofuran (30 ml) at 5 C. After addition was complete, the suspension was stirred for 3 h at 5 C. and then water (2 ml) was added dropwise. The suspension was stirred for a further 30 min at 5 C. and the precipitate was then filtered off cold. The yellowish filtrate was washed with saturated aqueous NaCl solution (330 ml). The combined aqueous phases were re-extracted with tetrahydrofuran (230 ml). The combined organic phases were dried over Na.sub.2SO.sub.4, filtered and concentrated on the rotary evaporator. The brownish oil had acetonitrile (250 ml) added to it to remove water and was concentrated on the rotary evaporator. The residue had diethyl ether (250 ml) added to it and was stirred at room temperature. The solvent was decanted off after 1 h. The brown oil was dried on the rotary evaporator and under fine vacuum. 3.19 g (7.9 mmol, 85% yield, mixture of exo and endo isomer) of a hygroscopic white foam was obtained.

(31) .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): =1.65-1.75 (m, 0.4H; exo), 1.75-1.85 (m, 2H; endo), 1.87 (s, 3.6H; exo/endo), 3.02 (dd, 2H; J=28.2 Hz, 6.4 Hz; endo), 3.29 (t, 0.4H; J=7.0 Hz; exo), 3.41-3.49 (m, 2.2H; exo/endo), 3.66 (dd, 0.2H; J=7.8 Hz, 5.6 Hz; exo), 3.94-4.08 (m, 3.4H; exo/endo), 4.32 (dd, 0.2H; J=12.2 Hz, 5.2 Hz; exo), 4.42 (dd, 0.2H; J=12.2 Hz, 5.8 Hz; exo), 4.54 (q, 1H; J=6.1 Hz; endo), 5.08-5.11 (m, 1H; endo), 5.25-5.29 (m, 0.2H; exo), 5.64-5.68 (m, 1.2H; exo/endo), 6.00-6.05 (m, 1.2H; exo/endo), 6.36 (d, 0.2H, J=5.5 Hz; exo), 6.44-6.50 (m, 1.2H; exo/endo), 6.54-6.58 (m, 1H; endo), 6.66 (br s, 2.4H; exo/endo). .sup.13C-NMR (DMSO-d.sub.6, 100 MHz): =17.9, 26.1 (exo), 26.2 (endo), 34.6 (exo), 34.8 (endo), 45.6 (exo), 47.3 (exo), 48.0 (endo), 49.8 (endo), 61.5 (endo), 61.6 (exo), 62.9 (d, J=5 Hz; endo), 63.3 (d, J=5 Hz; exo), 78.7 (exo), 80.4 (endo), 89.7 (d, J=10 Hz; endo), 90.0 (d, J=10 Hz; exo), 125.6, 134.5 (exo), 135.4 (exo), 135.8 (endo), 136.8 (endo), 137.0 (endo), 166.4, 174.7 (exo), 174.7 (endo), 174.8 (exo), 176.1 (endo).

Example 3

(32) Radical Photopolymerization of the Phosphoric Acid Methacrylate MATPA from Example 1

(33) A mixture of 2.97 g of the phosphoric acid methacrylate MATPA from Example 1, 6.95 g of the cross-linker N,N-diethyl-1,3-bis(acrylamido)-propane, 0.03 g of the photoinitiator camphorquinone and 0.05 g of the amine accelerator 4-(dimethylamino)-benzoate was prepared. A drop of the mixture was placed on a glass plate, covered with a PET film and irradiated with a Bluephase polymerization lamp (Ivoclar Vivadent AG, light intensity 1000 mW/cm.sup.2) for 20 s. The irradiated layer was then cured. The mixture was furthermore examined by means of photo DSC (Differential Scanning calorimetry, Perkin Elmer DSC 7) and a polymerization heat of 273 J/g was measured.

Example 4

(34) Preparation of a Light-Curing Adhesive Based on the Phosphoric Acid Methacrylate MATPA from Example 1

(35) An adhesive was prepared from 1.09 g of the phosphoric acid methacrylate MATPA from Example 1, 1.49 g of the monofunctional comonomer 2-hydroxyethyl methacrylate, 3.25 g of the cross-linker bis-GMA, 0.99 g of the cross-linker UDMA, 1.01 g of the cross-linker glycerol dimethacrylate, 0.02 g of the photoinitiator camphorquinone, 0.05 g of the amine accelerator 4-(dimethylamino)-benzoate, 0.10 g of the acylphosphine oxide photoinitiator Lucirin TPO and 2.00 g of the solvent ethanol. The adhesive was able to be cured by means of a Bluephase polymerization lamp (Ivoclar Vivadent AG, light intensity 1000 mW/cm.sup.2).

Example 5

Synthesis of methacrylic acid-3-[3,5-dioxo-1-(11-phosphonooxyundecyloxymethyl)-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-4-yl]-propyl ester

Step 1: 2-(11-bromoundecyloxy)-tetrahydropyran

(36) ##STR00028##

(37) 3,4-Dihydro-2H-pyran (21.87 g, 260 mmol) was added dropwise to a solution of 11-bromoundecanol (50.24 g, 200 mmol) and toluene-4-sulphonic acid monohydrate (80 mg, 0.4 mmol) in dichloromethane (100 ml). The reaction mixture was stirred at room temperature. After 24 h, the brown solution was filtered over a thin layer of silica gel. The filtrate was concentrated on the rotary evaporator and dried under fine vacuum. 65.85 g (196 mmol, 98% yield) of a light yellowish oil was obtained.

(38) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.23-1.37 (m, 12H), 1.37-1.47 (m, 2H), 1.48-1.64 (m, 6H), 1.65-1.76 (m, 1H), 1.77-1.90 (m, 3H), 3.35-3.42 (m, 3H), 3.46-3.53 (m, 1H), 3.70-3.75 (m, 1H), 3.84-3.90 (m, 1H), 4.56-4.58 (m, 1H).

(39) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =19.7, 25.4, 26.2, 28.2, 28.8, 29.4, 29.5, 29.6, 29.8, 30.8, 32.9, 33.9, 62.3, 67.7, 98.8.

