CZ200827A3 - Oligopyrrole macrocycles substituted in meso positions with glycosylated steroids and process for preparing thereof - Google Patents
Oligopyrrole macrocycles substituted in meso positions with glycosylated steroids and process for preparing thereof Download PDFInfo
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Abstract
Syntéza oligopyrrolových makrocyklu vzorcu I, II, III s glykosylovanými steroidy v "meso" polohách, vycházející ze steroidních aldehydu, nesoucích cukr pripojený glykosidovou vazbou, kde v závislosti na podmínkách reakce lze ovlivnit pocet steroidních jednotek pripojených k makrocyklu, a glykosidicky pripojený cukr lze na konci syntetického postupu zbavit chránících skupin s dobrými výtežky. Výše uvedené makrocykly jsou použitelné pro výrobu elektrochemických sensoru a výrobku sloužících jako detektory a prenašece vybraných substrátu.Synthesis of oligopyrrole macrocycles of formula I, II, III with glycosylated steroids in "meso" positions, based on steroid aldehydes carrying sugar attached by a glycosidic bond, whereby the number of steroid units attached to the macrocycle can be influenced depending on the reaction conditions, and glycosidically linked sugar can be at the end of the synthetic procedure to remove the protecting groups with good yields. The aforementioned macrocycles are useful for producing electrochemical sensors and articles serving as detectors and carriers for selected substrates.
Description
Oligopyrrolové makrocykly substituované v weso-polohách glykosylovanými steroidy a jejich přípravaOligopyrrole macrocycles substituted in weso positions by glycosylated steroids and their preparation
Oblast technikyTechnical field
Vynález se týká oligopyrrolových makrocyklů s glykosylovanými steroidy v polohách ,,meso“ a jejich syntézy.The invention relates to oligopyrrole macrocycles with glycosylated steroids at the meso positions and their synthesis.
Dosavadní stav technikyBACKGROUND OF THE INVENTION
V posledních letech se steroidni struktury stávají stále důležitějšími v mnoha oborech jako je farmakologie, supramolekulámí chemie a také nanotechnologie (Virtanen E., KolehmainenIn recent years, steroid structures have become increasingly important in many fields such as pharmacology, supramolecular chemistry and nanotechnology (Virtanen E., Kolehmainen
E.: Eur. J. Org. Chem, 2004, 3385). Řazení steroidů mezi přírodní látky je věcí historickou, protože dnes už je počet steroidů izolovaných z přírodních zdrojů menší, než počet steroidů připravených v laboratořích parciální či totální syntézou. Obměna struktury vede k látkám vhodnějších vlastností, popř. k látkám se zcela novými účinky. U systémů tetrapyrrolového makrocyklů s glykosylovanými steroidními substituenty v meso polohách lze očekávat nové velmi cenné vlastnosti např. komplexotvomé, schopnost selektivní molekulární interakce, fluorescenční a schopnost podílet se v excitovaných tripletových stavech na elektronové výměně. Tyto molekuly mohou mj. sloužit jako selektivní molekulární receptory na organické i anorganické sloučeniny, dále by se daly využít např. v oblastech chemie molekulového rozpoznání, k výstavbě iontových kanálů pro přenos iontů a nebo ve fotodynamické terapii (PDT). Jako příklad takových oligopyrrolových makrocyků lze uvést steroidni deriváty (DukhE .: Eur. J. Org. Chem., 2004, 3385). The classification of steroids among natural substances is a historical matter, because today the number of steroids isolated from natural sources is less than the number of steroids prepared in laboratories by partial or total synthesis. The modification of the structure leads to substances of more suitable properties, respectively. to substances with completely new effects. In tetrapyrrole macrocycles systems with glycosylated steroid substituents at the meso positions, new, very valuable properties such as complex-forming, selective molecular interaction, fluorescence, and the ability to participate in excited triplet states in electron exchange can be expected. These molecules can serve, among other things, as selective molecular receptors for organic and inorganic compounds, and could also be used, for example, in the field of molecular recognition chemistry, to build ion channels for ion transfer or in photodynamic therapy (PDT). An example of such oligopyrrole macrocytes is steroid derivatives (Dukh
M., Šaman D., Lang K., Pouzar V., Černý L, Drašar P., Král V.: Org. Biomol.Chem. 2003,1, 3458), které vykazují schopnost enantioselektivní rozpoznání aprotických organických aniontů, případně samoskladné vlastnosti (Štěpánek P., Dukh M., Šaman D., Moravcová J., Kniežo L., Monto D., Venanzi M., Mancini G., Drašar P.: Org. Biomol. Chem., 2007,5,960970). Sloučeniny tohoto druhu mají také významné elektrochemické vlastnosti (RumlerováLipsová A., Bárek J., Drašar P., Zelenka K., Pecková K.:, Int. J. Electrochem. Sci. 2007, 2, 235), což je předurčuje m.j. k možné výrobě sensorů.M., Shaman D., Lang K., Pouzar V., Cerny L, Drasar P., Kral V .: Org. Biomol.Chem. 2003,1, 3458), which show the ability of enantioselective recognition of aprotic organic anions, or self-storage properties (Stepanek P., Dukh M., Shaman D., Moravcova J., Knezo L., Monto D., Venanzi M., Mancini G , Drasar P .: Org. Biomol. Chem., 2007, 5, 960970). Compounds of this type also possess significant electrochemical properties (Rumler Lipips A., Barek J., Drasar P., Zelenka K., Peckova K., Int. J. Electrochem. Sci. 2007, 2, 235), which predetermines them, inter alia. possible production of sensors.
Podstata vynálezuSUMMARY OF THE INVENTION
Podstatou vynálezu je syntéza oligopyrrolových makrocyklů vzorců I, II, III v polohách „meso“ s glykosylovanými steroidy, vycházející ze steroidních aldehydů, které nesou cukr připojený glykosidovou vazbou, vyznačující se tím, že v závislosti na podmínkách reakce lze ovlivnit počet steroidních jednotek připojených k makrocyklů a tím, že glykosidícky připojený cukr lze na konci syntetického postupu zbavit chránících skupin s dobrými výtěžky.The present invention relates to the synthesis of oligopyrrole macrocycles of formulas I, II, III at the meso positions with glycosylated steroids, starting from steroid aldehydes carrying a glycosidic-linked sugar, characterized in that the number of steroid units attached to the macrocycles and by deprotecting the glycosidically linked sugar at the end of the synthetic process with good yields.
