SPECIFICALLY GLYCO-SUBSTITUTED PORPHYRINS AND CHLORINS FOR PHOTODYNAMIC THERAPY

Abstract

The present invention provides certain tetrapyrrolic compounds having a structure of Formula (1), (2), or (3) wherein B is (I), (II) (III) or (IV), O—R.sup.1 is a substituent in the meta or para position of the phenyl ring, R.sup.1 is a glyco-substituent derived from a mono-, di-, or trisaccharide group, and each R.sup.2 is independently selected from the group consisting of a linear or branched (fluoro-)alkyl group with 3 to 8 carbon atoms, phenyl, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl, 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl, meta- or para-hydroxyphenyl, meta- or para-carboxyphenyl, and meta- or para-YO-phenyl with Y being a polyethyleneglycol-residue with (CH.sub.2CH.sub.2O).sub.nCH.sub.3 with n=1-30.

##STR00001## ##STR00002##

Claims

1. A tetrapyrrolic compound having a structure of Formula 1, 2, or 3: ##STR00051## wherein B is ##STR00052## O—R.sup.1 is a substituent in the meta or para position of the phenyl ring, R.sup.1 is a glyco-substituent derived from a mono-, di-, or trisaccharide group, and each R.sup.2 is independently selected from the group consisting of a linear or branched (fluoro-)alkyl group with 3 to 8 carbon atoms, phenyl, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl, 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl, meta- or para-hydroxyphenyl, meta- or para-carboxyphenyl, and meta- or para-YO-phenyl with Y being a polyethyleneglycol-residue with (CH.sub.2CH.sub.2O).sub.nCH.sub.3 with n=1-30, wherein (a) in Formula 1 or 2, if B is ##STR00053## O—R.sup.1 is a substituent in the para position of the phenyl ring and R.sup.1 is glucosyl, then each R.sup.2 is independently selected from the group consisting of a linear or branched alkyl group with 5 to 8 carbon atoms, a linear or branched fluoroalkyl group with 3 to 8 carbon atoms, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl, 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl, meta- or para-hydroxyphenyl, meta- or para-carboxyphenyl, and meta- or para-YO-phenyl with Y being a polyethyleneglycol-residue with (CH.sub.2CH.sub.2O).sub.nCH.sub.3 with n=1-30, (b) in Formula 1 or 2, if B is ##STR00054## O—R.sup.1 is a substituent in the para position of the phenyl ring and R.sup.1 is galactosyl, then each R.sup.2 is independently selected from the group consisting of a linear or branched (fluoro-)alkyl group with 3 to 8 carbon atoms, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl, 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl, meta- or para-hydroxyphenyl, meta- or para-carboxyphenyl, and meta- or para-YO-phenyl with Y being a polyethyleneglycol-residue with (CH.sub.2CH.sub.2O).sub.nCH.sub.3 with n=1-30, (c) in Formula 1 or 2, if O—R.sup.1 is a substituent in the meta position of the phenyl ring and R.sup.1 is glucosyl and R.sup.2 is n-hexyl, phenyl or 3,5-bis(trifluoromethyl)phenyl, then B is ##STR00055## (d) in Formula 1 or 2, if O—R.sup.1 is a substituent in the meta position of the phenyl ring and R.sup.1 is galactosyl and R.sup.2 is phenyl, then B is ##STR00056## (e) in Formula 3, if B is ##STR00057## O—R.sup.1 is a substituent in the para position of the phenyl ring and R.sup.1 is glucosyl, then each R.sup.2 is independently selected from the group consisting of a linear or branched (fluoro-)alkyl group with 5 to 8 carbon atoms, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl, 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl, meta- or para-hydroxyphenyl, meta- or para-carboxyphenyl, and meta- or para-YO-phenyl with Y being a polyethyleneglycol-residue with (CH.sub.2CH.sub.2O).sub.nCH.sub.3 with n=1-30, (f) in Formula 3, if B is ##STR00058## O—R.sup.1 is a substituent in the meta position of the phenyl ring and R.sup.1 is glucosyl, then each R.sup.2 is independently selected from the group consisting of a linear or branched (fluoro-)alkyl group with 3 to 8 carbon atoms, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl, 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl, meta- or para-hydroxyphenyl, meta- or para-carboxyphenyl, and meta- or para-YO-phenyl with Y being a polyethyleneglycol-residue with (CH.sub.2CH.sub.2O).sub.nCH.sub.3 with n=1-30, and (g) in Formula 3, if B is ##STR00059## O—R.sup.1 is a substituent in the para position of the phenyl ring and R.sup.1 is galactosyl, then each R.sup.2 is independently selected from the group consisting of a linear or branched (fluoro-)alkyl group with 3 to 8 carbon atoms, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl, 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl, meta- or para-hydroxyphenyl, meta- or para-carboxyphenyl, and meta- or para-YO-phenyl with Y being a polyethyleneglycol-residue with (CH.sub.2CH.sub.2O).sub.nCH.sub.3 with n=1-30.

2. The tetrapyrrolic compound according to claim 1, wherein (a) in Formula 1 or 2, if B is ##STR00060## O—R.sup.1 is a substituent in the para position of the phenyl ring and R.sup.1 is glucosyl, then each R.sup.2 is independently selected from the group consisting of a linear or branched alkyl group with 5 to 8 carbon atoms, a linear or branched fluoroalkyl group with 3 to 8 carbon atoms, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl, and 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl, (b) in Formula 1 or 2, if B is ##STR00061## O—R.sup.1 is a substituent in the para position of the phenyl ring and R.sup.1 is galactosyl, then each R.sup.2 is independently selected from the group consisting of a linear or branched (fluoro-)alkyl group with 3 to 8 carbon atoms, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl, and 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl, (e) in Formula 3, if B is ##STR00062## O—R.sup.1 is a substituent in the para position of the phenyl ring and R.sup.1 is glucosyl, then each R.sup.2 is independently selected from the group consisting of a linear or branched (fluoro-)alkyl group with 5 to 8 carbon atoms, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl, and 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl, (f) in Formula 3, if B is ##STR00063## O—R.sup.1 is a substituent in the meta position of the phenyl ring and R.sup.1 is glucosyl, then each R.sup.2 is independently selected from the group consisting of a linear or branched (fluoro-)alkyl group with 3 to 8 carbon atoms, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl, and 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl, and (g) in Formula 3, if B is ##STR00064## O—R.sup.1 is a substituent in the para position of the phenyl ring and R.sup.1 is galactosyl, then each R.sup.2 is independently selected from the group consisting of a linear or branched (fluoro-)alkyl group with 3 to 8 carbon atoms, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl, 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl.

3. The tetrapyrrolic compound according to claim 1, wherein R.sup.1 is a glycosyl group of a mono- or disaccharide, wherein the mono- or disaccharide is preferably selected from the group consisting of glucose, galactose, mannose, ribose, fructose, rhamnose, lactose, partially deoxygenated derivatives thereof, aminosugars, such as glucosamines or galactosamines, neuraminic acids and combinations thereof.

4. The tetrapyrrolic compound according to claim 1, wherein R.sup.1 is mannosyl or lactosyl and R.sup.2 is a linear or branched (fluoro-)alkyl group with 3 to 8 carbon atoms, phenyl, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl or 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl.

5. The tetrapyrrolic compound according to claim 4, wherein B is ##STR00065## O—R.sup.1 is a substituent in the para position of the phenyl ring and R.sup.2 is phenyl.

6. The tetrapyrrolic compound according to claim 1, wherein in Formula 1 or 2 O—R.sup.1 is a substituent in the meta position of the phenyl ring, R.sup.1 is glucosyl and each R.sup.2 is a linear or branched fluoroalkyl group with 3 to 8 carbon atoms, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl or 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl.

7. The tetrapyrrolic compound according to claim 1, wherein in Formula 3 B is ##STR00066## R.sup.1 is glucosyl or galactosyl and each R.sup.2 is a linear or branched (fluoro-)alkyl group with 5 to 8 carbon atoms, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl or 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl.

8. The tetrapyrrolic compound according to claim 1, wherein in Formula 1 or 2 B is ##STR00067## R.sup.1 is glucosyl or galactosyl and each R.sup.2 is a linear or branched (fluoro-)alkyl group with 5 to 8 carbon atoms, pentafluorophenyl, 3,5-bis(trifluoromethyl)phenyl, 4-(1′-thio-β-D-glucosyl)-2,3,5,6-tetrafluorophenyl or 4-(1′-thio-β-D-galactosyl)-2,3,5,6-tetrafluorophenyl.

9. The tetrapyrrolic compound according to claim 8, wherein R.sup.1 is glucosyl and R.sup.2 is a linear or branched alkyl group with 5 to 8 carbon atoms.

10. The tetrapyrrolic compound according to claim 1 which compound is selected from the group consisting of ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072##

11. The tetrapyrrolic compound according to claim 10 selected from the group consisting of ##STR00073## ##STR00074##

12. The tetrapyrrolic compound according to claim 1, wherein O—R.sup.1 is a glycosidic bond.

13. A pharmaceutical composition comprising a tetrapyrrolic compound according to claim 1 wherein the pharmaceutical composition is preferably a liposomal formulation.

14. The pharmaceutical composition according to claim 13 further comprising PLGA particles, HSA particles, cyclodextrines and/or polymer particles.

15. The pharmaceutical composition according to claim 13, wherein the tetrapyrrolic compound is conjugated to a targeting agent, wherein the targeting agent is preferably selected from the group consisting of an antibody or fragment thereof.

16. A tetrapyrrolic compound according to claim 1 for use in photodynamic therapy, in particular photodynamic therapy of tumors, dermatological disorders, opthamological disorders, urological disorders, arthritis and other inflammatory diseases.

17. A tetrapyrrolic compound according to claim 1 for use in diagnosis.

Description

BRIEF DESCRIPTION OF FIGURES

[0080] FIG. 1 shows the results of the cell test of 5,15-bis-(4-β-D-glucosylphenyl)-10,20-dihexylporphyrin with the cell lines A431, CAL-27, L929 and HT29 (Example 4.1).

[0081] FIG. 2 shows the results of the cell test of 5,15-bis-(4-β-D-galactosylphenyl)-10,20-dihexylporphyrin with the cell lines A431, A253, CAL-27, L929 and HT29 (Example 4.2).

[0082] FIG. 3 shows the results of the cell test of 5-(4-β-D-lactosylphenyl)-10,15,20-triphenylporphyrin with cell lines A431, A253, CAL-27, L929 and HT29 (Example 4.3).

[0083] FIG. 4 shows the results of the cell test of 5-(3-β-D-glucosylphenyl)-10,15,20-trihexyl-17,18-dihydroxy-17,18-chlorin with the cell lines A431 and CAL-27 (Example 4.4).

[0084] FIG. 5 shows the results of the cell test of 5-(3-β-D-glucosylphenyl)-10,15,20-tris-(4-1′-thio-β-D-glucosyl-2,3,5,6-tetrafluorophenyl)-porphyrin with the cell lines A 253, CAL-27, L929 (Example 4.5).

[0085] FIG. 6 shows the results of the cell test of 5,10,15-tris-(3-β-D-galactosylphenyl)-20-[3,5-bis-(trifluoromethyl)-phenyl]-17,18-dihydroxy-17,18-chlorin with the cell line HT29 (Reference Example 4.6).

[0086] FIG. 7 shows the results of the cell test of 5,10,15-tris-(3-β-D-lactosylphenyl)-20-[3,5-bis-(trifluoromethyl)-phenyl]-17,18-dihydroxy-17,18-chlorin with the cell line HT29 (Reference Example 4.7).

[0087] FIG. 8 shows the results of the cell test of 5,10,15,20-tetrakis-(3-β-D-galactosyl)-porphyrin with the cell lines A431, A253, CAL-27, L929 and HT29 (Reference Example 4.8).

[0088] FIG. 9 shows the results of the cell test of 5,10,15,20-tetrakis-(4-β-D-glucosyl)-porphyrin with the cell lines A431, A253 and HT29 (Reference Example 4.9).