Step 2: 2-[11-(Furan-2-ylmethoxy)-undecyloxy]-tetrahydropyran

(40) ##STR00029##

(41) Furfuryl alcohol (9.81 g, 100 mmol) was added dropwise to a suspension of sodium hydride (2.40 g, 100 mmol) in THF (100 ml). The suspension was stirred for 1 h at room temperature, then a solution of 2-(11-bromoundecyloxy)-tetrahydropyran (33.53 g, 100 mmol) in THF (100 ml) was added dropwise. The reaction mixture was heated for 16 h under reflux. After the cooling, quenching was carried out with saturated aqueous NH.sub.4Cl solution (100 ml). The two-phase mixture was extracted with ethyl acetate (3100 ml). The combined organic phases were dried over Na.sub.2SO.sub.4, filtered, concentrated on the rotary evaporator and dried under fine vacuum. The crude product was purified by means of column chromatography (SiO.sub.2, dichloromethane). 20.58 g (58.4 mmol, 58% yield) of a yellowish oil was obtained.

(42) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.25-1.40 (m, 16H), 1.48-1.62 (m, 6H), 1.66-1.74 (m, 1H), 1.78-1.87 (m, 1H), 3.34-3.40 (m, 1H), 3.45 (t, 2H; J=6.8 Hz), 3.47-3.52 (m, 1H), 3.70-3.75 (m, 1H), 3.84-3.90 (m, 1H), 4.42 (s, 2H), 4.56-4.58 (m, 1H), 6.28-6.30 (m, 1H), 6.32-6.33 (s, 1H), 7.38-7.39 (m, 1H).

(43) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =19.7, 25.5, 26.1, 26.3, 29.1, 29.4, 29.5, 29.5, 29.5, 29.6, 29.7, 29.8, 30.8, 62.3, 64.7, 67.7, 70.4, 98.8, 108.9, 110.2, 142.6, 152.2.

Step 3: 11-(Furan-2-ylmethoxy)-undecan-1-ol

(44) ##STR00030##

(45) A solution of 2-[11-(furan-2-ylmethoxy)-undecyloxy]-tetrahydropyran (20.48 g, 58.1 mmol) and toluene-4-sulphonic acid monohydrate (480 mg, 2.4 mmol) in methanol (100 ml) was stirred for 20 h at room temperature. The reaction mixture was concentrated on the rotary evaporator and the crude product was purified by means of column chromatography (SiO.sub.2, ethyl acetate). 7.18 g (26.8 mmol, 46% yield) of a yellowish solid was obtained.

(46) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.25-1.37 (m, 14H), 1.51-1.62 (m, 4H), 1.84 (s, 1H), 3.45 (t, 2H; J=6.8 Hz), 3.61 (t, 2H; J=6.8 Hz), 4.43 (s, 2H), 6.29-6.30 (m, 1H), 6.32-6.34 (m, 1H), 7.39-7.40 (m, 1H).

(47) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =25.8, 26.1, 29.4, 29.5, 29.5, 29.6, 29.6, 32.8, 62.9, 64.7, 70.4, 108.9, 110.2, 142.6, 152.1.

Step 4: Methacrylic acid-3-[3,5-dioxo-1-(11-hydroxy-undecyloxymethyl)-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-4-yl]-propyl ester

(48) ##STR00031##

(49) A solution of 11-(furan-2-ylmethoxy)-undecan-1-ol (7.00 g, 26.1 mmol), methacrylic acid-3-(2,5-dioxo-2,5-dihydro-pyrrol-1-yl)-propyl ester (5.82 g, 26.1 mmol) and BHT (10 mg) in toluene (100 ml) was heated to 80 C. accompanied by the introduction of a light air stream. After 20 h, the solution was concentrated on the rotary evaporator and the crude product was purified by means of column chromatography (SiO.sub.2, ethyl acetate). 6.16 g (12.5 mmol, 48% yield, mixture of exo and endo isomer) was obtained as yellowish oil.

(50) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.25-1.36 (m, 22.4H; exo/endo), 1.51-1.63 (m, 6.6H; exo/endo), 1.76 (s, 1.6H; exo/endo), 1.81-1.88 (m, 1.2H; exo), 1.92-1.98 (m, 6.4H; exo/endo), 2.91 (dd, 2H; J=40.2 Hz, 6.4 Hz; endo), 3.43-3.51 (m, 2.4H; exo), 3.52-3.65 (m, 8.4H), 3.81 (d, 1H; J=11.6 Hz; endo), 4.01 (d, 0.6H; J=11.6 Hz; endo), 4.06-4.15 (m, 5H; exo/endo), 5.23-5.24 (m, 1H; endo), 5.28-5.30 (m, 0.6H; exo), 5.57-5.58 (m, 1.6H; exo/endo), 6.11-6.14 (m, 1.6H; exo/endo), 6.30-6.32 (d, 0.6H; J=5.8 Hz; exo), 6.44-6.46 (m, 0.6H; exo), 6.51-6.54 (m, 2H; endo). .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =18.3, 18.3, 25.7, 26.0, 26.7, 29.4, 29.4, 29.4, 29.5, 29.5, 29.5, 29.6, 32.8, 35.4, 35.7, 45.7, 47.8, 48.3, 49.9, 61.5, 61.6, 62.9, 67.9, 68.4, 72.1, 72.2, 79.6, 81.0, 90.7, 91.4, 125.6, 125.7, 135.1, 135.3, 136.1, 136.2, 136.6, 138.1, 167.2, 174.5, 174.8, 175.0, 176.0.

Step 5: Methacrylic acid-3-[3,5-dioxo-1-(11-phosphonooxyundecyloxymethyl)-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-4-yl]-propyl ester

(51) ##STR00032##

(52) A solution of methacrylic acid-3-[3,5-dioxo-1-(11-hydroxy-undecyloxymethyl)-10-oxa-4-aza-tricyclo[5.2.1.0.sup.2,6]dec-8-en-4-yl]-propyl ester (6.06 g, 12.3 mmol), BHT (10 mg) and triethylamine (1.37 g, 13.6 mmol) in THF (30 ml) was added dropwise at 5 C. to a solution of phosphoroxychloride (2.08 g, 13.6 mmol) in THF (50 ml). After addition was complete, the suspension was stirred for 3 h at 5 C. and then water (2 ml) was added dropwise. The suspension was stirred for a further 30 min in an ice bath and the precipitate was then filtered off cold. The yellowish filtrate was washed with saturated aqueous NaCl solution (350 ml). The combined aqueous phases were re-extracted with THF (230 ml). The combined organic phases were dried over Na.sub.2SO.sub.4, filtered and concentrated on the rotary evaporator. The brownish oil had acetonitrile (250 ml) added to it to remove water and was concentrated on the rotary evaporator. The brown oil had diethyl ether (4100 ml) added to it and was stirred at room temperature for 10 min. A dark-brown oil precipitated out. The solvent was decanted off. The combined ether solution was concentrated on the rotary evaporator and dried under fine vacuum. 3.87 g (6.8 mmol, 55% yield, mixture of exo and endo isomer) of a brownish oil was obtained.