Syntéza spočívá v kondenzaci vhodně zvoleného a chráněného aldehydu svolnými či substituovanými pyrroly. Uvedeným způsobem lze získat oligopyrroiové makrocykly substituované v meso-polohách glykosylovanými steroidy s jedním až čtyřmi steroidními substítuenty na kruhu a odstranit na závěr syntézy chránící skupiny.The synthesis consists in condensing a suitably selected and protected aldehyde with free or substituted pyrroles. In this way, oligopyrrole macrocycles substituted at the meso positions by glycosylated steroids with one to four steroid substituents on the ring can be obtained and removed at the end of the synthesis of the protecting group.
Nový způsob přípravy je doložen následujícími příklady, aniž by jimi byly jakkoliv omezeny.The new process is illustrated by the following examples without being limited thereto.
Příklad 1Example 1
Míchaný roztok 3a-(2,3,4,6-tetra-O-acetyl-3-D-glukopyranosyloxy)-5p-cholan-24-alu (243 mg, 0.35 mmol) a pyrrolu (24 mg, 25 μΐ, 0.35 mmol) v suchém dichlormethanu (35 ml) byl probubláván argonem 15 min. Poté byl šeptem přidán BF^^O (5 mg, 4.5 μΐ, 0.035 mmol) a reakční nádoba byla nadále uchovávána za nepřístupu světla a byla dále míchána 3 h pod argonem. Poté byl přidán DDQ (104 mg, 0.46 mmol) a směs byla dále míchána 8 h. Po přidání triethylaminu (3.6 mg, 5 μΙ, 0.035 mmol) byla rozpouštědla oddestilována ve vakuu. Zbytek byl rozpuštěn ve směsi ethyl-acetát - toluen (2:1) a sfiltrován přes kolonku silikageluA stirred solution of 3α- (2,3,4,6-tetra-O-acetyl-3-D-glucopyranosyloxy) -5β-cholan-24-alu (243 mg, 0.35 mmol) and pyrrole (24 mg, 25 μΐ, 0.35) mmol) in dry dichloromethane (35 mL) was bubbled with argon for 15 min. BF 2 O (5 mg, 4.5 μΐ, 0.035 mmol) was then added in a whisper and the reaction vessel was kept under light-free conditions and further stirred for 3 h under argon. DDQ (104 mg, 0.46 mmol) was then added and the mixture was further stirred for 8 h. After addition of triethylamine (3.6 mg, 5 μΙ, 0.035 mmol) the solvents were distilled off in vacuo. The residue was dissolved in ethyl acetate-toluene (2: 1) and filtered through a silica gel column.
MM ··· ··· (30 g) s tím, že byly posbírány pouze porfýrinové frakce. Chromatografií na koloně silikagelu (toluen-ethyl-acetát 5:1) byly získány dvě porfyrinové frakce. Prvá poskytla po odpaření červeno-hnědou amorfní látku, 5,10,15,20-tetrakis[3a-(2,3,4,6-tetra-O-acetyl-p-Dglukopyranosyloxy)-5p-cholan-24-yl]-porfyrin (40 mg, 15 %). UV-Vis: (CHCI3) 421 nm (log ε = 5.39). *H NMR (400 MHz, C6D6): -1.88 bs, 2 H (2 χ NH-pyrrol); 0.77 s, 12 H (4 x H18); 0.96 s, 12 H (4 x H-19); 1.49 d, 12 H (J= 6.4,4 x H-21); 1.69 s, 12 H; 1.71 s, 12 H; 1.72 s, 12 H; 1.80 s, 12 H (12 x OAc); 0.80-2.70,104 H (4 x steroidní fingerprint); 3.37 ddd, 4 H (Ji = 10.0, J2 = 4.4, J3 = 2.4,4 x H-5'); 3.64 bm, 4 H (4 χ H-3p); 4.10 dd, 4 H (Ji = 12.4, J2 =MM ··· ··· (30 g) except that only porphyrin fractions were collected. Silica gel column chromatography (toluene-ethyl acetate 5: 1) yielded two porphyrin fractions. The first gave, after evaporation, a red-brown amorphous substance, 5,10,15,20-tetrakis [3α- (2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy) -5β-cholan-24-yl] Porphyrin (40 mg, 15%). UV-Vis: (CHCl 3) 421 nm (log ε = 5.39). 1 H NMR (400 MHz, C 6 D 6 ): -1.88 bs, 2H (2 χ NH-pyrrole); 0.77 s, 12H (4 * H18); 0.96 s, 12H (4 * H-19); 1.49 d, 12 H (J = 6.4, 4 x H-21); 1.69 s, 12H; 1.71 s, 12H; 1.72 s, 12H; 1.80 s, 12H (12 * OAc); 0.80-2.70,104 H (4 x steroid fingerprint); 3.37 ddd, 4 H (J 1 = 10.0, J 2 = 4.4, J 3 = 2.4.4 x H-5 '); 3.64 bm, 4 H (4 'H-3β); 4.10 dd, 4 H (J 1 = 12.4, J 2 =