EXAMPLES

[0089] All reagents were used as purchased from commercial suppliers. Dichloromethane was purified by distillation over K.sub.2CO.sub.3 prior to use. Thin layer chromatography (TLC) was performed using Merck silica gel 60 (without fluorescence indicator) pre-coated on aluminum sheets. Flash chromatography was carried out using Fluka silica gel 60, 0.040-0.063 mm (230-400 mesh). .sup.1H and .sup.13C NMR spectra were recorded in CDCl.sub.3, (CD.sub.3).sub.2CO, CD.sub.3OD or (CD.sub.3).sub.2SO on Bruker (AC 500 and AVIII 700) and JOEL (Eclipse 500) instruments. Chemical shifts δ are given in ppm relative to TMS as internal standard or relative to the resonance of the residual solvent peak, J values are given in Hz. Mass spectra were recorded on an Agilent 6210 ESI-TOF, Agilent Technologies, Santa Clara, Calif., USA. Electronic absorption spectra were recorded on a Specord S300 (Analytik Jena) spectrophotometer using dichloromethane, ethanol, acetone or dimethyl sulfoxide as solvent.

Example 1—Preparation of Glycosubstituted Porphyrins

1.1 Preparation of 5-[4-(2,3,4,6-tetraacetyl-α-D-mannosyl)phenyl]-10,15,20-triphenylporphyrin

[0090] In a typical experiment, under argon atmosphere, Zn(II)-5-(4-hydroxyphenyl)-10,15,20-triphenylporphyrin (100 mg, 144 μmol) was dissolved in 20 ml dry dichloromethane and 0.5 ml dry acetonitrile. Then, 2,3,4,6-tetraacetyl-α-D-mannose trichloroacetimidate (862 mg, 1.75 mmol) and BF.sub.3-Et.sub.2O (7.5 μl, 60 μmol) were added. After stirring for 3 hours, the mixture was transferred to a separatory funnel. The organic layer was washed with water (2×100 ml) and the solvent was evaporated under reduced pressure. To remove the zinc, the residue was dissolved in 20 ml tetrahydrofuran, and 0.6 ml of hydrochloric acid (25%) were added. After stirring for 10 minutes, water (100 ml) and dichloromethane (150 ml) were added. The organic layer was separated and washed with water (2×100 ml). After drying with Na.sub.2SO.sub.4, the solvent was evaporated under reduced pressure. Further purification was achieved by flash chromatography, using dichloromethane/methanol 95:5 as the eluent. The analytically pure product (108 mg, 78%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol.

##STR00028##

[0091] mp: >300° C., .sup.1H NMR (700 MHz, (CD.sub.3).sub.2CO): δ=−2.73 (br s, 2H, NH), 2.04 (s, 3H, OAc), 2.06 (s, 3H, OAc), 2.13 (s, 3H, OAc), 2.24 (s, 3H, OAc), 4.25 (dd, J=2.8, 12.3 Hz, 1H, H-6.sub.A‘ose’), 4.37 (dd, J=6.4, 12.3 Hz, 1H, H-6.sub.B‘ose’), 4.45 (ddd, J=2.8, 6.4, 10.0 Hz, 1H, H-5‘ose’), 5.46 (dd, J=10.0, 10.0 Hz, 1H, H-4‘ose’), 5.64 (dd, J=1.9, 3.8 Hz, 1H, H-2‘ose’), 5.69 (dd, J=3.8, 10.0 Hz, 1H, H-3‘ose’), 6.02 (d, J=1.9 Hz, 1H, H-1 ‘ose’), 7.62 (d, J=8.7 Hz, 2H, Ar—H.sub.meta), 7.79-7.82 (m, 9H, 6×Ph-H.sub.meta, 3×Ph-H.sub.para), 8.21 (d, J=8.7 Hz, 2H, Ar—H.sub.ortho), 8.23-8.25 (m, 6H, Ph-H.sub.ortho), 8.86 (s, 6H, β-H), 8.90 (d, J=4.3 Hz, 2H, β-H) ppm. .sup.13C NMR (176 MHz, (CD.sub.3).sub.2CO): 6=21.69 (q, OCH.sub.3), 21.73 (q, OCH.sub.3), 21.76 (q, OCH.sub.3), 21.80 (q, OCH.sub.3), 64.21 (t, C-6‘ose’), 67.86 (d, C-4‘ose’), 70.96 (d, C-3‘ose’), 71.12 (d, C-5‘ose’), 71.58 (d, C-2‘ose’), 98.33 (d, C-1‘ose’), 117.32 (d, Ar—C.sub.meta), 121.51 (s, Ar—C.sub.meso), 122.10 (s, Ph-C.sub.meso), 122.14 (s, Ph-C.sub.meso), 128.76 (d, Ph-C.sub.meta), 129.86 (d, Ph-C.sub.para), 136.32 (d, Ar—C.sub.ortho), 137.37 (d, Ph-C.sub.ortho), 144.88 (s, Ph-C.sub.ipso), 157.82 (s, Ar—C.sub.OMan), 171.36 (s, C═O), 170.45 (s, C═0), 170.51 (s, C═0), 170.71 (s, C═0) ppm. ESI-HRMS: C.sub.58H.sub.49N.sub.4O.sub.10.sup.+ ([M+H].sup.+): calculated 961.3448, found 961.3444. UV/vis (CH.sub.2Cl.sub.2): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 415 (5.51), 513 (4.30), 547 (4.00), 591 (3.84), 647 (3.66) nm.

1.2 Preparation of 5-[4-(2,3,4,6,2′,3′,6′-heptaacetyl-β-D-lactosyl)phenyl]-10,15,20-triphenylporphyrin

[0092] In a typical experiment, under argon atmosphere, Zn(II)-5-(4-hydroxyphenyl)-10,15,20-triphenylporphyrin (60 mg, 86 μmol) was dissolved in 10 ml dry dichloromethane and 0.5 ml dry acetonitrile. Then, 2,3,4,6,2′,3′,6′-heptaacetyl-α-D-lactose trichloroacetimidate (500 mg, 640 μmol) and BF.sub.3-Et.sub.2O (10 μl, 80 μmol) were added. After stirring for 2 hours, the mixture was transferred to a separatory funnel. The organic layer was washed with water (2×100 ml) and the solvent was evaporated under reduced pressure. To remove the zinc, the residue was dissolved in 20 ml tetrahydrofuran, and 0.6 ml of hydrochloric acid (25%) were added. After stirring for 10 minutes, water (100 ml) and dichloromethane (150 ml) were added. The organic layer was separated and washed with water (2×100 ml). After drying with Na.sub.2SO.sub.4, the solvent was evaporated under reduced pressure. Further purification was achieved by flash chromatography, using dichloromethane/methanol 99:1 as the eluent. The analytically pure product (58 mg, 54%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol.

##STR00029##

[0093] mp: >300° C., .sup.1H NMR (700 MHz, CDCl.sub.3): δ=−2.80 (br s, 2H, NH), 1.99 (s, 3H, OAc), 2.09 (s, 3H, OAc), 2.11 (s, 3H, OAc), 2.13 (s, 3H, OAc), 2.15 (s, 3H, OAc), 2.19 (s, 3H, OAc), 2.21 (s, 3H, OAc), 3.96-4.04 (m, 3H, H-5′‘ose’, H-4′‘ose’, H-5‘ose’), 4.16 (dd, J=7.3, 11.2 Hz, 1H, H-6.sub.A‘ose’), 4.22 (dd, J=6.3, 11.2 Hz, 1H, H-6.sub.B‘ose’), 4.29 (dd, J=5.7, 11.9 Hz, 1H, H-6B′‘ose’), 4.58 (d, J=7.9 Hz, 1H, H-1 ‘ose’), 4.62 (dd, J=2.0, 11.9 Hz, 1H, H-6.sub.A′‘ose’), 5.00 (dd, J=3.4, 10.4 Hz, 1H, H-3‘ose’), 5.18 (dd, J=8.0, 10.4 Hz, 1H, H-2‘ose’), 5.39-5.47 (m, 4H, H-4‘ose’, H-1 ‘ose’, H-2‘ose’, H-3‘ose’), 7.38 (d, J=8.5 Hz, 2H, Ar—H.sub.meta), 7.76-7.83 (m, 9H, 6×Ph-H.sub.meta, 3×Ph-H.sub.para), 8.15 (d, J=8.5 Hz, 2H, Ar—H.sub.ortho), 8.21-8.24 (m, 6H, Ph-H.sub.ortho), 8.81-8.84 (m, 8H, β-H) ppm. .sup.13C NMR (176 MHz, CDCl.sub.3): δ=20.55 (q, CH.sub.3), 20.68 (q, CH.sub.3), 20.69 (q, CH.sub.3), 20.71 (q, CH.sub.3), 20.87 (q, CH.sub.3), 20.89 (q, CH.sub.3), 60.90 (t, C-6‘ose’), 62.27 (t, C-6′‘ose’), 66.68 (d, C‘ose’), 69.17 (d, C-2‘ose’), 70.85 (d, C‘ose’), 71.02 (d, C-3‘ose’), 71.70 (d, C‘ose’), 72.97 (d, C‘ose’), 73.10 (d, C‘ose’), 76.45 (d, C‘ose’), 98.95 (d, C-1′‘ose’), 101.25 (d, C-1‘ose’), 115.05 (d, Ar—C.sub.meta), 119.17 (s, Ar—C.sub.meso), 120.20 (s, Ph-C.sub.meso), 120.22 (s, Ph-C.sub.meso), 126.70 (d, Ph-C.sub.meta), 127.75 (d, Ph-C.sub.para), 134.56 (d, Ph-C.sub.ortho), 135.56 (d, Ar—C.sub.ortho), 137.25 (s, Ar—C.sub.ipso), 142.14 (s, Ph-C.sub.ipso), 156.64 (s, Ar—C.sub.OLac), 169.15 (s, C═0), 169.78 (s, C═0), 169.84 (s, C═0), 170.08 (s, C═0), 170.17 (s, C═0), 170.37 (s, C═0), 170.40 (s, C═0) ppm. ESI-HRMS: C.sub.70H.sub.65N.sub.4O.sub.18.sup.+ ([M+H].sup.+): calculated 1249.4294, found 1249.4248. UV/vis (CH.sub.2Cl.sub.2): A.sub.max (log E/dm.sup.3 mol.sup.−1 cm.sup.−1): 418 (5.56), 515 (4.26), 550 (3.94), 590 (3.81), 647 (370) nm.

1.3 Preparation of 5-[4-(2,3,4,6-tetraacetyl-β-D-glucosyl)phenyl]-10,15,20-tris-[3,5-bis-(trifluoro-methyl)phenyl]-porphyrin

[0094] In a typical experiment, under argon atmosphere, Zn(II)-5-(4-hydroxyphenyl)-10,15,20-tris-[3,5-bis-(trifluoromethyl)phenyl]-porphyrin (50 mg, 43 μmol) was dissolved in 10 ml dry dichloromethane. Then, 2,3,4,6-tetraacetyl-D-glucose trichloroacetimidate (40 mg, 81 μmol) and BF.sub.3-Et.sub.2O (20 μl, 0.2 mmol) were added. After stirring for 20 minutes, the mixture was transferred to a separatory funnel. The organic layer was washed with water (2×50 ml) and the solvent was evaporated under reduced pressure. To remove the zinc, the residue was dissolved in 10 ml tetrahydrofuran, and 1.0 ml of hydrochloric acid (25%) were added. After stirring for 10 minutes, water (50 ml) and dichloromethane (75 ml) were added. The organic layer was separated and washed with water (2×50 ml). After drying with Na.sub.2SO.sub.4, the solvent was evaporated under reduced pressure. Further purification was achieved by flash chromatography, using dichloromethane/ethyl acetate 95:5 as the eluent. The analytically pure product (49 mg, 83%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol.