(53) .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): =1.22-1.32 (m, 22.4H; exo/endo), 1.43-1.60 (m, 6.6H; exo/endo), 1.69-1.76 (m, 1.2H; exo), 1.80-1.85 (m, 2H; endo), 1.87-1.91 (m, 5.8H; exo/endo), 2.96 (dd, 2H; J=55.6 Hz, 6.4 Hz; endo), 3.30 (t, 1H; J=6.4 Hz; endo), 3.36-3.54 (m, 6H; endo), 3.59-3.66 (m, 1.6H; exo/endo), 3.90-4.09 (m, 7.2H; exo/endo), 5.08-5.09 (m, 1H; endo), 5.24-5.26 (m, 0.6H; exo), 5.67-5.69 (m, 1.6H; exo/endo), 6.00-6.06 (m, 1.6H; exo/endo), 6.32-6.34 (m, 0.6H; exo), 6.43-6.47 (m, 1.6H; exo/endo), 6.52-6.55 (m, 1H; endo), 8.68 (br s, 3.2H; exo/endo).

(54) .sup.13C-NMR (DMSO-d.sub.6, 100.6 MHz): =17.9, 25.1, 25.5, 26.1, 28.6, 28.8, 29.0, 29.0, 29.0, 29.8, 29.9, 30.4, 34.7, 45.5, 47.3, 48.1, 49.6, 61.3, 61.6, 65.2 (d; J=5 Hz), 67.6, 68.1, 70.9, 71.0, 78.7, 80.3, 90.3, 90.8, 125.6, 134.5, 135.9, 135.8, 136.4, 137.6, 166.3, 166.4, 174.7, 174.9, 175.0, 176.2.

(55) .sup.31P-NMR (DMSO-d.sub.6, 162 MHz): =1.1.

Example 6

Synthesis of methacrylic acid-3,5-dioxo-4-(10-phosphonooxy-decyl)-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-1-ylmethyl ester

Step 1: 4-(10-Hydroxy-decyl)-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-ene-3,5-dione

(56) ##STR00033##

(57) A solution of 10-amino-1-decanol (5.36 g, 30.9 mmol) in methanol (20 ml) was added dropwise to a suspension of 4,10-dioxatricyclo[5.2.1.0.sup.2,6]dec-8-ene-3,5-dione (5.13 g, 30.9 mmol) in methanol (30 ml). The reaction mixture was heated under reflux for 24 h and then concentrated on the rotary evaporator. The crude product was purified by means of column chromatography (SiO.sub.2, ethyl acetate). 1.52 g (4.7 mmol, 15% yield) of a yellowish solid was obtained.

(58) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.22-1.37 (m, 12H), 1.51-1.59 (m, 4H), 2.60 (br s, 1H), 2.84 (s, 2H), 3.46 (t, 2H; J=7.4 Hz), 3.62 (t, 2H; J=6.5 Hz), 5.26 (s, 2H), 6.51 (s, 2H).

(59) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =25.7, 26.6, 27.5, 29.0, 29.3, 29.3, 29.4, 32.7, 39.0, 47.4, 62.9, 80.9, 136.6, 176.4.

Step 2: 1-(10-Hydroxy-decyl)-pyrrole-2,5-dione

(60) ##STR00034##

(61) A suspension of 4-(10-hydroxy-decyl)-10-oxa-4-aza-tricyclo[5.2.1.0.sup.2,6]-dec-8-ene-3,5-dione (1.52 g, 4.7 mmol) in toluene (50 ml) was heated under reflux for 16 h. The solution was decanted off from the undissolved residue, concentrated on the rotary evaporator and dried under fine vacuum. 1.15 g (4.5 mmol, 97% yield) of a white solid was obtained.

(62) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.25-1.36 (m, 12H), 1.52-1.61 (m, 4H), 2.63 (br s, 1H), 3.50 (t, 2H; J=7.2 Hz), 3.63 (t, 2H; J=6.8 Hz), 6.69 (s, 2H).

(63) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =25.7, 26.7, 28.5, 29.0, 29.3, 29.4, 32.7, 37.9, 63.0, 134.0, 170.9.

Step 3: Methacrylic acid-4-(10-hydroxydecyl)-3,5-dioxo-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-1-ylmethyl ester

(64) ##STR00035##

(65) A solution of furfuryl methacrylate (750 mg, 4.5 mmol), 1-(10-hydroxy-decyl)-pyrrole-2,5-dione (1.05 g, 4.1 mmol) and BHT (5 mg) in toluene (30 ml) was heated to 80 C. accompanied by the introduction of a light air stream. After 20 h the reaction solution was concentrated on the rotary evaporator and dried under fine vacuum. The crude product was purified by column chromatography (SiO.sub.2, n-hexane/ethyl acetate 1:1). 560 mg (1.3 mmol, 33% yield) of the endo isomer was obtained as a white solid and 430 mg (1.0 mmol, 25% yield) of the exo isomer as a yellowish oil.

(66) Endo Isomer:

(67) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.19-1.36 (m, 12H), 1.37-1.46 (m, 2H), 1.52-1.61 (m, 3H), 1.97 (s, 3H), 3.31 (t, 2H; J=7.6 Hz), 3.38 (d, 1H; J=7.6 Hz), 3.61-3.66 (m, 3H), 4.69 (d, 1H; J=12.8 Hz), 4.91 (d, 1H; J=12.8 Hz), 5.31 (dd, 1H; J=5.3 Hz, 1.7 Hz), 5.61-5.61 (m, 1H), 6.17 (s, 1H), 6.36 (d, 1H; J=5.8 Hz), 6.45 (dd, 1H; J=5.7 Hz, 1.6 Hz).

(68) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =18.3, 25.7, 26.8, 27.4, 29.0, 29.3, 29.4, 32.8, 38.7, 46.8, 47.7, 62.2, 62.9, 79.6, 89.8, 126.5, 134.4, 135.6, 135.7, 166.8, 174.4, 174.6.