2.3,4 χ H-6a‘); 4.32 dd, 4 H (Ji = 12.4, J2 = 4.8,4 x H-6b‘); 4.51 d, 4 H (Ji = 8.4,4 χ H-1‘); 4.59 bm, 4 H (4 x H-23a); 4.87 bm, 4 H (4 χ H-23b); 5.301,4 H (J= 9.2,4 x H-4‘); 5.35 dd, 4 H (Ji = 9.2, J2 = 8.0,4 x H-2‘); 5.501,4 H (J= 9.2,4 x H-3‘); 9.42 bs, 8 H (8 x H-pyrrole). I3C NMR (100 MHz, C6D6): 13.11, 20.36, 20.85, 20.95, 20.98, 21.15, 22.02, 24.39, 25.21, 27.12,28.25(2C), 29.72,33.69,35.30, 35.55,36.31,36.69, 38.60,40.98,41.21,43.26,43.68, 46.65, 56.62,56.71,62.68,69.58,72.78,72.95,74.21, 80.55,100.45,119.69,169.47,169.78, 170.79, 170.80. Pro C168H238N4O40 vypočteno Exact Mass: 2951.67; MW 2953.69, m/z:2.3.4 (H-6a '); 4.32 dd, 4 H (J 1 = 12.4, J 2 = 4.8.4 x H-6b '); 4.51 d, 4 H (J 1 = 8.4.4 χ H-1 '); 4.59 bm, 4H (4 * H-23a); 4.87 bm, 4 H (4 < - >H-23b); 5.301.4 H (J = 9.2.4 x H-4 '); 5.35 dd, 4 H (J 1 = 9.2, J 2 = 8.0.4 x H-2 '); 5.501.4 H (J = 9.2.4 x H-3 '); 9.42 bs, 8H (8 * H-pyrrole). I3 C NMR (100 MHz, C 6 D 6): 13.11, 20.36, 20.85, 20.95, 20.98, 21.15, 22.02, 24.39, 25.21, 27.12,28.25 (2C), 29.72,33.69,35.30, 35.55,36.31,36.69, 38.60,40.98,41.21,43.26,43.68, 46.65, 56.62,56.71,62.68,69.58,72.78,72.95,74.21, 80.55,100.45,119.69,169.47,169.78, 170.79, 170.80. For C168H238N4O40 calculated Exact Mass: 2951.67; MW 2953.69, m / z:
2952.67 (100.0 %), 2953.68 (98.3 %), 2954.68 (65.8 %), 2951.67 (54.6 %), 2955.68 (32.5 %), 2956.69 (14.2 %), 2957.69 (5.4 %), 2955.69 (2.5 %), 2952.68 (2.3 %), 2958.69 (1.6 %),2952.67 (100.0%), 2953.68 (98.3%), 2954.68 (65.8%), 2951.67 (54.6%), 2955.68 (32.5%), 2956.69 (14.2%), 2957.69 (5.4%), 2955.69 (2.5%) 2.3%), 2958.69 (1.6%)
2953.67 (1.5 %), 2954.67 (1.4 %); nalezeno MS (MALDI, CHCI3), m/τ. 2952.27. Získaný2953.67 (1.5%); 2954.67 (1.4%); MS found (MALDI, CHCl 3) m / τ. 2952.27. Acquired
5.10.15.20- tetrakis[3a-(2,3,4,6-tetra-O-acetyl-P-D-glukopyranosyloxy)-5p-cholan-24-yl]porfyrin (30 mg, 10 pmol) byl rozpuštěn ve směsi suchého methanolu (10 ml) a suchého dichlormethanu (5 ml) a ke směsi byl přidán methanolát sodný (6 mg, 0.15 mmol). Směs byla míchána 1 den, a poté byla neutralizována Dowexem 50 v H+ cyklu (30 mg). Ke směsi byl přidán dichlormethan (35 ml) a směs byla zfíltrována přes Celit. Zbytek byl extrahován směsí dichlormethan-methanol (4:1) a pak pyridinem. Rozpouštědla byla odpařena a byl získán5.10.15.20-tetrakis [3- (2,3,4,6-tetra-O-acetyl-PD-glucopyranosyloxy) -5β-cholan-24-yl] porphyrin (30 mg, 10 pmol) was dissolved in dry methanol (10 mL) and dry dichloromethane (5 mL) and sodium methoxide (6 mg, 0.15 mmol) was added. The mixture was stirred for 1 day and then neutralized with Dowex 50 in an H + cycle (30 mg). Dichloromethane (35 mL) was added and the mixture was filtered through Celite. The residue was extracted with dichloromethane-methanol (4: 1) followed by pyridine. The solvents were evaporated and recovered
5.10.15.20- tetrakis[3a-(P-D-glukopyranosyloxy)-5p-cholan-24-yl]-porfyrin (20 mg, 86 %) jako hnědý prášek. UV-Vis: (pyridin) Xmax 421 nm (log ε = 5.50). 'Η NMR (400 MHz, C5D5N): -1.85 bs, 2 H (2 χ NH-pyrrol); 0.81 s, 12 H (4 x H-18); 0.92 s, 12 H (4 χ H-19); 1.67 d, 12 H (J= 6.4,4 x H-21); 0.80-2.90,104 H (4 χ steroidní fingerprint); 3.98-4.12,12 H; 4.27 t, 4 H (J= 8.8); 4.33 t, 4 H (J = 8.4) (4 χ Η-3β, H-2‘, H-3‘, H-4‘, H-5*); 4.44 dd, 4 H (Ji = 11.6, Λ = 5-6,4 x H-6a‘); 4.63 bd, 4 H (J= 11.6,4 x H-6b4); 5.00-5.30, 8 H (4 x H-23a,b); 5.09 d, 4 H (J= 7.6, 4 χ Η-Γ); 9.90 bs, 8 H (8 x H-pyrrol). 13C NMR (100 MHz, C5D5N): 12.37, 19.62, 21.11, 23.53, 24.52, 26.56, 27.27, 27.40, 29.04, 33.06, 34.63, 34.81, 35.37, 35.86, 38.00, 40.36, 40.60, 42.26, 43.08, 46.41, 56.36, 56.50, 62.90, 71.75, 75.40, 77.82, ··♦5.10.15.20-tetrakis [3α- (PD-glucopyranosyloxy) -5β-cholan-24-yl] -porphyrin (20 mg, 86%) as a brown powder. UV-Vis: (pyridine) λ max 421 nm (log ε = 5.50). 