##STR00030##

[0095] mp: 154° C., .sup.1H NMR (500 MHz, CDCl.sub.3): δ=−2.84 (br s, 2H, NH), 2.11 (s, 3H, OAc), 2.12 (s, 3H, OAc), 2.13 (s, 3H, OAc), 2.23 (s, 3H, OAc), 4.08 (ddd, J=2.5, 5.3, 10.0 Hz, 1H, H-5‘ose’), 4.33 (dd, J=2.5, 12.4 Hz, 1H, H-6.sub.A‘ose’), 4.43 (dd, J=5.3, 12.4 Hz, 1H, H-6.sub.B‘ose’), 5.33 (dd, J=9.5, 10.0 Hz, 1H, H-4‘ose’), 5.47 (dd, J=9.5, 9.5 Hz, 1H, H-3‘ose’), 5.49 (d, J=7.7 Hz, 1H, H-1 ‘ose’), 5.50-5.53 (m, 1H, H-2‘ose’), 7.44 (d, J=8.5 Hz, 2H, 2×Ar-H.sub.meta), 8.16 (d, J=8.5 Hz, 2H, 2×Ar-H.sub.ortho), 8.38 (br s, 3H, 3×Ar.sub.F—H.sub.para), 8.70 (br s, 6H, 6×Ar.sub.F—H.sub.ortho), 8.75 (d, J=4.8 Hz, 2H, β-H), 8.79 (s, 4H, β-H), 8.99 (d, J=4.8 Hz, 2H, β-H) ppm. .sup.13C NMR (126 MHz, CDCl.sub.3): δ=20.74 (q, OCH.sub.3), 20.78 (q, OCH.sub.3), 20.86 (q, OCH.sub.3), 20.91 (q, OCH.sub.3), 62.16 (t, C-6‘ose’), 68.43 (d, C-4‘ose’), 71.39 (d, C-2‘ose’), 72.44 (d, C-5‘ose’), 72.88 (d, C-3‘ose’), 99.19 (d, C-1‘ose’), 115.40 (d, Ar—C.sub.meta), 116.77 (s, Ar.sub.F—C.sub.meso), 117.19 (s, Ar.sub.F—C.sub.meso), 120.31 (s, Ar.sub.F—C.sub.meso), 121.59 (s, Ar—C.sub.meso), 122.27 (d, Ar.sub.F—C.sub.para), 122.48, 124.65, 126.82, 130.62 (q, CF.sub.3), 130.65 (q, CF.sub.3), 133.77 (d, Ar.sub.F—C.sub.ortho), 133.80 (d, Ar.sub.F—C.sub.ortho), 135.75 (d, Ar—C.sub.ortho), 136.37 (s, Ar—C.sub.ipso), 143.84 (s, Ar.sub.F—C.sub.ipso), 143.91 (s, Ar.sub.F—C.sub.ipso), 157.05 (s, Ar—C.sub.OGlu), 169.56 (s, C═0), 170.44 (s, C═0), 169.56 (s, C═0) ppm. .sup.19F-NMR (471 MHz, CDCl.sub.3): δ=−62.26 (s, 18 F, 6×CF.sub.3) ppm. ESI-HRMS: C.sub.64H.sub.43F.sub.18N.sub.4O.sub.10.sup.+ ([M+H].sup.+): calculated 1369.2692, found 1369.2683. UV/vis (CH.sub.2Cl.sub.2): λ.sub.max (log E/dm.sup.3 mol.sup.−1 cm.sup.−1): 420 (5.50), 515 (3.93), 554 (4.53), 593 (4.20), 645 (3.84) nm.

1.4 Preparation of 5,15-bis-[3-(2,3,4,6-tetraacetyl-β-D-glucosyl)-phenyl]-10,20-dihexylporphyrin

[0096] In a typical experiment, under argon atmosphere, Zn(II)-5,15-bis-(3-hydroxyphenyl)-10,20-dihexylporphyrin (75 mg, 0.10 mmol) was dissolved in 20 ml dry dichloromethane and 0.5 ml dry acetonitrile. Then, 2,3,4,6-tetraacetyl-D-glucose trichloroacetimidate (250 mg, 507 μmol) and BF.sub.3-Et.sub.2O (5.0 μl, 40 μmol) were added. After stirring for 2 hours, the mixture was transferred to a separatory funnel. The organic layer was washed with water (2×50 ml) and the solvent was evaporated under reduced pressure. To remove the zinc, the residue was dissolved in 20 ml tetrahydrofuran, and 1.0 ml of hydrochloric acid (25%) were added. After stirring for 10 minutes, water (50 ml) and dichloromethane (75 ml) were added. The organic layer was separated and washed with water (2×50 ml). After drying with Na.sub.2SO.sub.4, the solvent was evaporated under reduced pressure. Further purification was achieved by flash chromatography, using dichloromethane/ethyl acetate 95:5 as the eluent. The analytically pure product (108 mg, 78%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol.

##STR00031##

[0097] mp: 205° C., .sup.1H NMR (500 MHz, CDCl.sub.3): δ=−2.72 (m, 2H, NH), 0.91-0.96 (m, 6H, 2×CH.sub.3), 1.31 (s, 3H, OAc), 1.32 (s, 3H, OAc), 1.36-1.43 (m, 4H, 2×CH.sub.2), 1.48-1.57 (m, 4H, 2×CH.sub.2), 1.77-1.84 (m, 4H, 2×CH.sub.2), 1.98 (s, 6H, 2 xOAc), 2.04 (s, 6H, 2×OAc), 2.11 (s, 6H, 2×OAc), 2.47-2.57 (m, 4H, 2×CH.sub.2), 3.76-3.80 (m, 2H, H-5‘ose’), 4.03-4.07 (m, 2H, H-6.sub.A‘ose’), 4.14-4.19 (m, 2H, H-6.sub.B‘ose’), 4.93-5.00 (m, 4H, 2×CH.sub.2), 5.18 (dd, J=9.3, 9.3 Hz, 2H, H-4‘ose’), 5.32 (dd, J=9.3, 9.3 Hz, 2H, H-3‘ose’), 5.36 (d, J=7.9 Hz, 2H, H-1‘ose’), 5.41 (dd, J=7.9, 9.3 Hz, 2H, H-2‘ose’), 7.43-7.46 (m, 2H, Ar—H), 7.65-7.69 (m, 2H, Ar—H), 7.84-7.87 (m, 2H, Ar—H), 7.92-7.95 (m, 2H, Ar—H), 8.89 (d, J=4.7 Hz, 4H, β-H), 9.42-9.46 (m, 4H, β-H) ppm. .sup.13C NMR (126 MHz, CDCl.sub.3): δ=14.22 (q, CH.sub.3), 19.96 (q, OCH.sub.3), 20.60 (q, OCH.sub.3), 20.69 (q, OCH.sub.3), 20.80 (q, OCH.sub.3), 22.80 (t, CH.sub.2), 30.32 (t, CH.sub.2), 31.99 (t, CH.sub.2), 35.42 (t, CH.sub.2), 38.87 (t, CH.sub.2), 61.98 (t, C-6‘ose’), 68.38 (d, C-4‘ose’), 71.39 (d, C-2‘ose’), 72.26 (d, C-5‘ose’), 72.89 (d, C-3‘ose’), 99.38 (d, C-1‘ose’), 116.71 (d, Ar—C), 118.10 (s, Ar—C.sub.meso), 120.19 (s, Ar—C.sub.meso), 122.78 (d, Ar—C), 127.67 (d, Ar—C), 129.95 (d, Ar—C), 144.32 (s, Ar—C.sub.ipso), 155.35 (s, Ar—C.sub.OGlu), 169.45 (C═0), 170.31 (C═0), 170.46 (C═0) ppm. ESI-HRMS: C.sub.72H.sub.83N.sub.4O.sub.20.sup.+ ([M+H].sup.+): calculated 1323.5601, found 1323.5578. UV/vis (CH.sub.2Cl.sub.2): A.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 419 (5.59), 518 (4.28), 554 (4.03), 597 (3.71), 653 (3.81) nm.

1.5 Preparation of 5,15-bis-[4-(2,3,4,6-tetraacetyl-β-D-glucosyl)-phenyl]-10,20-dihexylporphyrin

[0098] In a typical experiment, under argon atmosphere, Zn(II)-5,15-bis-(4-hydroxyphenyl)-10,20-dihexylporphyrin (75 mg, 0.10 mmol) was dissolved in 20 ml dry dichloromethane and 0.5 ml dry acetonitrile. Then, 2,3,4,6-tetraacetyl-D-glucose trichloroacetimidate (250 mg, 507 μmol) and BF.sub.3-Et.sub.2O (5.0 μl, 40 μmol) were added. After stirring for 2 hours, the mixture was transferred to a separatory funnel. The organic layer was washed with water (2×50 ml) and the solvent was evaporated under reduced pressure. To remove the zinc, the residue was dissolved in 20 ml tetrahydrofuran, and 1.0 ml of hydrochloric acid (25%) were added. After stirring for 10 minutes, water (50 ml) and dichloromethane (75 ml) were added. The organic layer was separated and washed with water (2×50 ml). After drying with Na.sub.2SO.sub.4, the solvent was evaporated under reduced pressure. Further purification was achieved by flash chromatography, using dichloromethane/ethyl acetate 95:5 as the eluent. The analytically pure product (113 mg, 82%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol.

##STR00032##

[0099] mp: 204° C., .sup.1H NMR (500 MHz, CDCl.sub.3): δ=−2.70 (br s, 2H, NH), 0.91 (t, J=7.5 Hz, 6H, 2×CH.sub.3), 1.33-1.41 (m, 4H, 2×CH.sub.2), 1.46-1.52 (m, 4H, 2×CH.sub.2), 1.75-1.81 (m, 4H, 2×CH.sub.2), 2.11 (s, 6H, 2×OAc), 2.12 (s, 6H, 2×OAc), 2.14 (s, 6H, 2×OAc), 2.24 (s, 6H, 2×OAc), 2.47-2.53 (m, 4H, 2×CH.sub.2), 4.07 (ddd, J=2.4, 5.5, 10.2 Hz, 2H, 2×H-5‘ose’), 4.32 (dd, J=2.4, 12.3 Hz, 2H, 2×H-6.sub.A‘ose’), 4.44 (dd, J=5.5, 12.3 Hz, 2H, 2×H-6.sub.B‘ose’), 4.92-4.97 (m, 4H, 2×CH.sub.2), 5.32 (dd, J=9.4, 10.1 Hz, 2H, 2×H-4‘ose’), 5.45-5.53 (m, 6H, 2×H-1 ‘ose’, 2×H-2‘ose’, 2×H-3‘ose’), 7.38 (d, J=8.5 Hz, 4H, Ar—H.sub.meta), 8.11 (d, J=8.5 Hz, 4H, Ar—H.sub.ortho), 8.85 (d, J=4.8 Hz, 4H, β-H), 9.42 (d, J=4.8 Hz, 4H, β-H) ppm. .sup.13C NMR (126 MHz, CDCl.sub.3): δ=14.11 (q, CH.sub.3), 20.64 (q, OCH.sub.3), 20.72 (q, OCH.sub.3), 20.82 (q, OCH.sub.3), 22.69 (t, CH.sub.2), 30.32 (t, CH.sub.2), 31.89 (t, CH.sub.2), 35.31 (t, CH.sub.2), 38.68 (t, CH.sub.2), 62.14 (t, C-6‘ose’), 68.46 (d, C-4‘ose’), 71.38 (d, C-2‘ose’), 72.32 (d, C-5‘ose’), 72.89 (d, C-3‘ose’), 99.30 (d, C-1‘ose’), 114.93 (d, Ar—C.sub.meta), 117.96 (s, Ar—C.sub.meso), 119.93 (s, Ar—C.sub.meso), 135.40 (d, Ar—C.sub.ortho), 137.79 (s, Ar—C.sub.ipso), 156.57 (s, Ar—C.sub.OGlu), 169.48 (s, C═0), 170.35 (s, C═0), 170.65 (s, C═0) ppm. ESI-HRMS: C.sub.72H.sub.83N.sub.4O.sub.20.sup.+ ([M+H].sup.+): calculated 1323.5601, found 1323.5572. UV/vis (CH.sub.2Cl.sub.2): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 419 (5.59), 518 (4.28), 554 (4.03), 597 (3.71), 653 (3.81) nm.

1.6 Preparation of 5,15-bis-[4-(2,3,4,6-tetraacetyl-β-D-galactosyl)-phenyl]-10,20-dihexylporphyrin

[0100] In a typical experiment, under argon atmosphere, Zn(II)-5,15-bis-(4-hydroxyphenyl)-10,20-dihexylporphyrin (50 mg, 69 μmol) was dissolved in 15 ml dry dichloromethane and 0.3 ml dry acetonitrile. Then, 2,3,4,6-tetraacetyl-D-galactose trichloroacetimidate (165 mg, 335 μmol) and BF.sub.3-Et.sub.2O (5.0 μl, 40 μmol) were added. After stirring for 2 hours, the mixture was transferred to a separatory funnel. The organic layer was washed with water (2×50 ml) and the solvent was evaporated under reduced pressure. To remove the zinc, the residue was dissolved in 10 ml tetrahydrofuran, and 0.7 ml of hydrochloric acid (25%) were added. After stirring for 10 minutes, water (50 ml) and dichloromethane (75 ml) were added. The organic layer was separated and washed with water (2×50 ml). After drying with Na.sub.2SO.sub.4, the solvent was evaporated under reduced pressure. Further purification was achieved by flash chromatography, using dichloromethane/ethyl acetate 95:5 as the eluent. The analytically pure product (73 mg, 80%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol.