(69) Exo Isomer:

(70) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.25-1.35 (m, 12H), 1.52-1.58 (m, 4H), 1.95 (s, 3H), 1.99 (br s, 1H), 2.95 (dd, 2H; J=28.2 Hz, 6.5 Hz), 3.46 (t, 2H; J=7.5 Hz), 3.61 (t, 2H; J=6.8 Hz), 4.52 (d, 1H; J=12.8 Hz), 4.98 (d, 1H; J=12.8 Hz), 5.27 (d, 1H; J=1.6 Hz), 5.59-5.61 (m, 1H), 6.13 (s, 1H), 6.45 (d, 1H; J=5.8 Hz), 6.56 (dd, 1H; J=5.6 Hz, 1.6 Hz).

(71) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =18.3, 25.8, 26.6, 27.5, 29.0, 29.3, 29.3, 29.4, 32.8, 39.0, 48.3, 49.9, 61.6, 62.9, 81.1, 89.6, 126.3, 135.8, 137.1, 137.4, 166.8, 174.3, 175.8.

Step 4: Methacrylic acid-3,5-dioxo-4-(10-phosphonooxy-decyl)-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-1-ylmethyl ester

(72) ##STR00036##

(73) A solution of endo/exo methacrylic acid-4-(10-hydroxydecyl)-3,5-dioxo-10-oxa-4-aza-tricyclo[5.2.1.0.sup.2,6]dec-8-en-1-ylmethyl ester (890 mg, 2.1 mmol), BHT (5 mg) and triethylamine (240 mg, 2.3 mmol) in THF (30 ml) was added dropwise to a solution of phosphoroxychloride (360 mg, 2.3 mmol) in THF (20 ml) at 5 C. After addition was complete, the suspension was stirred for 3 h at 5 C. and then water (2 ml) was added dropwise. The suspension was stirred for a further 30 min in the ice bath and the precipitate was then filtered off cold. The yellowish filtrate was washed with saturated aqueous NaCl solution (350 ml). The combined aqueous phases were re-extracted with THF (230 ml). The combined organic phases were dried over Na.sub.2SO.sub.4, filtered and concentrated on the rotary evaporator. The brownish oil had acetonitrile (250 ml) added to it to remove water and was concentrated on the rotary evaporator. The residue was dried under fine vacuum. 1.01 g (2.0 mmol, 95% yield, mixture of exo and endo isomer) of a colourless oil was obtained.

Example 7

(74) Preparation of DoD Adhesives Based on the Methacrylate Phosphates from Examples 5 and 6

(75) 3 primer solutions were prepared in order to examine the shear adhesion between a ZrO.sub.2 ceramic and a composite cement according to the invention. These were solutions of 1 wt.-% each of the methacrylate phosphate from Example 5 (primer A), of the methacrylate phosphate from Example 6 (primer B) and of 10-methacryloyloxydecyl phosphate (primer C, comparison) in ethanol respectively.

(76) To determine the bond strength the respective primer solutions were applied to ZrO.sub.2 ceramic testpieces (IPS e.max ZirCAD, Ivoclar Vivadent, yttrium-stabilized zirconium oxide) and the solvent was blown off. The composite cement Multilink Automix (Ivoclar Vivadent) was then applied to the primer layer and cured for 20 s with the Bluephase C8 LED lamp (Ivoclar Vivadent) and then for 3 min in the Spectramat light furnace (Ivoclar Vivadent). The testpieces were then stored in water for 24 h at 37 C. and the adhesive shear strength was measured analogously to the ISO guideline ISO 1994-ISO TR 11405: Dental Materials Guidance on Testing of Adhesion to Tooth Structure. In a second run, the testpieces were additionally stored in a drying oven at 130 C. for 60 min after water storage and only then was the shear adhesion determined after rapid cooling of the testpieces. The results are presented in Tab. 1 and show that with a temperature load of the ceramic composite bond the primers with the adhesive monomers according to the invention display a much greater decrease in the bond strength and therefore such a bond can be more easily debonded.

(77) TABLE-US-00002 TABLE 1 Adhesive shear strength (ASS, in MPa) of the bond between ZrO.sub.2 ceramic and composite cement Primer ASS after WS.sup.a) ASS after WS + TT.sup.b) A 28.4 13.9 B 21.6 10.3 C 30.1 21.7 (comparison) .sup.a)WS = water storage, .sup.b)WS + TT = water storage and thermal treatment

Example 8

Synthesis of 4-[4(5)-(methacryloyloxymethyl) -2-pyridin-2-yl-3,6-dihydro-2H-thiopyran -2-ylsulphanylmethyl]-benzoic acid-2-(methacryloyloxy)-ethyl ester

Step 1: 2-Benzenesulphonylmethylpyridine

(78) ##STR00037##

(79) A suspension of 2-(chloromethyl)pyridine hydrochloride (32.81 g, 200 mmol) in acetonitrile (200 ml) had sodium phenyl sulphinate (49.24 g, 300 mmol), tetrapropylammonium bromide (10.64 g, 40 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (30.44 g, 200 mmol) added to it. The reaction mixture was heated under reflux for 16 h and then concentrated on the rotary evaporator. The residue was taken up in dichloromethane (200 ml), washed with saturated aqueous NaCl solution (3100 ml), dried over Na.sub.2SO.sub.4, filtered and concentrated to approximately half the volume on the rotary evaporator. The brown solution was filtered over a layer of silica gel. 41.55 g (178 mmol; 89% yield) of a yellowish solid was obtained.

(80) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =4.56 (s, 2H), 7.21-7.24 (m, 1H), 7.42-7.48 (m, 3H), 7.58-7.62 (m, 1H), 7.66-7.70 (m, 3H), 8.41-8.42 (m, 1H).

(81) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =64.6, 123.4, 125.7, 128.4, 129.0, 133.8, 136.7, 138.2, 148.8, 149.7.