1 H NMR (400 MHz, C 5 D 5 N): -1.85 bs, 2 H (2 χ NH-pyrrole); 0.81 s, 12H (4xH-18); 0.92 s, 12 H (4 χ H-19); 1.67 d, 12H (J = 6.4, 4H-21); 0.80-2.90,104 H (4 χ steroid fingerprint); 3.98-4.12,12 H; 4.27 t, 4H (J = 8.8); 4.33 t, 4 H (J = 8.4) (4 ' -3β, H-2 ', H-3', H-4 ', H-5 *); 4.44 dd, 4 H (J 1 = 11.6, J = 5-6.4 x H-6a '); 4.63 bd, 4 H (J = 11.6, 4 x H-6b 4 ); 5.00-5.30, 8H (4xH-23a, b); 5.09 d, 4 H (J = 7.6, 4 < -1 >); 9.90 bs, 8H (8 * H-pyrrole). 13 C NMR (100 MHz, C 5 D 5 N): 12.37, 19.62, 21.11, 23.53, 24.52, 26.56, 27.27, 27.40, 29.04, 33.06, 34.63, 34.81, 35.37, 35.86, 38.00, 40.36, 40.60, 42.26, 43.08, 46.41, 56.36, 56.50, 62.90, 71.75, 75.40, 77.82, ·· ♦
78,58, 78.70, 102.01, 119.69. Pro C136H206N4O24 vypočteno Exact Mass: 2279.50; MW78.58, 78.70, 102.01, 119.69. For C36H206N4O24 calculated Exact Mass: 2279.50; MW
2281.10, mJz\ 2280.51 (100.0 %), 2281.51 (77.9 %), 2279.50 (66.5 %), 2282.51 (41.2 %), 2283.52 (13.7 %), 2284.52 (5.7 %), 2283.51 (4.2 %), 2282.52 (1.7 %), 2285.52 (1.7 %), 2281.50 (1.5 %); nalezeno MS (MALDI, CHCl3/MeOH), mte. 2280.354. MS (ESI, MeOH/CHCh + HCOOH): 2281.1.2281.10, mJz \ 2280.51 (100.0%), 2281.51 (77.9%), 2279.50 (66.5%), 2282.51 (41.3%), 2283.52 (13.7%), 2284.52 (5.7%), 2283.51 (4.2%), 2282.52 (1.7%) ), 2285.52 (1.7%); 2281.50 (1.5%); MS found (MALDI, CHCl 3 / MeOH) mte. 2280.354. MS (ESI, MeOH / CHCl 3 + HCOOH): 2281.1.
Přiklad 2Example 2
Roztok 2,2'-[(pentafluorfenyl)methylen]bis(lH-pyrrolu) (71 mg, 0.22 mmol) a 3a-(2,3,4,6tetra-0-benzyl-p-D-glukopyranosyloxy)-5p-cholan-24-alu (200 mg, 0.22 mmol) v suchém dichlormethanu (46 ml) byl 10 minut probubláván argonem. K reakci byla jako katalyzátor přidána TFA (17.5 μΐ, 0.22 mmol). Reakční nádoba byla chráněna před světlem a obsah míchán pod inertní atmosférou za laboratorní teploty 18 h. Poté byl přidán triethylamin (32 μΐ, 0.22 mmol) a DDQ (102 mg, 0.45 mmol) a směs byla dále míchána další 3 h. Poté byla rozpouštědla odpařena ve vakuu. Zbytek byl nanesen na kolonku Celitu, jenž byl vymyt methanolem, nerozpuštěný zbytek byl převeden do toluenu (obsahujícího 0.5 % triethylaminu). Opakovaná chromatografie získané látky na koloně silikagelu (1-2. toluen + 0.5 % triethylamin, 3. toluen - ethyl-acetát 40:1 + 0.5 % triethylamin) poskytla 5,15bis(pentafluorfenyl)-10,20-bis[3a-(2,3,4,6-tetra-(?-benzyl-p-D-glukopyranosyloxy)-5pcholan-24-yl]-porfyrin (58 mg, 21 %) ve formě červenohnědé amorfní látky. UV-Vis: (CHCh) Xmax 416 nm (log ε = 5.53). *H NMR (400 MHz, C6D6): -2.38 bs, 2 H (2 x NHpyrrol); 0.72 s, 6 H (2 x H-18); 0.93 s, 6 H (2 x H-19); 1.36 d, 6 H (J= 6.4,2 x H-21); 0.802.46,52 H (2 x steroidní fingerprint); 3.50-3.81,14 H (2 χ Η-3β, 2 x H-2‘, H-3‘, H-4‘, H-5‘, H-6a‘, H-6b‘); 4.35 bm, 2 H (2 x H-23a); 4.44 d, 2 H (J= 12.2); 4.48 d, 2 H (J= 12.2); 4.54 d, 2 H (J- 11.5) (6 x H-benzyl); 4.61 d, 2 H (J= 7.6,2 χ Η-Γ); 4.64 bm, 2 H (2 x H-23b); 4.81 d, 2 H (J = 11.2); 4.84 d, 2 H (J = 11.5); 4.88 d, 2 H (J = 11.5); 5.03 d, 2 H (J= 11.2); 5.20 d, 2 H (J= 11.2) (10 x H-benzyl); 7.04-7.43,40 H (H-arom.); 8.66 d, 4 H (J= 4.6, 4 x H-pyrrol); 9.27 d, 4 H (J = 4.9, 4 x H-pyrrol). 13C NMR (100 MHz, C6D6): 13.05, 20.15, 21.96, 24.35, 25.15, 27.28, 28.24, 28.67, 29.63, 33.06, 35.55, 35.89, 36.36, 36.73, 38.37,A solution of 2,2 '- [(pentafluorophenyl) methylene] bis (1H-pyrrole) (71 mg, 0.22 mmol) and 3α- (2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyloxy) -5β-cholan- 24-alu (200 mg, 0.22 mmol) in dry dichloromethane (46 mL) was bubbled with argon for 10 min. TFA (17.5 μΐ, 0.22 mmol) was added as a catalyst. The reaction vessel was protected from light and stirred under an inert atmosphere at room temperature for 18 h. Then triethylamine (32 μΐ, 0.22 mmol) and DDQ (102 mg, 0.45 mmol) were added and the mixture was further stirred for another 3 h. evaporated in vacuo. The residue was applied to a Celite column which was washed with methanol, the insoluble residue was taken up in toluene (containing 0.5% triethylamine). Repeated chromatography on silica gel (1-2. Toluene + 0.5% triethylamine, 3. Toluene - ethyl acetate 40: 1 + 0.5% triethylamine) afforded 5.15bis (pentafluorophenyl) -10.20-bis [3a- ( 2,3,4,6-tetra- (β-benzyl-β-D-glucopyranosyloxy) -5-pholan-24-yl] -porphyrin (58 mg, 21%) as a red-brown amorphous substance UV-Vis: (CHCl3) X max 416 nm (log ε = 5.53). 