##STR00033##

[0101] mp: 161° C., .sup.1H NMR (500 MHz, CDCl.sub.3): δ=−2.70 (br s, 2H, NH), 0.91 (t, J=7.4 Hz, 6H, 2×CH.sub.3), 1.34-1.41 (m, 4H, 2×CH.sub.2), 1.46-1.54 (m, 4H, 2×CH.sub.2), 1.76-1.82 (m, 4H, 2×CH.sub.2), 2.07 (s, 6H, 2×OAc), 2.08 (s, 6H, 2 xOAc), 2.24 (s, 6H, 2×OAc), 2.27 (s, 6H, 2×OAc), 2.47-2.53 (m, 4H, 2×CH.sub.2), 4.22-4.26 (m, 2H, 2×H-5‘ose’), 4.29-4.39 (m, 4H, 2×H-6‘ose’), 4.94-4.96 (m, 4H, 2×CH.sub.2), 5.28 (dd, J=3.6, 10.0 Hz, 2H, 2×H-3‘ose’), 5.41 (d, J=8.2 Hz, 2H, 2×H-1‘ose’), 5.57 (dd, J=0.9, 3.6 Hz, 2H, 2×H-4‘ose’), 5.71 (dd, J=8.2, 10.0 Hz, 2H, 2×H-2‘ose’), 7.40 (d, J=8.4 Hz, 4H, Ar—H.sub.meta), 8.12 (d, J=8.4 Hz, 4H, Ar—H.sub.ortho), 8.86 (d, J=4.8 Hz, 4H, β-H), 9.42 (d, J=4.8 Hz, 4H, β-H) ppm. .sup.13C NMR (126 MHz, CDCl.sub.3): δ=14.20 (q, CH.sub.3), 20.74 (q, OCH.sub.3), 20.79 (q, OCH.sub.3), 20.83 (q, OCH.sub.3), 21.02 (q, OCH.sub.3), 22.78 (t, CH.sub.2), 30.29 (t, CH.sub.2), 31.98 (t, CH.sub.2), 35.40 (t, CH.sub.2), 38.78 (t, CH.sub.2), 61.63 (t, C-6‘ose’), 67.13 (d, C-4‘ose’), 68.96 (d, C-2‘ose’), 71.10 (d, C-3‘ose’), 71.41 (d, C-5‘ose’), 99.94 (d, C-1‘ose’), 115.05 (d, Ar—C.sub.meta), 118.08 (s, Ar—C.sub.meso), 120.01 (s, Ar—C.sub.meso), 135.48 (d, Ar—C.sub.ortho), 137.85 (s, Ar—C.sub.ipso), 156.70 (s, Ar—C.sub.OGal), 169.63 (s, C═0), 170.30 (s, C═0), 170.40 (s, C═0), 170.50 (s, C═0) ppm. ESI-HRMS: C.sub.72H.sub.83N.sub.4O.sub.20.sup.+ ([M+H].sup.+): calculated 1323.5601, found 1323.5558. UV/vis (CH.sub.2Cl.sub.2): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 419 (5.60), 519 (4.26), 554 (4.02), 597 (3.69), 654 (3.80) nm.

1.7 Preparation of 5,15-bis-[3-(2,3,4,6-tetraacetyl-β-D-glucosyl)-phenyl]-10,20-diphenylporphyrin

[0102] In a typical experiment, under argon atmosphere, Zn(II)-5,15-bis-(3-hydroxyphenyl)-10,20-diphenylporphyrin (20 mg, 28 μmol) was dissolved in 4 ml dry dichloromethane and 0.2 ml dry acetonitrile. Then, 2,3,4,6-tetraacetyl-D-glucose trichloroacetimidate (50 mg, 102 μmol) and BF.sub.3-Et.sub.2O (1.0 μl, 8.0 μmol) were added. After stirring for 2 hours, the mixture was transferred to a separatory funnel. The organic layer was washed with water (2×50 ml) and the solvent was evaporated under reduced pressure. To remove the zinc, the residue was dissolved in 4 ml tetrahydrofuran, and 0.2 ml of hydrochloric acid (25%) were added. After stirring for 10 minutes, water (50 ml) and dichloromethane (75 ml) were added. The organic layer was separated and washed with water (2×50 ml). After drying with Na.sub.2SO.sub.4, the solvent was evaporated under reduced pressure. Further purification was achieved by flash chromatography, using dichloromethane/ethyl acetate 95:5 as the eluent. The analytically pure product (28 mg, 75%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol.

##STR00034##

[0103] mp: >300° C., .sup.1H NMR (500 MHz, CDCl.sub.3): δ=−2.83 (br s, 2H, NH), 1.31-1.34 (m, 6H, 2×OAc), 1.97-1.98 (m, 6H, 2×OAc), 2.03 (m, 6H, 2×OAc), 2.09 (s, 6H, 2×OAc), 3.76-3.80 (m, 2H, H-5‘ose’), 4.00-4.04 (m, 2H, H-6.sub.A‘ose’), 4.13-4.17 (m, 2H, H-6.sub.B‘ose’), 5.13-5.18 (m, 2H, H-4‘ose’), 5.29-5.40 (m, 6H, H-1‘ose’, H-2‘ose’, H-3‘ose’), 7.41-7.44 (m, 2H, Ar—H), 7.64-7.69 (m, 2H, Ar—H), 7.75-7.79 (m, 6H, 4×Ph-H.sub.meta, 2×Ph-H.sub.para), 7.85-7.88 (m, 2H, Ar—H), 7.93-7.96 (m, 2H, Ar—H), 8.16-8.23 (m, 4H, Ph-H.sub.ortho), 8.84-8.88 (m, 8H, β-H) ppm. .sup.13C NMR (126 MHz, CDCl.sub.3): δ=19.99 (q, CH.sub.3), 20.63 (q, CH.sub.3), 20.70 (q, CH.sub.3), 20.81 (q, CH.sub.3), 61.96 (t, C-6‘ose’), 68.30 (d, C-4‘ose’), 71.30 (d, C-2‘ose’), 72.23 (d, C-5‘ose’), 72.81 (d, C-3‘ose’), 99.31 (d, C-1‘ose’), 116.71 (d, Ar—C), 119.31 (s, Ph-C.sub.meso), 120.50 (s, Ar—C.sub.meso), 122.84 (d, Ar—C), 126.88 (d, Ph-C.sub.meta), 127.84 (d, Ar—C), 127.95 (d, Ph-C.sub.para), 129.99 (d, Ar—C), 134.61 (d, Ph-C.sub.ortho), 142.01 (s, Ph-C.sub.ipso), 143.78 (s, Ar—C.sub.ipso), 155.41 (s, Ar—C.sub.OGlu), 169.46 (s, C═0), 170.32 (s, C═0), 170.48 (s, C═0) ppm. ESI-HRMS: C.sub.72H.sub.66N.sub.4O.sub.20Na.sup.+ ([M+Na].sup.+): calculated 1329.4120, found 1329.4168. UV/vis (CH.sub.2Cl.sub.2): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 415 (5.41), 513 (3.79), 547 (3.56), 591 (3.26), 648 (3.36) nm.

1.8 Preparation of 5,10,15,20-tetrakis-[4-(2,3,4,6-tetraacetyl-β-D-glucosyl)phenyl]-porphyrin (Reference example)

[0104] In a typical experiment, under argon atmosphere, Zn(II)-5,10,15,20-(4-hydroxyphenyl)-porphyrin (50 mg, 62 μmol) was dissolved in 8 ml dry dichloromethane, 1 ml tetrahydrofuran and 1 ml acetonitrile. Then, 2,3,4,6-tetraacetyl-D-glucose trichloroacetimidate (0.8 g, 1.5 mmol) and BF.sub.3-Et.sub.2O (4.0 μl, 32 μmol) were added. After stirring for 3 hours, the mixture was transferred to a separatory funnel. The organic layer was washed with water (2×50 ml) and the solvent was evaporated under reduced pressure. To remove the zinc, the residue was dissolved in 10 ml tetrahydrofuran, and 0.8 ml of hydrochloric acid (25%) were added. After stirring for 10 minutes, water (50 ml) and dichloromethane (75 ml) were added. The organic layer was separated and washed with water (2×50 ml). After drying with Na.sub.2SO.sub.4, the solvent was evaporated under reduced pressure. Further purification was achieved by flash chromatography, using dichloromethane/methanol 99:1 as the eluent. The analytically pure product (93 mg, 69%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol.

##STR00035##

[0105] mp: 287° C., .sup.1H NMR (500 MHz, CDCl.sub.3): δ=−2.83 (br s, 2H, NH), 2.10 (s, 12H, 4×OAc), 2.11 (s, 12H, 4×OAc), 2.12 (s, 12H, 4×OAc), 2.21 (s, 12H, 4×OAc), 4.06 (ddd, J=2.5, 5.4, 10.1 Hz, 4H, H-5‘ose’), 4.30 (dd, J=2.5, 12.3 Hz, 4H, H-6.sub.A‘ose’), 4.42 (dd, J=5.4, 12.3 Hz, 4H, H-6.sub.B‘ose’), 5.31 (dd, J=9.6, 10.1 Hz, 4H, H-4‘ose’), 5.45 (dd, J=9.6, 9.6 Hz, 4H, H-3‘ose’), 5.47 (d, J=7.6 Hz, 4H, H-1‘ose’), 5.49 (dd, J=7.6, 9.6 Hz, 4H, H-2‘ose’), 7.38 (d, J=8.5 Hz, 8H, 8×Ar-H.sub.meta), 8.12 (d, J=8.5 Hz, 8H, 8 xAr-H.sub.ortho), 8.85 (s, 8H, β-H) ppm. .sup.13C NMR (126 MHz, CDCl.sub.3): δ=20.73 (q, CH.sub.3), 20.77 (q, CH.sub.3), 20.86 (q, CH.sub.3), 20.90 (q, CH.sub.3), 62.18 (t, C-6‘ose’), 68.48 (d, C-4‘ose’), 71.43 (d, C-2‘ose’), 72.39 (d, C-5‘ose’), 72.93 (d, C-3‘ose’), 99.25 (d, C-1‘ose’), 115.17 (d, Ar—C.sub.meta), 119.43 (s, Ar—C.sub.meso), 135.62 (d, Ar—C.sub.ortho), 137.21 (s, Ar—C.sub.ipso), 156.74 (s, Ar—C.sub.OGlu), 169.55 (s, C═0), 170.41 (s, C═0), 170.70 (s, C═0) ppm. ESI-HRMS: C.sub.100H.sub.103N.sub.4O.sub.40.sup.+ [M+H].sup.+: calculated 1999.6149, found 1999.6078. UV/vis (CH.sub.2Cl.sub.2): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 420 (5.20), 515 (3.89), 551 (3.66), 594 (3.46), 649 (3.39) nm.

1.9 Preparation of 5,10,15,20-tetrakis-[3-(2,3,4,6-tetraacetyl-β-D-galactosyl)-phenyl]-porphyrin (Reference Example)

[0106] In a typical experiment, under argon atmosphere, Zn(II)-5,10,15,20-(3-hydroxyphenyl)-porphyrin (50 mg, 62 μmol) was dissolved in 8 ml dry dichloromethane, 1 ml tetrahydrofuran and 1 ml acetonitrile. Then, 2,3,4,6-tetraacetyl-D-galactose trichloroacetimidate (0.8 g, 1.5 mmol) and BF.sub.3-Et.sub.2O (3.5 μl, 28 μmol) were added. After stirring for 3 hours, the mixture was transferred to a separatory funnel. The organic layer was washed with water (2×50 ml) and the solvent was evaporated under reduced pressure. To remove the zinc, the residue was dissolved in 8 ml tetrahydrofuran, and 0.4 ml of hydrochloric acid (25%) were added. After stirring for 10 minutes, water (50 ml) and dichloromethane (75 ml) were added. The organic layer was separated and washed with water (2×50 ml). After drying with Na.sub.2SO.sub.4, the solvent was evaporated under reduced pressure. Further purification was achieved by flash chromatography, using dichloromethane/methanol 99:1 as the eluent. The analytically pure product (97 mg, 78%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol.

[0107] This porphyrin is an atropisomer.