Step 2: 4-(Pyridine-2-carbothioylsulphanylmethyl)-benzoic acid

(82) ##STR00038##

(83) A solution of 1,8-diazabicyclo[5.4.0]undec-7-ene (79.56 g, 523 mmol) in acetonitrile (100 ml) was added dropwise to a suspension of 2-benzenesulphonylmethylpyridine (40.64 g, 174 mmol) and sulphur (16.76 g, 523 mmol) in acetonitrile (500 ml) accompanied by ice cooling. After addition was complete, the dark red solution was stirred for 22 h at room temperature. 4-(Bromomethyl)benzoic acid (37.46 g, 174 mmol) was then added in portions. The reaction mixture was stirred for a further 4 h at room temperature and then had 2N hydrochloric acid (200 ml) added to it (pH=1). A red precipitate precipitated out of the red solution. The suspension was filtered and the filtration residue was washed with acetonitrile (100 ml). The filtrate had tert-butyl methyl ether (200 ml) and saturated aqueous NaCl solution (100 ml) added to it. The phases were separated and the organic phase was washed with saturated aqueous NaCl solution (2100 ml). The combined aqueous phases were then re-extracted with tert-butyl methyl ether (100 ml). The combined organic phases were dried over Na.sub.2SO.sub.4, filtered and concentrated on the rotary evaporator. The residue was combined with the previously obtained filtration residue, had acetonitrile (200 ml) added to it and was stirred for 4 h at room temperature. The obtained suspension was then filtered. The filtration residue was washed with acetonitrile (50 ml) and dried in the vacuum drying oven (50 C., 125 mbar). 44.95 g (155 mmol; 89% yield) of a red solid was obtained.

(84) .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): =4.66 (s, 2H), 7.56-7.58 (m, 2H), 7.70-7.73 (m, 1H), 7.94-7.96 (m, 2H), 7.00-8.03 (m, 1H), 8.26-8.28 (m, 1H), 8.66-8.68 (m, 1H), 13.03 (s, 1H). .sup.13C-NMR (DMSO-d.sub.6, 100.6 MHz): =39.6, 121.9, 127.8, 129.4, 129.5, 129.9, 137.7, 140.6, 148.3, 155.3, 166.9, 226.0.

Step 3: 4-(Pyridine-2-carbothioylsulphanylmethyl)-benzoic acid-2-(methacryloyloxy)-ethyl ester

(85) ##STR00039##

(86) A suspension of 4-(pyridine-2-carbothioylsulphanylmethyl)-benzoic acid (10.39 g, 35.9 mmol), 2-hydroxyethyl methacrylate (4.67 g, 35.9 mmol), N,N-dimethylaminopyridine (600 mg, 5.0 mmol) and BHT (10 mg) in dichloromethane (100 ml) was cooled to 0 C. 3-(Ethyliminomethylideneamino)-N,N-dimethyl-propane-1-aminehydrochloride (8.26 g, 43.1 mmol) was added and the reaction mixture was stirred for 1 h at 0 C. and for 16 h at room temperature. The red reaction solution was filtered over a layer of silica gel (SiO.sub.2, dichloromethane) and the filtrate was concentrated on the rotary evaporator. The oily red solid had n-hexane (100 ml) added to it, was stirred for 20 h at room temperature and filtered. The filtration residue was washed with n-hexane (50 ml) and dried in the vacuum drying oven (50 C., 125 mbar). 11.22 g (27.9 mmol; 78% yield) of a light red solid was obtained.

(87) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.95 (s, 3H), 4.47-4.50 (m, 2H), 4.54-4.58 (m, 4H), 5.58-5.59 (m, 1H), 6.13-6.14 (m, 1H), 7.46-7.49 (m, 3H), 7.7-7.81 (m, 1H), 7.98-8.00 (m, 2H), 8.31-8.33 (m, 1H), 8.59-8.61 (m, 1H).

(88) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =18.3, 40.8, 62.4, 62.7, 122.3, 126.2, 127.0, 129.0, 129.5, 130.0, 135.9, 137.0, 141.0, 148.0, 156.1, 166.0, 167.1, 225.4.

Step 4: Methacrylic acid-2-methylene-but-3-enyl ester

(89) ##STR00040##

(90) Lithium diisopropylamide (30 wt.-% in paraffin oil, 53.58 g, 150 mol) had diethyl ether (150 ml) added to it and was cooled to 5 C. Isoprene monoxide (11.78 g, 140 mmol) was then added dropwise. The reaction mixture was stirred for 3 h at 5 C. and then for 1 h at room temperature. Accompanied by ice cooling, 2N hydrochloric acid (100 ml) was added and the phases were separated. The organic phase was washed with aqueous NaHCO.sub.3 solution (5 wt.-%; 100 ml) and the combined aqueous phases were re-extracted with diethyl ether (550 ml). The combined organic phases were then dried over Na.sub.2SO.sub.4, filtered and concentrated on the rotary evaporator (40 C., 750 mbar90 mbar). The obtained yellowish oil was extracted with acetonitrile (3100 ml) and the combined acetonitrile solutions were concentrated on the rotary evaporator (40 C., 150 mbar90 mbar). The thus-obtained yellow liquid was dissolved in dichloromethane (70 ml). Triethylamine (5.06 g, 50.0 mmol) and N,N-dimethylaminopyridine (600 mg, 5.0 mmol) were added and the solution was cooled to 5 C. A solution of methacrylic anhydride (7.71 g, 50.0 mmol) and BHT (10 mg) in dichloromethane (30 ml) was added dropwise. The reaction mixture was stirred for 2 h at 5 C. and for 22 h at room temperature, washed with water (3100 ml), dried over Na.sub.2SO.sub.4, filtered and concentrated on the rotary evaporator. The yellow-brown oil was dissolved in dichloromethane (50 ml) and filtered over a layer of silica gel. The filtrate was concentrated on the rotary evaporator and dried under fine vacuum. 3.85 g (25.3 mmol; 51% yield) of a yellow liquid was obtained.

(91) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.97 (s, 3H), 4.84 (s, 2H), 5.14 (d, J=11.2 Hz; 1H), 5.22-5.29 (m, 3H), 5.58 (s, 1H), 6.14 (s, 1H), 6.39 (dd, J=11.0 Hz, 17.8 Hz; 1H).

(92) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =18.3, 63.7, 114.6, 117.8, 125.7, 136.2, 136.2, 140.7, 167.0.

Step 5: 4-[4(5)-(Methacryloyloxymethyl)-2-pyridin-2-yl-3,6-dihydro-2H-thiopyran-2-ylsulphanylmethyl]-benzoic acid-2-(methacryloyloxy)-ethyl ester

(93) ##STR00041##

(94) 4-(Pyridine-2-carbothioylsulphanylmethyl)-benzoic acid-2-(methacryl-oyloxy)-ethyl ester (6.59 g, 16.4 mmol) and trifluoroacetic acid (1.87 g, 16.4 mmol) were dissolved in chloroform (70 ml). A solution of methacrylic acid-2-methylene-but-3-enyl ester (3.75 g, 24.6 mmol) in chloroform (30 ml) was added dropwise. The initially red solution was stirred for 24 h at room temperature, wherein an increasing decolourization occurred. The solution was then washed with aqueous NaHCO.sub.3 solution (5 wt.-%; 350 ml), dried over Na.sub.2SO.sub.4, filtered and concentrated on the rotary evaporator. The slightly reddish crude product was purified by column chromatography (SiO.sub.2, n-hexane/ethyl acetate 4:1). 7.22 g (13.0 mmol; 80% yield) of the inseparable isomer mixture was obtained as a yellowish oil.