1 H NMR (400 MHz, C 6 D 6 ): -2.38 bs, 2H (2 x NH-pyrrole); 0.72 s, 6 H (2 x H-18); 0.93 s, 6 H (2 x H-19); 1.36 d, 6 H (J = 6.4.2 x H-21); 0.802.46.52 H (2 x steroid fingerprint); 3.50-3.81.14 H (2 χ Η -3β, 2 x H-2 ', H-3', H-4 ', H-5', H-6a ', H-6b'); 4.35 bm, 2 H (2 x H-23a); 4.44 d, 2H (J = 12.2); 4.48 d, 2H (J = 12.2); 4.54 d, 2H (J-11.5) (6 * H-benzyl); 4.61 d, 2H (J = 7.6.2) χ Η-Γ) 4.64 dm, 2H (2 x H-23b); 4.81 d, 2H (J = 11.2); 4.84 d, 2H (J = 11.5); 4.88 d, 2H (J = 11.5) 5.03 d, 2H (J = 11.2); 5.20 d, 2H (J = 11.2) (10 * H-benzyl); 7.04-7.43.40 H (H-arom.); 8.66 d, 4 H ( J = 4.6, 4 x H-pyrrole) 9.27 d, 4 H (J = 4.9, 4 x H-pyrrole). 13 C NMR (100 MHz, C 6 D 6 ): 13.05, 20.15, 21.96, 24.35, 25.15, 27.28, 28.24, 28.67, 29.63, 33.06, 35.55, 35.89, 36.36, 36.73, 38.37,
41.10, 41.37, 43.16, 43.69, 46.75, 56.62, 56.96, 70.41, 74.10, 75.50, 75.68, 76.09, 76.22, 79.20, 80.64, 83.71, 85.95, 101.86, 103.66, 118.28, 122.64, 129.93, 130.96, 139.79, 139.93, 140.24,140.28,146.35,148.82.19F NMR (376 MHz, C6D6): -137.74 m, 4 F; -153.03 m, 2 F; 162.65 m, 4 F. Pro C146H156F10N4O12 vypočteno Exact Mass: 2347.16; MW 2348.80, m/z:41.10, 41.37, 43.16, 43.69, 46.75, 56.62, 56.96, 70.41, 74.10, 75.50, 75.68, 76.10, 76.22, 79.20, 80.64, 83.71, 85.95, 101.86, 103.66, 118.28, 122.64, 129.93, 130.96, 139.79, 139.93, 140.24,140.28,146.35,148.82. 19 F NMR (376 MHz, C 6 D 6 ): -137.74 m, 4 F; -153.03 m 2 F; 162.65 m, 4 F. For C146H156F10N4O12 calculated Exact Mass: 2347.16; MW 2348.80, m / z:
··· • ·· * · 4 «♦ • · ·♦ »44» 444«« • ·44· 4 ♦ ♦ 44 44 44 444 «44 44
4 4 44 • · ·4 ··*44 4 44 4
2348.16 (100.0 %), 2349.16 (80.8 %), 2347.16 (62.4 %), 2350.17 (41.9 %), 2351.17 (18.4 %),2348.16 (100.0%), 2348.16 (80.8%), 2347.16 (62.4%), 2350.16 (41.9%), 2351.17 (18.4%),
2352.17 (6.1 %), 2350.16 (3.6 %), 2349.17 (1.8 %), 2353.18 (1.3 %); nalezeno MS (FAB, CHCI3), w/z: 2348.9, MS (ESI, MeOH/CHCb): 2369.9 (M + Na+). K roztoku takto získaného2352.17 (6.1%); 2350.17 (3.6%); 2349.17 (1.8%); 2353.18 (1.3%); MS (FAB, CHCl 3) m / z 2348.9 found, MS (ESI, MeOH / CHCl 3): 2369.9 (M + Na + ). To the solution thus obtained
5.15- bis(pentafluorfenyl)-l 0,20-bis[3a-(2}3,4,6-tetra-O-benzyl-p-D-glukopyranosyloxy)-53cholan-24-yl]-porfyrinu (40 mg, mmol) bylo ve směsi suchého dichlormethanu (1.5 ml) a methanolu (3 ml) přidáno 10% Pd(C) (40 mg). Reakční směs byla míchána pod atmosférou H2 (za atmosférického tlaku) při laboratorní teplotě 8 h. Pak bylo ke směsi přidáno několik kapek triethylaminu, směs byla zfíltrována přes Celit a promyta směsí chloroform-methanol (4:1), filtrát byl odpařen dosucha ve vakuu. Zbytek byl suspendován v toluenu a zfiltrován přes vatu. Vymytím směsí chloroform-methanol (4:1) a odpařením byl získán amorfní hnědý5.15-bis (pentafluorophenyl) -1,20,20-bis [3- (2 ) 3,4,6-tetra-O-benzyl-β-D-glucopyranosyloxy) -53cholan-24-yl] porphyrin (40 mg, mmol) 10% Pd (C) (40 mg) was added in a mixture of dry dichloromethane (1.5 mL) and methanol (3 mL). The reaction mixture was stirred under an atmosphere of H 2 (at atmospheric pressure) at room temperature for 8 h. Then, a few drops of triethylamine were added, the mixture was filtered through Celite and washed with chloroform-methanol (4: 1), the filtrate evaporated to dryness in vacuo. . The residue was suspended in toluene and filtered through cotton wool. Washing with chloroform-methanol (4: 1) and evaporation gave an amorphous brown