##STR00036##

[0108] mp: 225° C., .sup.1H NMR (500 MHz, (CD.sub.3).sub.2CO): δ=−2.84 (br s, 2H, NH), 0.97-1.04 (m, 12H, 4×OAc), 1.90-1.93 (m, 12H, 4×OAc), 2.06-2.09 (m, 12H, 4×OAc), 2.12 (s, 12H, 4×OAc), 4.00-4.09 (m, 8H, H-6‘ose’), 4.32-4.37 (m, 4H, H-5‘ose’), 5.24-5.28 (m, 4H, H-3‘ose’), 5.37-5.40 (m, 4H, H-4‘ose’), 5.50-5.55 (m, 4H, H-2‘ose’), 5.71-5.75 (m, 4H, H-1‘ose’), 7.53-7.57 (m, 4H, Ar—H), 7.75-7.80 (m, 4H, Ar—H), 7.92-8.06 (m, 8H, Ar—H), 8.93-8.97 (m, 8H, β-H) ppm. ESI-HRMS: C.sub.100H.sub.103N.sub.4O.sub.40.sup.+ ([M+H].sup.+): calculated 1999.6149, found 1999.6140. UV/vis ((CH.sub.3).sub.2CO): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 418 (5.54), 513 (4.22), 548 (3.74), 589 (3.69), 645 (3.38) nm.

1.10 Preparation of 5-[3-(2,3,4,6-tetraacetyl-β-D-glucosyl)phenyl]-10,15,20-tris-(pentafluorophenyl)-porphyrin

[0109] In a typical experiment, under argon atmosphere, Zn(II)-[5-(3-hydroxyphenyl)-10,15,20-tris-(pentafluorophenyl)-porphyrin (60 mg, 62 μmol) was dissolved in 10 ml dry dichloromethane. Then, 2,3,4,6-tetraacetyl-D-glucose trichloroacetimidate (132 mg, 268 μmol) and BF.sub.3-Et.sub.2O (2.8 μl, 22 μmol) were added. After stirring for 20 minutes, the mixture was transferred to a separatory funnel. The organic layer was washed with water (2×50 ml) and the solvent was evaporated under reduced pressure. To remove the zinc, the residue was dissolved in 10 ml tetrahydrofuran, and 1.5 ml of hydrochloric acid (25%) were added; this step was repeated two more times. Then water (50 ml) and dichloromethane (75 ml) were added. The organic layer was separated and washed with water (2×50 ml). After drying with Na.sub.2SO.sub.4, the solvent was evaporated under reduced pressure. Further purification was achieved by flash chromatography, using dichloromethane/ethyl acetate 98:2 as the eluent. The analytically pure product (32 mg, 44%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol.

##STR00037##

[0110] mp: 190° C., .sup.1H NMR (700 MHz, CDCl.sub.3): δ=−2.84 (m, 2H, NH), 1.41 (s, 3H, OAc), 2.01 (s, 3H, OAc), 2.06 (s, 3H, OAc), 2.13 (s, 3H, OAc), 3.83 (ddd, J=2.4, 5.6, 10.1 Hz, 1H, H-5‘ose’), 4.11 (dd, J=2.4, 12.2 Hz, 1H, H-6.sub.A‘ose’), 4.18 (dd, J=5.6, 12.2 Hz, 1H, H-6.sub.B‘ose’), 5.21 (dd, J=9.2, 10.1 Hz, 1H, H-4‘ose’), 5.35 (dd, J=9.2, 9.2 Hz, H-3‘ose’), 5.39 (d, J=7.7 Hz, 1H, H-1‘ose’), 5.42 (dd, J=7.7, 9.2 Hz, 1H, H-2‘ose’), 7.49-7.51 (m, 1H, Ar—H), 7.73-7.76 (m, 1H, Ar—H), 7.88-7.92 (m, 1H, Ar—H), 7.95-7.98 (m, 1H, Ar—H), 8.86-8.88 (m, 2H, β-H), 8.91-8.94 (m, 4H, β-H), 9.01-9.03 (m, 2H, β-H) ppm. .sup.13C NMR (176 MHz, CDCl.sub.3): δ=19.87 (OCH.sub.3), 20.53 (OCH.sub.3), 20.60 (OCH.sub.3), 20.72 (OCH.sub.3), 61.94 (C-6‘ose’), 68.26 (C-4‘ose’), 71.23 (C-2‘ose’), 72.19 (C-5‘ose’), 72.70 (C-3‘ose’), 99.07 (C-1‘ose’), 102.07 (Ar.sub.F—C.sub.meso), 103.11 (Ar.sub.F—C.sub.meso), 115.60-115.94 (Ar.sub.F—C.sub.ipso), 117.21 (Ar—C), 122.12 (Ar—C.sub.meso), 122.81 (Ar—C), 128.05 (Ar—C), 129.90 (Ar—C), 136.77-136.94 (Ar.sub.F—C), 138.21-138.32 (Ar.sub.F—C), 141.48-141.56 (Ar.sub.F—C), 142.47 (Ar—C.sub.ipso), 142.86-142.95 (Ar.sub.F—C), 145.76-145.96 (Ar.sub.F—C), 147.12-147.35 (Ar.sub.F—C), 155.33 (Ar—C.sub.OGlu), 169.34 (C═0), 169.35 (C═0), 170.21 (C═0), 170.31 (C═0) ppm. .sup.19F NMR (471 MHz, CDCl.sub.3): δ=−161.54-−161.27 (m, 6 F, Ar—F.sub.meta), −151.57-−151.42 (m, 3 F, Ar—F.sub.para), −136.75-−136.39 (m, 6 F, Ar—F.sub.ortho) ppm. ESI-HRMS: C.sub.58H.sub.33F.sub.15N.sub.4O.sub.10Na.sup.+ ([M+Na].sup.+): calculated 1253.1849, found 1253.1855. UV/vis (CH.sub.2Cl.sub.2): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 414 (5.50), 508 (4.33), 585 (3.83) nm.

Example 2—Preparation of Glycosylated Deacetylated Porphyrins

2.1 Preparation of 5-(4-α-D-mannosylphenyl)-10,15,20-triphenylporphyrin

[0111] In a typical experiment, under argon atmosphere, 5-[4-(2,3,4,6-tetraacetyl-α-D-mannosyl)phenyl]-10,15,20-triphenylporphyrin (40 mg, 42 μmol) was dissolved in 5.0 ml dry tetrahydrofuran and 5.0 ml methanol. Then a solution of sodium methanolate in dry methanol (1.5 ml, 0.06 N) was added. After 2 h, the solvent was evaporated under reduced pressure and the crude product was purified by flash chromatography, using dichloromethane/methanol 9:1 as the eluent. The desired product (32 mg, 98%) was obtained as a violet crystalline solid.

##STR00038##

[0112] mp: 251° C., .sup.1H NMR (500 MHz, (CD.sub.3).sub.2SO): δ=−2.91 (br s, 2H, NH), 3.60-3.66 (m, 2H, H-4‘ose’, H-6.sub.A‘ose’), 3.68-3.72 (m, 1H, H-5‘ose’), 3.76-3.81 (m, 1H, H-6.sub.B‘ose’), 3.86-3.90 (m, 1H, H-3‘ose’), 4.04-4.07 (m, 1H, H-2‘ose’), 4.63 (dd, J=5.9, 5.9 Hz, 1H, OH-6‘ose’), 4.87 (d, J=5.6 Hz, 1H, OH-3‘ose’), 4.95 (d, J=5.6 Hz, 1H, OH-4‘ose’), 5.17 (d, J=4.6 Hz, 1H, OH-2‘ose’), 5.72 (d, J=1.8 Hz, 1H, H-1‘ose’), 7.53 (d, J=8.7 Hz, 2H, Ar—H.sub.meta), 7.80-7.85 (m, 9H, 6×Ph-H.sub.meta, 3×Ph-H.sub.para), 8.13 (d, J=8.7 Hz, 2H, Ar—H.sub.ortho), 8.20-8.23 (m, 6H, Ph-H.sub.ortho), 8.82 (s, 6H, β-H), 8.88 (d, J=4.6 Hz, 2H, β-H) ppm. .sup.13C NMR (126 MHz, (CD.sub.3).sub.2SO): 6=61.79 (t, C-6‘ose’), 67.44 (d, C-4‘ose’), 70.84 (d, C-2‘ose’), 71.42 (d, C-3‘ose’), 75.89 (d, C-5‘ose’), 100.00 (d, C-‘ose’), 115.91 (d, Ar—C.sub.meta), 120.43 (s, Ar—C.sub.meso), 120.52 (s, Ar—C.sub.meso), 127.56 (d, Ph-C.sub.meta), 128.64 (d, Ph-C.sub.para), 134.78 (d, Ph-C.sub.ortho), 135.28 (s, Ar—C.sub.ipso), 135.92 (Ar—C.sub.ortho), 141.78 (s, Ph-C.sub.ipso), 157.15 (s, Ar—C.sub.OMan) ppm. ESI-HRMS: C.sub.50H.sub.41N.sub.4O.sub.6.sup.+ ([M+H].sup.+): calculated 793.3021, found 793.3067. UV/vis ((CH.sub.3).sub.2SO): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 415 (5.38), 513 (4.10), 547 (3.77), 591 (4.01), 647 (3.40) nm.

2.2 Preparation of 5-(4-β-D-lactosylphenyl)-10,15,20-triphenylporphyrin

[0113] In a typical experiment, under argon atmosphere, 5-[4-(2,3,4,6,2′,3′,6′-heptaacetyl-β-D-lactosyl)phenyl]-10,15,20-triphenylporphyrin (37 mg, 30 μmol) was dissolved in 6.0 ml dry tetrahydrofuran and 6.0 ml methanol. Then a solution of sodium methanolate in dry methanol (2.0 ml, 0.06 N) was added. After 2 h, the solvent was evaporated under reduced pressure and the crude product was purified by flash chromatography, using dichloromethane/methanol 9:1 as the eluent. The desired product (28 mg, 98%) was obtained as a violet crystalline solid.

##STR00039##

[0114] mp: >300° C., .sup.1H NMR (500 MHz, (CD.sub.3).sub.2SO): δ=−2.93 (s, 2H, NH), 2.98-3.03 (m, 2H, H‘ose’), 3.48-3.79 (m, 9H, ‘ose’), 3.85-3.89 (m, 1H, ‘ose’), 4.35 (d, J=7.2 Hz, 1H, H‘ose’), 4.68 (d, J=4.6 Hz, 1H, OH‘ose’), 4.82-4.88 (m, 2H, OH‘ose’), 4.93 (d, J=1.6 Hz, 1H, ‘ose’), 4.96 (d, J=5.3 Hz, 1H, ‘ose’), 5.20 (d, J=4.0 Hz, 1H, ‘ose’), 5.33 (d, J=7.8 Hz, 1H, H‘ose’), 5.70 (d, J=5.3 Hz, 1H, OH‘ose’), 7.48 (d, J=8.6 Hz, 2H, Ar—H.sub.meta), 7.81-7.86 (m, 9H, 6×Ph-H.sub.meta, 3×Ph-H.sub.para), 8.13 (d, J=8.6 Hz, 2H, Ar—H.sub.ortho), 8.20-8.23 (m, 6H, Ph-H.sub.ortho), 8.81 (s, 6H, β-H), 8.88 (d, J=4.7 Hz, 2H, β-H) ppm. .sup.13C NMR (126 MHz, (CD.sub.3).sub.2SO): δ=60.62 (C‘ose’), 60.83 (C‘ose’), 68.61 (C‘ose’), 71.33 (C‘ose’), 73.77 (C‘ose’), 73.95 (C‘ose’), 75.45 (C‘ose’), 75.70 (C‘ose’), 76.13 (C‘ose’), 80.61 (C‘ose’), 104.34 (C‘ose’), 115.12 (d, Ar—C.sub.meta), 120.42 (s, Ar—C.sub.meso), 120.45 (s, Ph-C.sub.meso), 120.54 (s, Ph-C.sub.meso), 127.59 (d, Ph-C.sub.meta), 128.67 (d, Ph-C.sub.para), 134.78 (d, Ph-Coho), 135.81 (d, Ar—C.sub.ortho), 141.76 (s, Ph-C.sub.ipso), 157.91 (s, Ar—C.sub.OLac) ppm. ESI-HRMS: C.sub.56H.sub.51N.sub.4O.sub.11.sup.+ ([M+H].sup.+): calculated 955.3554, found 955.3554. UV/vis ((CH.sub.3).sub.2SO): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 419 (4.79), 515 (3.54), 551 (3.27), 592 (3.10), 647 (3.05) nm.