(95) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.94 (s, 3H), 1.95 (s, 3H), 2.84-2.95 (m, 1H), 3.07-3.20 (m, 2H), 3.44-3.56 (m, 2H), 3.78 (d, J=12.8 Hz; 1H), 4.46-4.48 (m, 2H), 4.53-4.55 (m, 2H), 4.57-4.63 (m, 2H), 5.56-5.59 (m, 2H), 5.88-5.89 (m, 0.7H), 5.97-5.98 (m, 0.3H), 6.12 (s, 1H), 6.13 (s, 1H), 7.13-7.16 (m, 3H), 7.60-7.65 (m, 1H), 7.69-7.74 (m, 1H), 7.82-7.85 (m, 2H), 8.51-8.54 (m, 1H). .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =18.3, 18.3, 26.1, 26.4, 35.1, 38.9, 39.4, 61.1, 62.4, 62.6, 68.1, 68.7, 121.5, 121.6, 122.5, 122.6, 124.9, 125.8, 126.1, 128.2, 128.2, 129.0, 129.0, 129.6, 129.7, 129.8, 132.2, 135.9, 136.1, 136.7, 136.7, 143.2, 143.4, 148.1, 148.2, 161.2, 161.4, 166.0, 167.0, 167.1.

Example 9

Synthesis of methacrylic acid-4-[3-(methacryloyloxy)-propyl]-3,5-dioxo-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-1-ylmethyl ester

(96) ##STR00042##

(97) 1-Hydroxymethyl-4-(3-hydroxy-propyl)-10-oxa-4-aza-tricyclo[5.2.1.0.sup.2,6]dec-8-ene-3,5-dione (18.29 g, 72.2 mmol), triethylamine (16.08 g, 159 mmol), N,N-dimethylaminopyridine (600 mg, 5.0 mmol) and BHT (10 mg) were dissolved in dichloromethane (100 ml). A solution of methacrylic anhydride (24.49 g, 159 mmol) in dichloromethane (50 ml) was added dropwise at 0 C. The clear yellow solution was stirred for 2 h at 0 C., then the ice bath was removed and stirring was continued at room temperature. After 22 h the reaction solution was washed with water (3100 ml). The combined aqueous phases were re-extracted with dichloromethane (100 ml). The combined organic phases were dried over Na.sub.2SO.sub.4, filtered and concentrated on the rotary evaporator. The brownish oil was purified by means of column chromatography (SiO.sub.2, n-hexane/ethyl acetate 2:1). 15.04 g (38.6 mmol, 53% yield, mixture of exo and endo isomer) of a yellow oil was obtained.

(98) .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): =1.81-1.90 (m, 9.6H; exo/endo), 3.04 (d, 1H; J=6.5 Hz; endo), 3.10 (d, 1H; J=6.5 Hz; endo), 3.31-3.35 (m, 0.4H; exo), 3.47-3.51 (m, 2.2H; exo/endo), 3.70-3.73 (m, 0.2H; exo), 3.99-4.05 (m, 2.4H; exo/endo), 4.41 (d, 1H; J=12.6 Hz; endo), 4.63 (d, 0.2H; J=12.8 Hz; exo), 4.79 (d, 0.2H; J=12.8 Hz; exo), 4.84 (d, 1H; J=12.6 Hz; endo), 5.15 (d, 1H; J=1.6 Hz; endo), 5.32 (dd, 0.2H; J=5.6 Hz, 1.5 Hz; exo), 5.67-5.69 (m, 2.2H; exo/endo), 5.71-5.73 (m, 0.2H; exo), 6.01-6.08 (m, 2.4H; exo/endo), 6.42 (d, 0.2H; J=6.1 Hz; exo), 6.49-6.53 (m, 1.2H; exo/endo), 6.60-6.62 (m, 1H; endo).

(99) .sup.13C-NMR (DMSO-d.sub.6, 100.6 MHz): =17.8 (endo), (17.8; exo), 17.9, (26.2), 26.2, (34.6), 34.9, (46.4), (47.3), 48.2, 49.7, 61.4, (61.5), 61.6, (62.0), (78.8), 80.5, 88.8 (89.1), 125.5, 126.1, (126.3), (134.3), (135.4), 135.5, (135.7), 135.8, 136.6, 137.2, 166.0, 166.4, (174.5), (174.6), 174.7, 176.0.

Example 10

Synthesis of methacrylic acid-3,5-dioxo-4-(3-triethoxysilylpropyl)-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-1-ylmethyl ester

Step 1: N-(3-Triethoxysilylpropyl)-maleimide (SI126)

(100) ##STR00043##

(101) Maleic anhydride (29.42 g, 300 mmol) was suspended in toluene (100 ml). A solution of 3-aminopropyltriethoxysilane (66.41 g, 300 mmol) in toluene (75 ml) was added dropwise and the reaction solution was stirred at room temperature. After 2 h zinc chloride (13.63 g, 100 mmol) was added first, then a solution of hexamethyldisilazane (60.52 g, 375 mmol) in toluene (75 ml) was added dropwise. The suspension was heated under reflux for 24 h and filtered over Celatom after cooling to room temperature. The filtrate was concentrated on the rotary evaporator and dried under fine vacuum. The crude product was purified by vacuum distillation (bp: 125 C./0.03 mbar). 15.14 g (50.3 mmol, 17% yield) of a colourless liquid was obtained.

(102) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =0.41-0.49 (m, 2H), 1.08 (t, 9H; J=7.1 Hz), 1.49-1.60 (m, 2H), 3.37 (t, 2H; J=7.3 Hz), 3.60-3.70 (m, 6H), 6.59 (s, 2H).

(103) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =6.1, 16.7, 20.5, 38.7, 56.8, 132.5, 169.2.

(104) .sup.29Si-NMR (CDCl.sub.3, 79.5 MHz): =46.4.