5.15- bÍs(pentafluorfenyl)-10,20-bis[3a-(3-D-glukopyranosyloxy)-5P-cholan-24-yl]-porfyrin (20 mg, 72 %). UV-Vis: (pyridin) Xmax 417 nm (log ε - 5.29). ]H NMR (400 MHz, C5D5N): -5.15-bis (pentafluorophenyl) -10,20-bis [3α- (3-D-glucopyranosyloxy) -5β-cholan-24-yl] porphyrin (20 mg, 72%). UV-Vis: (pyridine) λ max 417 nm (log ε - 5.29). 1 H NMR (400 MHz, C 5 D 5 N): -
2.26 bs, 2 H (2 x NH-pyrrol); 0.74 s, 6 H (2 x H-l 8); 0.90 s, 6 H (2 x H-19); 1.58 d, 6 H (J= 6.0,2 x H-21); 0.80-2.80, 52 H (2 x steroidní fíngerprint); 3.98-4.64,14 H (2 x Η-3β, 2 χ H2‘, H-3‘, H-4‘, H-5‘, H-6a‘, H-6b‘); 5.00 bm, 2 H (2 x H-23a); 5.07 d, 2 H (J= 7.2,2 x H-l ‘);2.26 bs, 2H (2 * NH-pyrrole); 0.74 s, 6H (2 * H-18); 0.90 s, 6H (2 * H-19); 1.58 d, 6H (J = 6.0.2 * H-21); 0.80-2.80, 52 H (2 x steroid digerprint); 3.98-4.64,14 H (2 x Η-3β, 2 H2 H2 ‘, H-3‘, H-4 ‘, H-5‘, H-6a ‘, H-6b‘); 5.00 rm, 2H (2 x H-23a); 5.07 d, 2H (J = 7.2.2 * H-l ');
5.26 bm, 2 H (2 χ H-23b). 9,43 d, 4 H (J= 4.2,4 χ H-pyrrol), 9.94 d, 4H (J= 4.9, 4 x Hpyrrol). UC NMR (100 MHz, C5D5N): 12.30,19.47, 21.10,23.51,24.47, 26.54,27.28, 27.40, 28.91, 32.70, 34.66, 34.82, 35.38, 35.86, 37.93, 40.33, 40.60, 42.28, 43.06, 46.56, 56.33, 56.49, 62.94, 71.81, 75.41, 77.86, 78.55, 78.71, 101.48, 102.04, 117.40, 122.96, 130.38, 131.16, 145.94, 148.29. l9F NMR (376 MHz, C5D5N): -138.61 m, 4 F; -153.89 m, 2 F; 163.01 m, 4 F. Pro C90H108F10N4O12 vypočteno Exact Mass: 1626.78; Mol. Wt. 1627.82, mlz\5.26 bm, 2 H (2 χ H-23b). 9.43 d, 4H (J = 4.2, 4 H-pyrrole), 9.94 d, 4H (J = 4.9, 4 x H-pyrrole). 1 H NMR (100 MHz, C 5 D 5 N): 12.30, 19.47, 21.10, 23.51, 24.47, 26.54, 27.28, 27.40, 28.91, 32.70, 34.66, 34.82, 35.38, 35.86, 37.93, 40.33, 40.60, 42.28, 43.06, 46.56, 56.33, 56.49, 62.94, 71.71, 75.41, 77.86, 78.55, 78.71, 101.48, 102.04, 117.40, 122.96, 130.38, 131.16, 145.94, 148.29. 19 F NMR (376 MHz, C 5 D 5 N): -138.61 m, 4 F; -153.89 m 2 F; 163.01 m, 4 F. For C90H108F10N4O12 calculated Exact Mass: 1626.78; Mol. Wt. 1627.82, mlz \
1626.78 (100.0 %), 1627.78 (99.3 %), 1628.79 (48.5 %), 1629.79 (18.1 %), 1630.79 (5.0 %),1626.78 (100.0%), 1627.78 (99.3%), 1628.79 (48.5%), 1629.79 (18.1%), 1630.79 (5.0%),
1628.78 (3.9 %), 1627,79 (1.2 %); nalezeno MS (FAB, MeOH), m!r. 1627.6 (M+). MS (ESI, MeOH/CHClj): 1627.3 (M+).1628.78 (3.9%); 1627.79 (1.2%); MS (FAB, MeOH) m / z found. 1627.6 (M & lt ; + & gt ; ). MS (ESI, MeOH / CHCl 3): 1627.3 (M + ).
Příklad 3Example 3
Roztok 3a-(2,3,4,6-tetra-0-acetyl-p-D-glukopyranosyloxy)-5p-cholan-24-al (240 mg, 0.34 mmol), pyrrolu (95 mg, 100 μΐ, 1.39 mmol) a pentafluorbenzaldehydu (210 mg, 1.04 mmol) v suchém dichlormethanu (140 ml) byl probubláván argonem po dobu 15 min. Ke směsi byl šeptem přidán BF3.Et2O (20 mg, 18 μΐ, 0.14 mmol) a směs byla odstíněna od světla a míchána pod argonem za laboratorní teploty 4 h, poté byl přidán DDQ (410 mg, 1.8 mmol), směs byla míchána dalších 8 h. Po této době byl ke směsi přidán triethylamin (20 μΐ, 0.14 mmol) a směs byla míchána dalších 5 min. Rozpouštědla byla poté odpařena ve vakuu. Zbytek byl rozpuštěn v chloroformu, k roztoku byl přidán silíkagel (2 g) a směs byla odpařena dosucha. Opakovaná chromatografie na sloupci silikagelu (30g) (1. toluen-ethyl acetát 25:1, 2-3. toluen-ethyl acetát 19:1) poskytla 5,10}15-tris(pentafluorfenyl)-20-[3a-(2,3,4,6-tetra-O-acetyl-p-Dglukopyranosyioxy)-5p-cholan-24-yl]-porfyrin (65 mg, 12 %) ve formě Červenofialové amorfní pevné látky. UV-Vis: (CHClj) 415 nm (log ε = 5.69). lH NMR (300 MHz, C6D6): -2.71 bs, 2 H (2 x NH-pyrrol); 0.66 s, 3 H (H-18); 0.91 s, 3 H (H-19); 1.35 d, 3 H (J= 6.3, H-21); 1.68 s, 6 H; 1.70 s, 3 H; 1.76 s, 3 H (4 x OAc); 0.80-2.54, 26 H (steroidní fingerprint); 3.53 ddd, 1 H (J, = 9.9, J2 = 4.5, J3 = 2.4, H-5‘); 3.60 m, 1 Η (Η-3β); 4.11 dd, 1 H (Ji = 12.3, J2 = 2.4, H-6a‘); 4.30 dd, 1 H (Jj = 12.3, J2 = 4.5, H-6b‘); 4.37 bm, 1 H (H-23a); 4.48 d, 1 H (J= 7.8, Η-Γ); 4.64 bm, 1 H (H-23b); 5.291,1 H (J= 9.6, H-4‘); 5.33 dd, 1 H (Jj = 9.3, J2 = 7.8, H-2‘); 5.481,1 H (J= 9.6, H-3‘); 8.62 d, 2 H (J= 4.8); 8.70 d, 2 H (J= 5.1); 8.74 d, 2 H (J- 4.8); 9.29 d, 2 H (J= 4.8) (8 x H-pyrrol). 