2.3 Preparation of 5,15-bis-(3-β-D-glucosylphenyl)-10,20-dihexylporphyrin

[0115] In a typical experiment, under argon atmosphere, 5,15-bis-[3-(2,3,4,6-tetraacetyl-β-D-glucosyl)-phenyl]-10,20-dihexylporphyrin (25 mg, 19 μmol) was dissolved in 5 ml methanol. Then a solution of sodium methanolate in dry methanol (1.0 ml, 0.02 N) was added. After 4 h, the solvent was evaporated under reduced pressure and the crude product was purified by flash chromatography, using dichloromethane/methanol 8:2 as the eluent. The desired product (17 mg, 91%) was obtained as a violet crystalline solid.

##STR00040##

[0116] mp: >300° C., .sup.1H NMR (500 MHz, CD.sub.3OD): δ=0.86-0.91 (br m, 6H, 2×CH.sub.3), 1.31-1.44 (br m, 8H, 4×CH.sub.2), 1.66-1.74 (br m, 4H, 2×CH.sub.2), 2.33-2.43 (br m, 4H, 2×CH.sub.2), 3.40-3.89 (br m, 10H, H‘ose’), 4.62-4.65 (br m, 2H, H‘ose’), 4.85-4.93 (4H, 2×CH.sub.2), 5.22-5.25 (br m, 2H, H‘ose’), 7.57-7.61 (br m, 2H, Ar—H), 7.66-7.70 (br m, 2H, Ar—H), 7.75-7.80 (br m, 2H, Ar—H), 7.90-7.94 (br m, 2H, Ar—H), 8.80-8.92 (br m, 4H, β-H), 9.34-9.46 (br m, 4H, β-H) ppm. ESI-HRMS: C.sub.56H.sub.67N.sub.4O.sub.12.sup.+ ([M+H].sup.+): calculated 987.4750, found 987.4723. UV/vis ((CH.sub.3).sub.2CO): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 416 (5.18), 514 (3.86), 548 (3.58), 593 (3.30), 650 (3.40) nm.

2.4 Preparation of 5,15-bis-(4-β-D-glucosylphenyl)-10,20-dihexylporphyrin

[0117] In a typical experiment, under argon atmosphere, 5,15-bis-[4-(2,3,4,6-tetraacetyl-β-D-glucosyl)-phenyl]-10,20-dihexylporphyrin (50 mg, 38 μmol) was dissolved in 9.0 ml dry tetrahydrofuran and 9.0 ml methanol. Then a solution of sodium methanolate in dry methanol (3.0 ml, 0.02 N) was added. After 4 h, the solvent was evaporated under reduced pressure and the crude product was purified by flash chromatography, using dichloromethane/methanol 8:2 as the eluent. The desired product (36 mg, 97%) was obtained as a violet crystalline solid.

##STR00041##

[0118] mp: 226° C., .sup.1H NMR (500 MHz, (CD.sub.3).sub.2SO): δ=−2.92 (br s, 2H, NH), 0.84 (t, J=7.3 Hz, 6H, 2×CH.sub.3), 1.24-1.30 (m, 4H, 4×CH.sub.2), 1.35-1.41 (m, 4H, 4×CH.sub.2), 1.69-1.75 (m, 4H, 4×CH.sub.2), 2.32-2.37 (m, 4H, 4×CH.sub.2), 3.38-3.43 (m, 4H, H‘ose’), 3.48-3.53 (m, 2H, H‘ose’), 3.55-3.61 (m, 2H, H‘ose’), 3.79-3.83 (m, 2H, H‘ose’), 4.69-4.72 (m, 2H, H‘ose’), 4.91-4.98 (m, 4H, 2×CH.sub.2), 5.25 (d, J=7.4 Hz, 2H, H-1‘ose’), 7.46 (d, J=8.6 Hz, 4H, Ar—H.sub.meta), 8.08 (d, J=8.6 Hz, 4H, Ar—H.sub.ortho), 8.82 (d, J=4.8 Hz, 4H, β-H), 9.64 (d, J=4.8 Hz, 4H, β-H) ppm. .sup.13C NMR (126 MHz, (CD.sub.3).sub.2SO): δ=14.53 (q, CH.sub.3), 22.72 (t, CH.sub.2), 29.79 (t, CH.sub.2), 29.94 (t, CH.sub.2), 31.90 (t, CH.sub.2), 39.24 (t, CH.sub.2), 61.35 (t, C-6‘ose’), 70.36 (d, C‘ose’), 74.00 (d, C‘ose’), 77.26 (d, C‘ose’), 77.80 (d, C‘ose’), 101.12 (d, C-1‘ose’), 114.97 (d, Ar—C.sub.meta), 118.78 (s, Ar—C.sub.meso), 120.49 (s, Alkyl-C.sub.meso), 135.68 (d, Ar—C.sub.ortho), 157.90 (s, Ar—C.sub.OGlu) ppm. ESI-HRMS: CO.sub.56H.sub.67N.sub.4O.sub.12.sup.+ ([M+H].sup.+): calculated 987.4750, found 987.4746. UV/vis ((CH.sub.3).sub.2SO): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 420 (5.19), 519 (3.89), 554 (3.73), 597 (3.43), 654 (3.56) nm.

2.5 Preparation of 5,15-bis-(4-β-D-galactosylphenyl)-10,20-dihexylporphyrin

[0119] In a typical experiment, under argon atmosphere, 5,15-bis-[4-(2,3,4,6-tetraacetyl-β-D-galactosyl)-phenyl]-10,20-dihexylporphyrin (30 mg, 23 μmol) was dissolved in 5.0 ml dry tetrahydrofuran and 5.0 ml methanol. Then a solution of sodium methanolate in dry methanol (1.8 ml, 0.02 N) was added. After 4 h, the solvent was evaporated under reduced pressure and the crude product was purified by flash chromatography, using dichloromethane/methanol 8:2 as the eluent. The desired product (21 mg, 93%) was obtained as a violet crystalline solid.

##STR00042##

[0120] mp: 176° C., .sup.1H NMR (500 MHz, (CD.sub.3).sub.2SO): δ=−2.89 (br s, 2H, NH), 0.86 (t, J=7.5 Hz, 6H, 2×CH.sub.3), 1.28-1.35 (m, 4H, 2×CH.sub.2), 1.39-1.44 (m, 4H, 2×CH.sub.2), 1.71-1.78 (m, 4H, 2×CH.sub.2), 2.35-2.42 (m, 4H, 2×CH.sub.2), 3.56-3.58 (m, 2H, 2×H-5‘ose’), 3.67-3.71 (m, 4H, 2×H-6‘ose’), 3.77-3.84 (m, 6H, 2×H-2‘ose’, 2×H-3‘ose’, 2×H-4‘ose’), 4.64 (d, J=4.7 Hz, 2H, 2×OH), 4.75-4.78 (m, 2H, 2×OH), 4.92-4.98 (m, 4H, 2×CH.sub.2), 4.99 (d, J=5.6 Hz, 2H, 2×OH), 5.20 (d, J=7.8 Hz, 2H, 2×H-1‘ose’), 5.40 (d, J=5.2 Hz, 2H, 2×OH), 7.48 (d, J=8.5 Hz, 4H, Ar—H.sub.meta), 8.09 (d, J=8.5 Hz, 4H, Ar—H.sub.ortho), 8.84 (d, J=4.4 Hz, 4H, β-H), 9.65 (d, J=4.4 Hz, 4H, β-H) ppm. .sup.13C NMR (126 MHz, (CD.sub.3).sub.2SO): δ=14.52 (q, CH.sub.3), 22.71 (t, CH.sub.2), 29.94 (t, CH.sub.2), 30.98 (t, CH.sub.2), 31.89 (t, CH.sub.2), 34.91 (t, CH.sub.2), 39.22 (t, CH.sub.2), 61.12 (t, C-6‘ose’), 68.86 (d, C‘ose’), 71.08 (d, C‘ose’), 74.01 (d, C-5‘ose’), 76.31 (d, C‘ose’), 101.83 (d, C-1‘ose’), 115.03 (d, Ar—C.sub.meta), 118.81, 120.47, 135.67 (d, Ar—C.sub.ortho), 158.02 (s, Ar—C.sub.OGal) ppm. ESI-HRMS: CO.sub.56H.sub.67N.sub.4O.sub.12.sup.+ ([M+H].sup.+): calculated 987.4750, found 987.4697. UV/vis ((CH.sub.3).sub.2SO): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 421 (5.19), 519 (3.92), 555 (3.76), 597 (3.47), 654 (3.56) nm.

2.6 Preparation of 5,15-bis-(3-β-D-glucosylphenyl)-10,20-diphenylporphyrin

[0121] In a typical experiment, under argon atmosphere, 5,15-bis-[3-(2,3,4,6-tetraacetyl-β-D-glucosyl)-phenyl]-10,20-diphenylporphyrin (20 mg, 15 μmol) was dissolved in 4.0 ml dry tetrahydrofuran and 4.0 ml methanol. Then a solution of sodium methanolate in dry methanol (1.6 ml, 0.02 N) was added. After 4 h, the solvent was evaporated under reduced pressure and the crude product was purified by flash chromatography, using dichloromethane/methanol 8:2 as the eluent. The desired product (13 mg, 89%) was obtained as a violet crystalline solid.

##STR00043##

[0122] mp: >300° C., .sup.1H NMR (700 MHz, (CD.sub.3).sub.2SO): δ=−2.92 (br s, 2H, NH), 3.20-3.24 (m, 2H, H‘ose’), 3.29-3.35 (m, 6H, H‘ose’), 3.46-3.50 (m, 2H, H-6.sub.A‘ose’), 3.66-3.69 (m, 2H, H-6.sub.B‘ose’), 4.54-4.56 (m, 2H, OH‘ose’), 4.98-5.00 (m, 2H, OH‘ose’), 5.09 (d, J=4.9 Hz, 1H, OH‘ose’), 5.19-5.21 (m, 2H, H-1‘ose’), 5.42 (d, J=4.8 Hz, 1H, OH‘ose’), 7.52-7.55 (m, 2H, Ar—H), 7.72-7.75 (m, 2H, Ar—H), 7.83-7.89 (m, 8H, 4×Ph-H.sub.meta, 2×Ph-H.sub.para, 2×Ar—H), 7.89-7.91 (m, 2H, Ar—H), 8.23-8.25 (m, 4H, Ph-H.sub.ortho), 8.84-8.93 (m, 8H, β-H) ppm. .sup.13C NMR (176 MHz, (CD.sub.3).sub.2SO): δ=61.11 (t, C-6‘ose’), 70.16 (d, C‘ose’), 73.87 (d, C‘ose’), 77.03 (d, C‘ose’), 77.44 (d, C‘ose’), 100.83-100.85 (d, C-1‘ose’), 116.28 (d, Ar—C), 120.06 (s, Ar—C.sub.meso), 120.46 (s, Ph-C.sub.meso), 122.88 (d, Ar—C), 127.50 (d, Ph-C.sub.meta), 128.34 (d, Ar—C), 128.58 (d, Ph-C.sub.para), 128.93 (d, Ar—C), 134.66-134.72 (d, Ph-C.sub.ortho), 141.66 (s, Ph-C.sub.ipso), 142.82 (s, Ar—C.sub.ipso), 156.35 (s, Ar—C.sub.OGlu) ppm. ESI-HRMS: CO.sub.56H.sub.51N.sub.4O.sub.12.sup.+ ([M+H].sup.+): calculated 971.3503, found 971.3530. UV/vis ((CH.sub.3).sub.2SO): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 416 (5.26), 513 (3.84), 547 (3.54), 590 (3.32), 649 (3.30) nm.

2.7 Preparation of 5,10,15,20-tetrakis-(4-β-D-glucosyl)-porphyrin (Reference Example)

[0123] In a typical experiment, under argon atmosphere, 5,10,15,20-tetrakis-[4-(2,3,4,6-tetraacetyl-β-D-glucosyl)phenyl]-porphyrin (30 mg, 15 μmol) was dissolved in 6 ml dry tetrahydrofuran and 6 ml methanol. Then, a solution of sodium methanolate in dry methanol (0.6 ml, 0.12 N) was added. After 4 h, the solvent was evaporated under reduced pressure and the crude product was purified by RP.sub.18 flash chromatography, using methanol/water 9:1 as the eluent. The desired product (17 mg, 84%) was obtained as a violet crystalline solid.

