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CAS No. : | 54-47-7 | MDL No. : | MFCD00006333 |
Formula : | C8H10NO6P | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | NGVDGCNFYWLIFO-UHFFFAOYSA-N |
M.W : | 247.14 | Pubchem ID : | 1051 |
Synonyms : |
Pyridoxal 5′-phosphate;Pyridoxyl phosphate;MC-1;Vitamin B6 phosphate;PLP;PAL-P;pyridoxal 5'-phosphate
|
Chemical Name : | (4-Formyl-5-hydroxy-6-methylpyridin-3-yl)methyl dihydrogen phosphate |
Num. heavy atoms : | 16 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.25 |
Num. rotatable bonds : | 4 |
Num. H-bond acceptors : | 7.0 |
Num. H-bond donors : | 3.0 |
Molar Refractivity : | 53.65 |
TPSA : | 126.76 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -8.57 cm/s |
Log Po/w (iLOGP) : | -0.14 |
Log Po/w (XLOGP3) : | -1.07 |
Log Po/w (WLOGP) : | 0.37 |
Log Po/w (MLOGP) : | -1.91 |
Log Po/w (SILICOS-IT) : | 0.21 |
Consensus Log Po/w : | -0.51 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.56 |
Log S (ESOL) : | -0.71 |
Solubility : | 48.0 mg/ml ; 0.194 mol/l |
Class : | Very soluble |
Log S (Ali) : | -1.1 |
Solubility : | 19.5 mg/ml ; 0.0789 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -0.81 |
Solubility : | 38.7 mg/ml ; 0.157 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 2.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.44 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With manganese(IV) oxide; Celite in schwach saurer wss.Loesung; | ||
With manganese(IV) oxide; sulfuric acid; water at 70℃; | ||
With copper(II) sulfate; 2-oxo-propionic acid in wss.Loesung; |
With copper diacetate; 2-oxo-propionic acid in wss.Loesung; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With manganese(IV) oxide; sulfuric acid; water at 70℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With potassium hydroxide; sodium tetrahydroborate In methanol at -15℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With sodium hydroxide for 1h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With sodium hydroxide for 1h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.2% | With potassium phosphate buffer at 37℃; | |
In water at 50 - 55℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 25℃; depending on pH; | ||
In water at 90℃; | 2.4. The synthesis of hydrazones General procedure: Synthesis was performed in accordance with Scheme 1. The preliminarilyheated to 90 °C solution of 0.309 g (1.25 mmol) of pyridoxal 5′-phosphate in 25 ml of water was quickly added to the solution of1.25 mmol of isoniazid or nicotinoyl hydrazide or picolinoyl hydrazidein the 25 ml ofwater (at 90 °C). The reaction mixturewas cooled during1 h at room temperature. The precipitated crystalline products werethen filtrated,washedwith small quantities of icy distilledwater and acetoneand dried at 90 °C in the air until their weight became constant. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
in neutraler wss. Loesung bei Raumtemperatur (Imin-Bildung); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Stage #1: meta-fluoroaniline With hydrogenchloride; sodium nitrite In water at 0℃; for 0.0833333h; Stage #2: pyridoxal 5'-phosphate With sodium hydroxide In water at 0℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | Stage #1: 4-Chloro-3-nitroaniline With hydrogenchloride; sodium nitrite In water at 0℃; for 0.0833333h; Stage #2: pyridoxal 5'-phosphate With sodium hydroxide In water at 0℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Stage #1: 2-Fluoroaniline With hydrogenchloride; sodium nitrite In water at 0℃; for 0.0833333h; Stage #2: pyridoxal 5'-phosphate With sodium hydroxide In water at 0℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | Stage #1: 2-iodophenylamine With hydrogenchloride; sodium nitrite In water at 0℃; for 0.0833333h; Stage #2: pyridoxal 5'-phosphate With sodium hydroxide In water at 0℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | Stage #1: 4-Fluoro-3-nitroaniline With hydrogenchloride; sodium nitrite In water at 0℃; for 0.0833333h; Stage #2: pyridoxal 5'-phosphate With sodium hydroxide In water at 0℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26% | Stage #1: 2,4-difluorophenylamine With hydrogenchloride; sodium nitrite In water at 0℃; for 0.0833333h; Stage #2: pyridoxal 5'-phosphate With sodium hydroxide In water at 0℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | Stage #1: 4-chloro-aniline With hydrogenchloride; sodium nitrite In water at 0℃; for 0.0833333h; Stage #2: pyridoxal 5'-phosphate With sodium hydroxide In water at 0℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | Stage #1: 3-chloro-aniline With hydrogenchloride; sodium nitrite In water at 0℃; for 0.0833333h; Stage #2: pyridoxal 5'-phosphate With sodium hydroxide In water at 0℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | Stage #1: 3-nitro-aniline With hydrogenchloride; sodium nitrite In water at 0℃; for 0.0833333h; Stage #2: pyridoxal 5'-phosphate With sodium