Step 2: Methacrylic acid-3,5-dioxo-4-(3-triethoxysilylpropyl)-10-oxa-4-aza-tricyclo[5.2.1.02,6]dec-8-en-1-ylmethyl ester

(105) ##STR00044##

(106) A solution of furfuryl methacrylate (8.24 g, 49.6 mmol), N-(3-triethoxysilylpropyl)-maleimide (14.94 g, 49.6 mmol) and BHT (10 mg) in toluene (150 ml) was heated to 80 C. accompanied by the introduction of a light air stream. After 20 h the solvent was concentrated on the rotary evaporator and the crude product was purified by means of column chromatography (SiO.sub.2, n-hexane/ethyl acetate 2:1). 5.67 g (12.1 mmol, 24% yield, mixture of exo and endo isomer) of a colourless oil was obtained.

(107) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =0.43-0.47 (m, 2.2H; exo/endo), 1.06-1.10 (m, 9.9H; exo/endo), 1.37-1.46 (m, 0.2H; exo), 1.50-1.58 (m, 2H, endo), 1.82 (s, 3H; endo), 1.84 (s, 0.3H; exo), 2.85 (dd, 2H, J=28.2 Hz, 6.4 Hz; endo), 3.19 (t, 0.2H; J=7.3 Hz; exo), 3.28 (d, 0.2H; J=7.3 Hz; exo), 3.35 (t, 2H; J=7.3 Hz; endo), 3.63-3.71 (m, 6.6H; exo/endo), 4.38 (d, 1H, J=12.7 Hz; endo), 4.56 (d, 0.1H, J=12.7 Hz; exo), 4.78 (d, 0.1H, J=12.7 Hz; exo), 4.87 (d, 1H, J=12.7 Hz; endo), 5.15 (s, 1H; endo), 5.18-5.20 (m, 0.1H; exo), 5.48 (s, 1H; endo), 5.50 (s, 0.1H; exo), 6.00 (s, 1H; endo), 6.05 (s, 0.1H; exo), 6.22 (d, 0.1H, J=5.4 Hz; exo), 6.34 (d, 1.1H, J=5.4 Hz; endo/exo), 6.45-6.47 (m, 1H; endo).

(108) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =5.9 (endo), 6.3 (exo), 16.6, 19.5, 45.2 (exo), 46.1 (exo), 46.7 (endo), 48.3 (endo), 56.7, 60.0 (endo), 60.6 (exo), 77.9 (exo), 79.4 (endo), 87.9 (endo), 78.1 (exo), 124.6 (endo), 124.8 (exo), 132.8 (exo), 134.0 (exo), 134.1 (exo), 134.1 (endo), 135.5 (endo), 135.8 (endo), 165.1, 172.7 (endo), 172.8 (exo), 172.9 (exo), 174.2 (endo).

(109) .sup.29Si-NMR (CDCl.sub.3, 79.5 MHz): =46.6 (exo), 46.3 (endo).

Example 11

Synthesis of bis-(4-methacryloyloxybenzoyl)-diethylgermanium

Step 1: 2-(4-Methoxyphenyl)-1,3-dithiane

(110) ##STR00045##

(111) A solution of p-anisaldehyde (136.2 g, 1.0 mol) in chloroform (500 ml) had 1,3-propanedithiol (108.2 g, 1.0 mol) added to it and was cooled to 10 C. An HCl gas stream was passed through the suspension for 45 min. Stirring was then carried out for a further 30 min at 0 C., then the cooling bath was removed and the reaction mixture was stirred for 16 h at room temperature. The solvent was removed on the rotary evaporator and the residue had methanol (300 ml) added to it. The suspension was stirred for 24 h at room temperature and filtered. The filtration residue was washed with methanol (50 ml) and dried in the vacuum drying oven (125 mbar, 50 C.). 219.9 g (970 mmol, 97% yield) of a white solid was obtained (mp: 117-119 C.)

(112) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.87-1.97 (m, 1H, CH.sub.2), 2.13-2.20 (m, 1H, CH.sub.2), 2.88-2.93 (m, 2H, SCH.sub.2), 3.02-3.09 (m, 2H, SCH.sub.2), 3.79 (s, 3H, OCH.sub.3), 5.13 (s, 1H, SCHS), 6.85-6.87 (m, 2H, ArH.sup.3,5), 7.38-7.40 (m, 2H, ArH.sup.2,6).

(113) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =25.1 (CH.sub.2), 32.2 (CH.sub.2), 50.1 (SCS), 55.3 (OCH.sub.3), 114.1 (ArC.sup.3,5), 128.9 (ArC.sup.2,6), 131.3 (ArC.sup.1), 159.6 (ArC.sup.4).

Step 2: Bis-[2-(4-methoxyphenyl)-1,3-dithian-2-yl]-diethylgermanium

(114) ##STR00046##

(115) 2-(4-Methoxyphenyl)-1,3-dithiane (113.2 g, 500 mmol) was dissolved in absolute THF (500 ml) under protective gas and cooled to 5 C. A 2.5 M butyllithium solution in n-hexane (200 ml, 500 mmol) was added dropwise. The brown reaction solution was then stirred for 3 h at 5 C., then a solution of diethylgermanium dichloride (42.0 g, 208 mmol) in absolute THF (100 ml) was added dropwise. The reaction mixture was stirred further overnight in the thawing ice bath, then water (200 ml) and ethyl acetate (400 ml) were added and the phases were separated. The organic phase was washed with water (2125 ml) and the combined aqueous phases were re-extracted with ethyl acetate (150 ml). The combined organic phases were washed with saturated aqueous NaCl solution (150 ml), dried over Na.sub.2SO.sub.4, filtered, concentrated on the rotary evaporator and dried under fine vacuum. The residue had ethyl acetate (100 ml) added to it and the suspension was stirred at room temperature. After 20 h methanol (100 ml) was added and after a further 24 h the suspension was filtered. The filtration residue was washed with ethyl acetate (20 ml) and dried in the vacuum drying oven (125 mbar, 50 C.). 88.8 g (153 mol, 73% yield) of a white solid was obtained (mp: 115-116 C.)

(116) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.15 (m, 6H, CH.sub.3), 1.28 (m, 4H, GeCH.sub.2), 1.77-1.81 (m, 2H, CH.sub.2), 1.94-2.05 (m, 2H, CH.sub.2), 2.24-2.29 (m, 4H, SCH.sub.2), 2.70-2.77 (m, 4H, SCH.sub.2), 3.82 (s, 6H, OCH.sub.3), 6.80-6.82 (m, 4H, ArH.sup.3,5), 7.78-7.80 (m, 4H, ArH.sup.2,6).