13C NMR (75 MHz, C6D6): 12.95,A solution of 3α- (2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy) -5β-cholan-24-al (240 mg, 0.34 mmol), pyrrole (95 mg, 100 μΐ, 1.39 mmol) and of pentafluorobenzaldehyde (210 mg, 1.04 mmol) in dry dichloromethane (140 mL) was bubbled with argon for 15 min. BF3.Et2O (20 mg, 18 μΐ, 0.14 mmol) was whispered to the mixture and the mixture was shielded from light and stirred under argon at room temperature for 4 h, then DDQ (410 mg, 1.8 mmol) was added, the mixture was stirred for additional After this time, triethylamine (20 μ (, 0.14 mmol) was added to the mixture and stirred for an additional 5 min. The solvents were then evaporated in vacuo. The residue was dissolved in chloroform, silica gel (2 g) was added to the solution, and the mixture was evaporated to dryness. Repeated chromatography on a silica gel (30g) column (1. toluene-ethyl acetate 25: 1, 2-3, toluene-ethyl acetate 19: 1) afforded 5,10 } 15-tris (pentafluorophenyl) -20- [3a- (2 3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy) -5β-cholan-24-yl] -porphyrin (65 mg, 12%) as a red-violet amorphous solid. UV-Vis: (CHCl 3) 415 nm (log ε = 5.69). 1 H NMR (300 MHz, C 6 D 6): -2.71 bs, 2 H (2 x NH-pyrrole); 0.66 s, 3H (H-18); 0.91 s, 3H (H-19); 1.35 d, 3 H (J = 6.3, H-21); 1.68 s, 6H; 1.70 s, 3H; 1.76 s, 3 H (4 * OAc); 0.80-2.54, 26 H (steroid fingerprint); 3.53 ddd, 1H (J 1 = 9.9, J 2 = 4.5, J 3 = 2.4, H-5 '); 3.60 m, 1Η (Η-3β); 4.11 dd, 1H (J 1 = 12.3, J 2 = 2.4, H-6a '); 4.30 dd, 1H (J 1 = 12.3, J 2 = 4.5, H-6b '); 4.37 bm, 1H (H-23a); 4.48 d, 1H (J = 7.8, [delta]); 4.64 bm, 1H (H-23b); 5.291.1 H (J = 9.6, H-4 '); 5.33 dd, 1H (J 1 = 9.3, J 2 = 7.8, H-2 '); 5.481.1 H (J = 9.6, H-3 '); 8.62 d, 2H (J = 4.8); 8.70 d, 2H (J = 5.1); 8.74 d, 2H (J = 4.8); 9.29 d, 2H (J = 4.8) (8 * H-pyrrole). 13 C NMR (75 MHz, C 6 D 6 ): 12.95,
20.10, 20.83, 20.91, 20.93, 21.08, 21.94, 24.29, 25.03, 27.05, 28.12, 28.33, 29.59, 33.35, 35.32, 35.49, 36.28, 36.63, 38.31, 40.96, 41.20, 43.18, 43.65, 47.01,56.53, 56.69, 62.70, 69.63 , 72.86, 73.04, 74.21, 80.61, 100.61, 102.11, 103.38, 116.83, 117.47, 125.43, 130.96, 131.96, 136.80,140.16, 141.28, 144.67, 145.85, 149.14, 169.42, 169.73, 170.70, 170.73.19F NMR (282 MHz, C6D6): -137.30 m, 6 F; -151.471,1 F (J= 22.0), -151.791,2 F (J= 21.7), 161.91 m, 6 F. Pro C75H67F15N4O10 vypočteno Exact Mass: 1468.46; MW 1469.33, m/z:20.10, 20.83, 20.91, 20.93, 21.08, 21.94, 24.38, 25.03, 27.05, 28.12, 28.33, 29.59, 33.35, 35.32, 35.49, 36.28, 36.63, 38.31, 40.96, 41.20, 43.18, 43.65, 47.01,56.53, 56.69, 62.70, 69.63, 72.86, 73.04, 74.20, 80.61, 100.61, 102.11, 103.38, 116.83, 117.47, 125.43, 130.96, 131.96, 136.80,140.16, 141.28, 144.67, 145.85, 149.14, 169.42, 169.73, 170.70, 170.73. 19 F NMR (282 MHz, C 6 D 6 ): -137.30 m, 6 F; -151,471.1 F (J = 22.0), -151,791.2 F (J = 21.7), 161.91 m, 6 F. For C75H67F15N4O10 calculated Exact Mass: 1468.46; MW 1469.33, m / z:
1468.46 (100.0 %), 1469.47 (82.3 %), 1470.47 (35.5 %), 1471.47 (11.1 %), 1472.48 (1.8 %),1468.46 (100.0%), 1469.47 (82.3%), 1470.47 (35.5%), 1471.47 (11.1%), 1472.48 (1.8%),
1469.46 (1.5 %), 1470.46 (1.2 %); nalezeno MS (ESI, MeOH), m/z\ 1492.3 (M + Na+).1469.46 (1.5%); 1470.46 (1.2%); MS (ESI, MeOH) m / z 1492.3 (M + Na + ) found.