##STR00044##

[0124] mp: >300° C., .sup.1H NMR (500 MHz, (CD.sub.3).sub.2SO): δ=−2.91 (br s, 2H, NH), 3.27-3.31 (m, 4H, H‘ose’), 3.40-3.45 (m, 8H, H‘ose’), 3.49-3.54 (ddd, J=1.9, 5.7, 9.5 Hz, 4H, H-5‘ose’), 3.56-3.62 (dd, J=5.7, 11.8 Hz, 4H, H-6.sub.B‘ose’), 3.79-3.83 (m, 4H, H-6.sub.A‘ose’), 4.73 (t, J=5.8 Hz, 4H, OH‘ose’), 5.12 (d, J=5.4 Hz, 4H, OH‘ose’), 5.21 (d, J=4.2 Hz, 4H, OH‘ose’), 5.23 (d, J=7.2 Hz, 4H, H-1 ‘ose’), 5.52 (d, J=4.7 Hz, 4H, OH‘ose’), 7.48 (d, J=8.5 Hz, 8H, 8×Ar-H.sub.meta), 8.13 (d, J=8.5 Hz, 8H, 8×Ar-H.sub.ortho), 9.87 (s, 8H, β-H) ppm. .sup.13C NMR (126 MHz, (CD.sub.3).sub.2SO): δ=61.36 (t, C-6‘ose’), 70.35 (d, C‘ose’), 74.01 (d, C‘ose’), 77.26 (d, C‘ose’), 77.79 (d, C‘ose’), 101.13 (d, C-1‘ose’), 115.11 (d, Ar—C.sub.meta), 120.18 (s, Ar—C.sub.meso), 135.21 (s, Ar—C.sub.ipso), 135.78 (d, Ar—C.sub.ortho), 158.06 (s, Ar—C.sub.OGlu) ppm. ESI-HRMS: C.sub.68H.sub.71N.sub.4O.sub.24.sup.+ [M+H].sup.+: calculated 1327.4458, found 1327.4490. UV/vis ((CH.sub.3).sub.2SO): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 423 (5.67), 518 (4.62), 555 (4.51), 594 (4.33), 650 (4.31) nm.

2.8 Preparation of 5,10,15,20-tetrakis-(3-β-D-galactosyl)-porphyrin (Reference Example)

[0125] In a typical experiment, under argon atmosphere, 5,10,15,20-tetrakis-[3-(2,3,4,6-tetraacetyl-β-D-galactosyl)phenyl]-porphyrin (55 mg, 28 μmol) was dissolved in 2 ml dry tetrahydrofuran and 10 ml methanol. Then a solution of sodium methanolate in dry methanol (1.0 ml, 0.12 N) was added. After 4 h, the solvent was evaporated under reduced pressure and the crude product was purified by RP.sub.18 flash chromatography, using methanol/water 9:1 as the eluent. The desired product (30 mg, 82%) was obtained as a violet crystalline solid.

[0126] This porphyrin is an atropisomer.

##STR00045##

[0127] mp: 253° C., .sup.1H NMR (700 MHz, (CH.sub.3).sub.2SO): δ=−2.95 (br s, 2H, NH), 3.42-3.45 (m, 4H, H‘ose’), 3.48-3.52 (m, 4H, H‘ose’), 3.55-3.59 (m, 8H, H‘ose’), 3.66-3.70 (m, 8H, H‘ose’), 4.59 (br s, 8H, OH-‘ose’), 4.92 (br s, 4H, OH-‘ose’), 5.12-5.18 (m, 4H, H-1‘ose’), 5.30 (br s, 4H, OH-‘ose’), 7.50-7.53 (m, 4H, Ar), 7.71-7.75 (m, 4H, Ar), 7.79-7.84 (m, 4H, Ar), 7.87-7.90 (m, 4H, Ar), 8.87-8.93 (m, 8H, β-H) ppm. ESI-HRMS: C.sub.68H.sub.70N.sub.4O.sub.24Na.sup.+ ([M+Na].sup.+): calculated 1349.4278, found 1349.4297. UV/vis ((CH.sub.3).sub.2CO): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 416 (5.09), 513 (3.67), 546 (3.45), 589 (3.36), 644 (3.30) nm.

2.9 Preparation of 5-(3-β-D-glucosylphenyl)-10,15,20-tris-(4-1′-thio-β-D-glucosyl-2,3,5,6-tetra-fluorophenyl)-porphyrin

[0128] In a typical experiment, under argon atmosphere, 5-(4-β-D-glucosylphenyl)-10,15,20-tris-(pentafluorophenyl)-porphyrin (30 mg, 28 μmol) and 1-thio-β-D-glucose sodium salt (20 mg, 93 μmol) were reacted in 4 ml dry DMF overnight at room temperature. Purification was achieved by column chromatography on silica using ethyl acetate/methanol (17:3) as the eluent. The analytically pure product (40 mg, 89%) was obtained as a violet crystalline solid.

##STR00046##

[0129] mp: 243° C., .sup.1H NMR (700 MHz, CD.sub.3OD): δ=−2.89 (s, 2H, NH), 3.45-3.63 (m, 16H, H-2′‘ose’, H-2‘ose’, H-3′‘ose’, H-3‘ose’, H-4′‘ose’, H-4‘ose’, H-5′‘ose’, H-5‘ose’), 3.72 (dd, J=4.8, 11.9 Hz, 1H, H-6.sub.B‘ose’), 3.82 (dd, J=6.2, 12.0 Hz, 2H, H-6.sub.B‘ose’), 3.83 (dd, J=6.2, 12.0 Hz, 1H, H-6.sub.B‘ose’), 3.88 (dd, J=1.9, 12.0 Hz, 1H, H-6.sub.A‘ose’), 4.05 (dd, J=2.2, 11.9 Hz, 2H, H-6.sub.A′‘ose’), 4.06 (dd, J=2.2, 11.9 Hz, 1H, H-6.sub.A′‘ose’), 5.19-5.23 (m, 3H, H-1′‘ose’), 5.27 (d, J=7.7 Hz, 1H, H-1‘ose’), 7.59-7.63 (m, 1H, Ar—H), 7.64-7.68 (m, 1H, Ar—H), 7.81-7.84 (m, 1H, Ar—H), 8.02-8.05 (m, 1H, Ar—H), 8.98-9.30 (m, 8H, β-H) ppm. .sup.13C NMR (176 MHz, (CD.sub.3OD): 6=61.04 (C-6‘ose’), 61.70 (C-6′‘ose’), 69.96 (C‘ose’), 70.32 (C-4′‘ose’), 73.63 (C‘ose’), 74.59 (C-2′‘ose’), 76.56 (C‘ose’), 76.68 (C‘ose’), 78.37 (C-3′‘ose’), 81.37 (C-5′‘ose’), 85.41 (C-1′‘‘ose’), 100.75 (C-1‘ose’), 102.86 (Ar.sub.F—C.sub.meso), 103.92 (Ar.sub.F—C.sub.meso), 113.41-113.64 (Ar.sub.F—C.sub.SGlu), 116.31 (Ar—C), 120.53-120.93 (Ar.sub.F—C.sub.ipso), 122.41 (Ar—C.sub.meso), 122.83 (Ar—C), 127.59 (Ar—C), 128.78 (Ar—C), 142.15 (Ar—C.sub.ipso), 145.58-145.67 (Ar.sub.F—C), 146.43-146.56 (Ar.sub.F—C), 146.98-147.07 (Ar.sub.F—C), 147.87-147.95 (Ar.sub.F—C), 156.20 (Ar—C.sub.OGlu) ppm. .sup.19F NMR (471 MHz, CD.sub.3OD): δ=−140.47-−140.28 (m, 6 F, Ar—F.sub.meta), −135.11-−134.98 (m, 6 F, Ar—F.sub.ortho) ppm. ESI-HRMS: C.sub.68H.sub.58F.sub.12N.sub.4NaO.sub.21S.sub.3.sup.+ ([M+Na].sup.+): calculated 1613.2462, found 1613.2351. UV/vis (CH.sub.3OH): λ.sub.max(log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 411 (5.53), 506 (4.42), 580 (3.77), 636 (3.11) nm.

2.10 Preparation of 5-(3-β-D-glucosylphenyl)-10,15,20-tris-(4-1′-thio-β-D-galactosyl-2,3,5,6-tetra-fluorophenyl)-porphyrin

[0130] In a typical experiment, under argon atmosphere, 5-(4-β-D-glucosylphenyl)-10,15,20-tris-(pentafluorophenyl)-porphyrin (30 mg, 28 μmol) and 1-thio-β-D-galactose sodium salt (20 mg, 93 μmol) were reacted in 4 ml dry DMF overnight at room temperature. Purification was achieved by column chromatography on silica using methanol/water (8:2) as the eluent. The analytically pure product (36 mg, 81%) was obtained as a violet crystalline solid.

##STR00047##

[0131] mp: 267° C. .sup.1H NMR (700 MHz, CD.sub.3OD): δ=−2.92 (s, 2H, NH), 3.44-3.47 (m, 1H, H-5‘ose’), 3.48 (dd, J=8.4, 9.8 Hz, 1H, H-4‘ose’), 3.54 (dd, J=8.4, 9.0 Hz, 1H, H-3‘ose’), 3.61 (dd, J=7.8, 9.0 Hz, 1H, H-2‘ose’), 3.69 (dd, J=3.3, 9.3 Hz, 3H, H-3′‘ose’), 3.72 (dd, J=4.9, 12.0 Hz, 1H, H-6.sub.B‘ose’), 3.75-3.78 (m, 3H, H-5′‘ose’), 3.85-3.93 (m, 10H, 1×H-6.sub.A‘ose’, 3×H-2′‘ose’, 3×H-6.sub.A′‘ose’, 3×H-6B′‘ose’), 4.03-4.05 (m, 3H, H-4′‘ose’), 5.12 (d, J=9.5 Hz, 3H, H-1′‘ose’), 5.26 (d, J=7.8 Hz, 1H, H-1‘ose’), 7.58-7.62 (m, 1H, Ar—H), 7.64-7.68 (m, 1H, Ar—H), 7.78-7.81 (m, 1H, Ar—H), 8.00-8.03 (m, 1H, Ar—H), 8.93-9.32 (m, 8H, β-H) ppm. .sup.13C NMR (176 MHz, (CD.sub.3OD): δ=61.00 (C-6‘ose’), 61.33 (C-6′‘ose’), 69.22 (C-4′‘ose’), 69.93 (C-4‘ose’), 71.43 (C-2′‘ose’), 73.60 (C-2‘ose’), 74.94 (C-3′‘ose’), 76.52 (C-3‘ose’), 76.63 (C-5‘ose’), 79.91 (C-5′‘ose’), 86.28 (C-1′‘ose’), 100.70 (C-1‘ose’), 102.86 (Ar.sub.F—C.sub.meso), 103.92 (Ar.sub.F—C.sub.meso), 113.28-113.52 (Ar.sub.F—C.sub.SGal), 116.31 (Ar—C), 120.65-121.05 (Ar.sub.F—C.sub.ipso), 122.39 (Ar—C.sub.meso), 122.82 (Ar—C), 127.62 (Ar—C), 128.80 (Ar—C), 142.11 (Ar—C.sub.ipso), 145.56-145.66 (Ar.sub.F—C), 146.63-146.71 (Ar.sub.F—C), 146.96-147.05 (Ar.sub.F—C), 148.01-148.10 (Ar.sub.F—C), 156.14 (Ar—C.sub.OGlu) ppm. .sup.19F NMR (471 MHz, CD.sub.3OD): δ=−140.52-−140.32 (m, 6 F, Ar—F.sub.meta), −134.34-−134.70 (m, 6 F, Ar—F.sub.ortho) ppm. ESI-HRMS: C.sub.68H.sub.58F.sub.12N.sub.4NaO.sub.21S.sub.3.sup.+ ([M+Na].sup.+): calculated 1613.2462, found 1613.2384. UV/vis (CH.sub.3OH): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 412 (5.57), 506 (4.29), 581 (3.81), 636 (2.98) nm.