(117) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =4.5 (CH.sub.3), 10.2 (GeCH.sub.2), 25.2 (CH.sub.2), 25.6 (SCH.sub.2), 51.2 (GeCS), 55.2 (OCH.sub.3), 113.3 (ArC.sup.3,5), 131.4 (ArC.sup.2,6), 132.5 (ArC.sup.1), 157.5 (ArC.sup.4).

Step 3: Bis-(4-methoxybenzoyl)-diethylgermanium

(118) ##STR00047##

(119) A solution of bis-[2-(4-methoxyphenyl)-1,3-dithian-2-yl]-diethylgermanium (87.21 g, 150 mol) in THF (900 ml) had water (220 ml) added to it. Calcium carbonate (180.2 g, 1.80 mol) and iodine (456.9 g, 1.80 mol) were divided into eight identical portions each. After intervals of 30 min in each case, one portion each of CaCO.sub.3 and iodine was added to the reaction mixture accompanied by intermittent ice-cooling. After addition was complete, the reaction mixture was stirred for 24 h at room temperature and then filtered over a thin layer of silica gel. The red-brown filtrate had saturated aqueous sodium dithionite solution (1600 ml) added to it accompanied by intensive stirring, until the colour changed completely to yellow. The suspension was filtered and the filtration residue was washed with ethyl acetate (400 ml). The filtrate was diluted with ethyl acetate (800 ml) and the phases were separated. The organic phase was washed with water (2250 ml) and the combined aqueous phases were re-extracted with ethyl acetate (2200 ml). The combined organic phases were washed with saturated aqueous NaCl solution (200 ml), dried over Na.sub.2SO.sub.4, filtered, concentrated on the rotary evaporator and dried under fine vacuum. The crude product was purified by means of column chromatography (SiO.sub.2, n-hexane/ethyl acetate 9:1). 38.4 g (95.9 mmol, 64% yield) of a yellow solid was obtained (mp: 47-50 C.)

(120) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.12 (t, 6H; J=7.9 Hz, CH.sub.3), 1.47 (q, 4H; J=7.9 Hz, GeCH.sub.2), 3.80 (s, 6H, OCH.sub.3), 6.87-6.91 (m, 4H, ArH.sup.3,5), 7.71-7.75 (m, 4H, ArH.sup.2,6).

(121) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =6.4 (CH.sub.3), 9.0 (GeCH.sub.2), 55.5 (OCH.sub.3), 114.1 (ArC.sup.3,5), 130.5 (ArC.sup.2,6), 135.0 (ArC.sup.1), 163.8 (ArC.sup.4), 227.4 (CO).

Step 4: Bis-(4-hydroxybenzoyl)-diethylgermanium

(122) ##STR00048##

(123) Bis-(4-methoxybenzoyl)diethylgermanium (8.0 g, 20.0 mmol) was dissolved in anhydrous toluene (200 ml) under protective gas and had Celatom (10 g) and aluminium chloride (9.6 g, 72.0 mmol) added to it. The reaction mixture was heated for 2 h under reflux. After cooling, water (10 ml) was added and the suspension was stirred for 10 min at room temperature. The solvent was removed on the rotary evaporator. The residue had ethyl acetate (300 ml) added to it. The suspension was stirred for 16 h at room temperature and filtered over a thin layer of silica gel. The filtrate was concentrated on the rotary evaporator. The oily brown residue had chloroform (200 ml) added to it. The suspension was stirred for 16 h at room temperature and filtered. The filtration residue was washed with chloroform (80 ml) and dried in the vacuum drying oven (50 C., 125 mbar). 4.23 g (11.3 mmol, 57% yield) of a light yellow solid was obtained (mp: 167-168 C.)

(124) .sup.1H-NMR (DMSO-d.sub.6, 400 MHz): =1.04 (t, 6H; J=7.9 Hz, CH.sub.3), 1.38 (q, 4H; J=7.9 Hz, GeCH.sub.2), 6.88 (d, 4H; J=8.5 Hz, ArH.sup.3,5), 7.58 (d, 4H; J=8.5 Hz, ArH.sup.2,6), 10.53 (s, 2H, OH).

(125) .sup.13C-NMR (DMSO-d.sub.6, 100.6 MHz): =6.1 (CH.sub.3), 8.9 (GeCH.sub.2), 115.7 (ArC.sup.3,5), 130.3 (ArC.sup.2,6), 133.3 (ArC.sup.1), 162.7 (ArC.sup.4), 225.5 (CO).

Step 5: Bis-(4-methacryloyloxybenzoyl)-diethylgermanium

(126) ##STR00049##

(127) A solution of methacrylic anhydride (5.89 g, 38.2 mmol) and BHT (10 mg) in dichloromethane (50 ml) was added dropwise to a solution of bis-(4-hydroxybenzoyl)-diethylgermanium (6.78 g, 18.2 mmol), triethylamine (3.86 g, 38.2 mmol) and N,N-dimethylaminopyridine (240 mg, 2.0 mmol) in dichloromethane (100 ml) at 5 C. After addition was complete, the solution was stirred for 1 h at 5 C. and for 20 h at room temperature. The reaction solution was washed with water (3100 ml). The combined aqueous phases were re-extracted with dichloromethane (250 ml). The combined organic phases were dried over Na.sub.2SO.sub.4, filtered, concentrated on the rotary evaporator and dried under fine vacuum. The crude product was purified by means of column chromatography (SiO.sub.2, n-hexane/ethyl acetate 4:1). 4.40 g (8.6 mmol, 47% yield) of a yellow solid was obtained.

(128) .sup.1H-NMR (CDCl.sub.3, 400 MHz): =1.13 (t, 6H; J=7.9 Hz, CH.sub.3), 1.51 (q, 4H; J=7.9 Hz, GeCH.sub.2), 2.04 (s, 6H, CH.sub.3), 5.79-5.77 (m, 2H, CCH), 6.34 (s, 2H, CCH), 7.23-7.20 (m, 4H, ArH.sup.3,5), 7.80-7.77 (m, 4H, ArH.sup.2,6).

(129) .sup.13C-NMR (CDCl.sub.3, 100.6 MHz): =6.5 (GeCH.sub.2), 9.0 (GeCH.sub.2CH.sub.3), 18.3 (CH.sub.3), 122.3 (Ar C.sup.3,5), 128.0 (CCH.sub.2), 129.6 (ArC.sup.2,6), 135.4 (CC), 138.6 (ArC.sup.1), 155.0 (ArC.sup.4), 165.1 (CO), 228.3 (GeCO).