K míchanému roztoku takto získaného 5,10,15-tris(pentafluorfenyl)-20-[3a-(2,3,4,6-tetra-0 acetyl-P-D-glukopyranosyloxy)-5p-cholan-24-yl]-porfyrinu (50 mg, 34 pmol) ve směsi suchého methanolu (25 ml) a dichlormethanu (5 ml) byl přidán methanolát sodný (5 mg), směs byla míchána 4 h a poté zneutralizována Dowexem 50 v H+ cyklu (25 mg). Ke směsi byl přidán dichlormethan (20 ml) a směs byla zfiltrována přes vatu, rozpouštědla odpařena ve vakuu. Zbytek byl rozpuštěn ve směsi chloroform - methanol (9:1) a roztok byl zfíltrován přes kolonku silikagelu (0.5 g). Po odpaření rozpouštědel byl získán 5,10,15-tris(pentafluorfenyl)20-[3a-(p-D-glukopyranosyloxy)-5p-cholan-24-yl]-porfyrin (38 mg, 85 %) jako červenohnědá pevná látka. UV-Vis: (CHCh) Xmax 415 nm (log ε = 5.48). lH NMR (300 MHz, C5D5N): -2.49 bs, 2 H (2 x NH-pyrrol); 0.73 s, 3 H (H-18); 0.90 s, 3 H (H-19); 1.59 d, 3 H (J = 6.3, H-21); 0.80-2.85, 26 H (steroidní fingerprint); 3.96-4.68, 7 Η (Η-3β, H-2‘, H-3‘, H-4‘, H-5‘, H-6a‘, H-6b‘); 4.90-5.40, 3 H (H-1‘, H-23a,b); 6.52 bs, 1 H; 7.05 bs, 1 H; 7.16 bs, 2H (4 x OH); 9.49 d, 2 H (J= 4.8); 9.54 d, 2 H (J= 4.8); 9.57 d, 2 H (J=4.8); 10.03 d, 2 H (J= 4.8) (8 x H-pyrrol). 13C NMR (75 MHz, CSD5N): 12.27, 19.45, 21.09, 23.50, 24.46, 26.54, 27.29, 27.41, 28.89, 33.12, 34.66, 34.82, 35.39, 35.86, 37.95, 40.34, 40.60, 42.28, 43.06, 46.84, 56.29, 56.48,62.94, 71.81, 75.40, 77.88, 78.54, 78.71,101.61,102.04,102.99,116.08, 116.68,125.85,131.41,132.44,139.73,140.70,144.07,145.46,148.67. ,9F NMR (282 MHz, CsD5N): -138.15 m, 6 F; -152.991,1 F (J= 21.2), -153.011,2 F (J= 22.0), -162.38 m, 6 F. Pro C67H59F15N4O6 vypočteno Exact Mass: 1300.42; MW 1301.18, m/z: 1300.42 (100.0 %), 1301.42 (74.2 %), 1302.43 (26.5 %), 1303.43 (7.2 %), 1302.42 (2.3 %), 1304.43 (1.5 %); nalezeno MS (ESI, MeCN/CHClj), m/z: 1302.0 (M+). MS (ESI, MeOH) 1301.9 (M+) 1323.9 (M + Na+).To a stirred solution of the thus obtained 5,10,15-tris (pentafluorophenyl) -20- [3- (2,3,4,6-tetra-O-acetyl-PD-glucopyranosyloxy) -5β-cholan-24-yl] -porphyrin (50 mg, 34 pmol) in a mixture of dry methanol (25 mL) and dichloromethane (5 mL) was added sodium methoxide (5 mg), stirred for 4 h and then neutralized with Dowex 50 in an H + cycle (25 mg). Dichloromethane (20 mL) was added to the mixture and the mixture was filtered through cotton wool, the solvents evaporated in vacuo. The residue was dissolved in chloroform-methanol (9: 1) and the solution was filtered through a silica gel column (0.5 g). Evaporation of the solvents gave 5,10,15-tris (pentafluorophenyl) -2O- [3α- (β-D-glucopyranosyloxy) -5β-cholan-24-yl] porphyrin (38 mg, 85%) as a red-brown solid. UV-Vis: (CHCl 3) λ max 415 nm (log ε = 5.48). 1 H NMR (300 MHz, C 5 D 5 N): -2.49 bs, 2 H (2 x NH-pyrrole); 0.73 s, 3H (H-18); 0.90 s, 3H (H-19); 1.59 d, 3H (J = 6.3, H-21); 0.80-2.85, 26 H (steroid fingerprint); 3.96-4.68,7 Η (Η-3β, H-2 ', H-3', H-4 ', H-5', H-6a ', H-6b'); 4.90-5.40, 3H (H-1 ', H-23a, b); 6.52 bs, 1H; 7.05 bs, 1H; 7.16 bs, 2H (4 * OH); 9.49 d, 2H (J = 4.8); 9.54 d, 2H (J = 4.8); 9.57 d, 2H (J = 4.8); 10.03 d, 2H (J = 4.8) (8 * H-pyrrole). 13 C NMR (75 MHz, CSD 5 N): 12.27, 19.45, 21.09, 23.50, 24.46, 26.54, 27.29, 27.41, 28.89, 33.12, 34.66, 34.82, 35.39, 35.86, 37.95, 40.34, 40.60, 42.28, 43.06, 46.84, 56.29, 56.48,62.94, 71.81, 75.40, 77.88, 78.54, 78.71,101.61,102.04,102.99,116.08, 116.68,125.85,131.41,132.44,139.73,140.70,144.07,145.46,148.67. 9 F NMR (282 MHz, CsD 5 N): -138.15 m, 6 F; -152.991.1 F (J = 21.2), -153.011.2 F (J = 22.0), -162.38 m, 6 F. For C67H59F15N4O6 calculated Exact Mass: 1300.42; MW 1301.18, m / z: 1300.42 (100.0%); 1301.42 (74.2%); 1302.43 (26.5%); 1303.43 (7.2%); 1302.42 (2.3%); 1304.43 (1.5%); MS (ESI, MeCN / CHCl 3) found, m / z: 1302.0 (M + ). MS (ESI, MeOH) 1301.9 (M & lt ; + & gt ; ) 1323.9 (M + Na < + & gt ; ).
Průmyslová využitelnostIndustrial applicability
Sloučeniny podle vynálezu jsou použitelné pro výrobu elektrochemických sensorů a výrobků sloužících jako detektory a přenašeče vybraných substrátů.The compounds of the invention are useful for the manufacture of electrochemical sensors and products serving as detectors and carriers of selected substrates.
Patentové nárokyPatent claims
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