Example 3—Preparation of Glycosylated Chlorins

3.1 Preparation of 5-(3-β-D-glucosylphenyl)-10,15,20-trihexyl-17,18-dihydroxy-17,18-chlorin

[0132] In a typical experiment, osmium tetroxide (37 mg, 0.2 mmol) was added to a stirred solution of 5-[3-(2,3,4,6-tetraacetyl-β-D-glucosyl)phenyl]-10,15,20-trihexylporphyrin (120 mg, 0.12 mmol) in dichloromethane/pyridine 2:1 (6 ml). After stirring for 30 minutes at 0° C. and additional 8 hours at room temperature, a saturated solution of sodium bisulfite in water/methanol 1:1 (25 ml) was added and the mixture was stirred for 18 h. The reaction mixture was filtered through Celite and dried over anhydrous sodium sulfate. The solvent was evaporated and the residue was purified by flash chromatography with dichloromethane/ethyl acetate 95:5 as eluent, followed by recrystallization from dichloromethane/methanol. The chlorin (30 mg, 24%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol, as a regioisomeric mixture.

[0133] To a stirred solution of 5-[3-(2,3,4,6-tetraacetyl-β-D-glucosyl)phenyl]-10,15,20-trihexyl-17,18-dihydroxy-17,18-chlorin (25 mg, mmol) in dry tetrahydrofuran/methanol 1:1 (5 ml) under an argon atmosphere, a solution of sodium methanolate in dry methanol (1.0 ml, 0.02 N) was added. After 3 h, the solvent was evaporated under reduced pressure and the crude product was purified by RP.sub.18 flash chromatography, using methanol/water 9:1 as the eluent. The desired product (19 mg, 91%) was obtained after recrystallization from dichloromethane/aqueous methanol as a violet crystalline solid.

##STR00048##

[0134] mp: 135° C., .sup.1H NMR (500 MHz, (CD.sub.3).sub.2CO): δ=−1.95 (s, 1H, NH), −1.91 (s, 1H, NH), 0.88-0.98 (m, 9H, 3×CH.sub.3), 1.32-1.55 (m, 12H, 6×CH.sub.2), 1.73-1.85 (m, 6H, 3×CH.sub.2), 2.21-2.44 (m, 6H, 3×CH.sub.2), 3.52-3.63 (m, 5H), 3.67-3.74 (m, 1H), 3.82-3.88 (m, 1H), 4.18-4.20 (br s, 1H), 4.30-4.32 (m, 1H), 4.39-4.49 (m, 2H, CH.sub.2), 4.61-4.67 (m, 2H, CH.sub.2), 4.68-4.70 (m, 1H), 4.74-4.80 (m, 2H, CH.sub.2), 5.25-5.28 (m, 3H), 6.57-6.60 (m, 2H, β-H), 7.47-7.51 (m, 1H, Ar—H), 7.63-7.67 (m, 1H, Ar—H), 7.71-7.73 (m, 1H, Ar—H), 7.79-7.82 (m, 1H, Ar—H), 8.47-8.49 (m, 1H, β-H), 8.71-8.73 (m, 1H, β-H), 9.15-9.18 (m, 2H, β-H), 9.24-9.26 (m, 1H, β-H), 9.49-9.51 (m, 1H, β-H) ppm. ESI-HRMS: C.sub.50H.sub.67N.sub.4O.sub.8.sup.+ [M+H].sup.+: calculated 851.5, found 851.5. UV/vis ((CH.sub.3).sub.2CO): λ.sub.max(log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 406 (5.32), 428 (5.21), 525 (4.25), 551 (4.34), 596 (3.95), 649 (4.37) nm.

3.2 Preparation of 5,10,15-tris-(3-β-D-galactosylphenyl)-20-[3,5-bis-(trifluoromethyl)-phenyl]-17,18-dihydroxy-17,18-chlorin

[0135] In a typical experiment, osmium tetroxide (100 mg, 0.39 mmol) was added to a stirred solution of 5,10,15-tris-[3-(2,3,4,6-tetraacetyl-β-D-galactosyl)phenyl]-20-[3,5-bis-(trifluoromethyl)phenyl]-porphyrin (300 mg, 0.17 mmol) in dichloromethane/pyridine 1:1 (26 ml). After stirring for 30 minutes at 0° C. and additional 2 hours at room temperature, a saturated solution of sodium bisulfite in water/methanol 1:1 (25 ml) was added and the mixture was stirred for 18 h. The reaction mixture was filtered through Celite and dried over anhydrous sodium sulfate. The solvent was evaporated and the residue was purified by flash chromatography with dichloromethane/methanol 95:5 as eluent, followed by recrystallization from dichloromethane/aqueous methanol. The chlorin (129 mg, 42%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol, as a regioisomeric mixture.

[0136] To a stirred solution of 5,10,15-tris-[3-(2,3,4,6-tetraacetyl-β-D-galactosyl)phenyl]-20-[3,5-bis-(trifluoromethyl)phenyl]-17,18-dihydroxy-17,18-chlorin (46 mg, 25 μmol) in dry tetrahydrofuran/methanol 1:1 (10 ml) under an argon atmosphere, a solution of sodium methanolate in dry methanol (1.0 ml, 0.1 N) was added. After 4 h, the solvent was evaporated under reduced pressure and the crude product was purified by RP.sub.18 flash chromatography, using methanol/water 85:15 as the eluent. The desired product (33 mg, 99%) was obtained as a violet crystalline solid after washing with dichloromethane.

[0137] This chlorin is an atropisomer.

##STR00049##

[0138] mp: >300° C., .sup.1H NMR (500 MHz, CD.sub.3OD): δ=3.54-3.88 (m, 18H, H‘ose’), 5.02-5.12 (3H, H‘ose’), 6.13-6.36 (m, 2H, β-H), 7.39-8.79 (m, 21H, 6×β-H, 15 Ar—H) ppm. ESI-HRMS: C.sub.64H.sub.60F.sub.6N.sub.4O.sub.20Na.sup.+ ([M+Na].sup.+): calculated 1341.3597, found 1341.3594. UV/vis ((CH.sub.3).sub.2CO): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 407 (4.51), 515 (3.53), 541 (3.49), 594 (3.18), 646 (3.78) nm.

3.3 Preparation of 5,10,15-tris-(3-β-D-lactosylphenyl)-20-[3,5-bis-(trifluoromethyl)-phenyl]17,18-dihydroxy-17,18-chlorin

[0139] In a typical experiment, osmium tetroxide (100 mg, 0.39 mmol) was added to a stirred solution of 5,10,15-tris-[3-(2,3,4,6,2′,3′,6′-heptaacetyl-β-D-lactosyl)-phenyl]-20-[3,5-bis-(trifluoro-methyl)phenyl]-porphyrin (350 mg, 0.13 mmol) in dichloromethane/pyridine 1:1 (15 ml). After stirring for 30 minutes at 0° C. and additional 2 hours at room temperature, a saturated solution of sodium bisulfite in water/methanol 1:1 (25 ml) was added and the mixture was stirred for 18 h. The reaction mixture was filtered through Celite and dried over anhydrous sodium sulfate. The solvent was evaporated and the residue was purified by flash chromatography with dichloromethane/methanol 95:5 as eluent, followed by recrystallization from dichloromethane/aqueous methanol. The chlorin (39 mg, 8%) was obtained as a violet crystalline solid after recrystallization from dichloromethane/aqueous methanol, as a regioisomeric mixture.

[0140] To a stirred solution of 5,10,15-tris-[3-(2,3,4,6,2′,3′,6′-heptaacetyl-D-lactosyl)phenyl]-20-[3,5-bis-(trifluoromethyl)phenyl]-17,18-dihydroxy-17,18-chlorin (32 mg, 12 μmol) in dry tetrahydrofuran/methanol 1:1 (10 ml) under an argon atmosphere, a solution of sodium methanolate in dry methanol (1.5 ml, 0.1 N) was added. After 4 h, the solvent was evaporated under reduced pressure and the crude product was purified by RP.sub.18 flash chromatography, using methanol/water 85:15 as the eluent. The desired product (21 mg, 98%) was obtained as a violet crystalline solid after washing with dichloromethane.

[0141] This chlorin is an atropisomer.

##STR00050##

[0142] mp: >300° C., .sup.1H NMR (500 MHz, CD.sub.3OD): δ=3.43-3.84 (m, 36H, H‘ose’), 4.31-4.38 (m, 3H, H‘ose’), 5.17-5.25 (m, 3H, H‘ose’), 6.13-6.32 (m, 2H, β-H), 7.39-8.80 (m, 21H, 6×β-H, 1 Ar—H) ppm. ESI-HRMS: C.sub.82H.sub.90F.sub.6N.sub.4O.sub.35Na.sup.+ ([M+Na].sup.+): calculated 1827.5182, found 1827.5282. UV/vis (CH.sub.3CH.sub.2OH): λ.sub.max (log ε/dm.sup.3 mol.sup.−1 cm.sup.−1): 415 (4.92), 514 (3.86), 541 (3.83), 594 (3.49), 646 (4.12) nm.

Example 4—Cell Tests of Selected Compounds in the HT 29 and Other Cell Lines

[0143] The photosensitizing activity was determined in the following cell lines: [0144] HT29 (human colon adenocarcinoma cell line) [0145] L929 (mouse fibroblast cell line) [0146] A431 (human epidermoid carcinoma cell line) [0147] A253 (submaxillary salivary gland, epidermoid cell line) [0148] CAL-27 (human tongue squamous cell carcinoma cell line).

[0149] The cell lines were grown in DMEM (PAA Laboratories GmbH) supplemented with 10% heat-inactivated fetal calf serum (FCS, PAA Laboratories GmbH), 1% penicillin (10000 IU) and streptomycin (10000 μg/ml, PAA Laboratories GmbH). Cells were kept as a monolayer culture in a humidified incubator (5% CO.sub.2 in air at 37° C.).

[0150] A photosensitizer stock solution (2 mM) was performed in DMSO and was kept in the dark at 4° C. Further dilution was performed in DMEM medium without phenol red supplemented with 10% FCS to reach a final photosensitizer concentration of 2 or 10 μM, respectively.

[0151] 2.Math.10.sup.4 cells/ml were seeded in micro plates (2.Math.10.sup.5 cells/well). Cells were incubated with fresh medium (DMEM without phenol red) containing 10% FCS with 2 or 10 μM of the photosensitizer for 24 h before light exposure. Before photosensitization, cells were washed, cell culture medium was exchanged with DMEM without phenol red and 10% FCS, then irradiated at room temperature with a 652 nm diode laser (Ceralas PDT 652, biolitec AG) at a fixed fluence rate of 100 mW/cm.sup.2 (50 J/cm.sup.2). Following irradiation, cells were incubated in a humidified incubator (5% CO.sub.2 in air at 37° C.) for 24 h until cell viability assay.

[0152] The cell viability was assessed by the XTT assay. 500 mg XTT (sodium 3′-[phenylaminocarbonyl)-3,4-tetrazolium]-bis(4-methoxy-6-nitro)benzene sulfonic acid, Applichem GmbH) is dissolved in 500 ml PBS-Buffer (without Ca.sup.2+ and Mg.sup.2+) and sterile filtered. Solution was stored in the dark at −20° C. until use. A sterile solution containing PMS (N-methyl dibenzopyrazine methyl sulfate, Applichem GmbH) was needed as an activation reagent for the XTT. 0.383 mg PMS was dissolved in 1 ml PBS-Buffer. The solution should be stored frozen and should not be exposed to light. The XTT reagent solution was thawed in a 37° C. water bath and the activation solution (PMS) was added immediately prior to use. To prepare a reaction solution sufficient for one micro plate (96 wells), 0.1 ml activation solution (PMS) was given to 5 ml XTT reagent. The medium in the micro plate was exchanged with RPMI without phenol red and 10% FCS (100 μl) prior adding 50 μl XTT reaction solution per well. The micro plate was incubated for 2-3 hours at 37° C. and 5% CO.sub.2 until an orange dye is to be formed. The micro plate has been shaken gently to evenly distribute the dye in the wells.

[0153] The absorbance of the samples was measured with a spectrophotometer (Infinite 200, Tecan Group Ltd.) at a wavelength of 490 nm. In order to measure reference absorbance (to measure non-specific readings) a wavelength of 630-690 nm was used.

[0154] The results of Examples 4.1 to 4.5, which are shown in FIGS. 1 to 5, illustrate the photodynamic activity (“DT” means dark toxicity and “Laser” means photo toxicity) of photosensitizers having a substitution pattern according to the present invention. Specifically the photosensitizers according to the invention exhibit a strong photodynamic activity even in the HT29 cell line, which is known to be very resistant against cell-toxic agents and PDT as well.

[0155] The results of Examples 4.6 to 4.9, which are shown in FIGS. 6 to 9, are included to illustrate, that photosensitizers which do not have a substitution pattern as referred to in the present invention exhibit a less promising photodynamic activity in the cell experiments, in particular with respect to cell line HT29.