hydroxide In water at 0℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | Stage #1: 2-bromoaniline With hydrogenchloride; sodium nitrite In water at 0℃; for 0.0833333h; Stage #2: pyridoxal 5'-phosphate With sodium hydroxide In water at 0℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water | 2 INVENTIVE EXAMPLE 2 A 50 ml portion of fresh bovine erythrocytes were washed four times at 4° C. with 50 ml of 0.9% sodium chloride aqueous solution using a centrifuge. A 40 ml portion of the thus obtained erythrocyte solution was subjected to hemolysis by adding 80 ml of water for injection use, the lysate was centrifuged at 8,000 rpm for 1 hour and then the membrane components were separated from hemoglobin using an ultrafiltration membrane (cutoff limit, 100,000 daltons). [00109] A 3.87 g (0.06 mmol) portion of the thus obtained hemoglobin was dissolved in 0.1 M phosphate buffer (pH 8.0), and the solution was adjusted to a total volume of 25 ml. After de-oxidation of the solution by vigorous blowing of argon until the partial pressure of oxygen reached 2 mmHg or less, addition of pyridoxal 5'-phosphate was effected in accordance with a known method (R. Benesch et al., J. Biol. Chem., 257 (3), 1320-1324, 1982) to obtain pyridoxal-modified hemoglobin. The thus obtained pyridoxal-modified hemoglobin solution was adjusted to a total volume of one liter by adding 0.1 M borate buffer (pH 8.2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | To the solution of 189 mg (1 mmol) 3-amino-1-hydroxy-propylidene-1,1-bisphosphonic acid in water (0.5 ml), triethylamine (0.6 ml) and ethanol (2 ml), pyridoxal-5'-phosphate (265 mg, 1 mmol) was added under stirring. The reaction mixture was stirred one (1) 1 h. at room temperature, then NaBH4 (38 mg, 1 mmol) was added. The solution was stirred 1 h. at room temperature. To the solution 6 N HCl (0.9 ml) was added. Ethanol was evaporated and the Ph of the solution was adjusted to Ph 7 with NH4OH and chromatographed on DEAE-cellulose (HCO3, 100 ml). The column was washed with water (200 ml) and then eluted with the use of a linear gradient NH4HCO3 (0.05-0.3M). The peak elude was evaporated and the residue coevaporated with water (5*10 ml). Lyophilisation of the aqueous solution afforded ammonium salt.. Yield 236 mg, 44% Rf 0.05 (B); Rf 0.19 (C); Rf 0.1 (D); Rf 0.03 (E); Rf 0.32 (F); 1H NMR (D2O) delta: 7.65 ('H, 6-H); 4.35 (2H, 5-CH2); 3.4 t (2H, CH2); 2.45 (3H, 2-CH3); 2.3 m (2H, CH2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | Stage #1: ammonium salt of aminomethylenediphosphonic acid; pyridoxal 5'-phosphate With triethylamine In water at 20℃; for 2h; Stage #2: With sodium tetrahydroborate at 20℃; for 1h; Stage #3: With hydrogenchloride; ammonia more than 3 stages; | 4.B B. Synthesis 1-(N-(5'-[phospho]-pyridoxylamino)-methylen-1,1-bisphosphonic acid. 57 mg (0.25 mmol) of ammonium salt of aminomethylenediphosphonic acid (Alferov I. S., Bobkov S. Yu., Kotlyarevsky I. L. Izvestiya AN SSSR, ser. khim., 1987, N4, 865-868) was added to the solution of 132.5 mg (0.5 mmol) of pyridoxal-5'-phosphate in 1 ml of H2O with 0.3 ml of triethylamine. The solution was stirred at room temperature for two hours. Then 20 mg (0.5 mmol) of NaBH4 was added and the reaction mixture was stirred for an hour at room temperature, then neutralized up to PH 7.0 with 2N HCl. The mixture was loaded on the column with DEAE-cellulose (HCO3-form); the column was washed with water and then the product of the reaction was eluted in the gradient of NH4HCO3 (0.05-0.2 M). Fractions, containing the product were evaporated with water and loaded on the column with Dowex-50 (H+), the column was washed with water and then the product was eluted. To the aqueous solution of the corresponding acid the aqueous ammonium solution (2.5%) was added, then the mixture was evaporated to a small volume and loaded on the column with Dowex-50 (Na+), the column was washed with water and Na-salt of the product was eluted and lyophilized. The yield was 46.5 mg, 40%. HPLC-the column Nucleosil C18, 4-50 mm. Purity-99.5%. TLC: Rf 0.08 on PEI-cellulose in the system 0,5M NH4HCO3; Rf 0.2 on silufol UV 254 in the system isopropanol-ammonium-H2O (3:1:2). 1H-NMR (D2O) δ (delta): 7.75 (1H, 6-H; 4.95 (2H, 4'-CH2); 4.6 s (2H, 5'-CH2); 3.3 dd (1H, JHP=16.49; N-CH); 2.45 s (3H, CH3). 31P NMR (D2O) δ: 9.1 s (2P);2.2 s (1P). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In methanol at 4 - 25℃; for 4h; | 2.2 To a solution of pyridoxal 5-phosphate (alkaline CH3OH) a methanolic solution of 1,4,7-tris(carbobutoxymethyl)-10-(2-aminoethyl)-1,4,7,10-tetraazacyclododecane (3'b) was added slowly at 4°C. The reaction mixture was stirred at ambient temperature (25°C) for 4 hours and the reaction was monitored by mass spectrometry. After completion of the reaction the desired product was filtered and dried under reduced pressure yielding 85% of 1,4,7 tris(carbobutoxymethyl)-10-{2-[(3-hydroxy-2-methyl-5-phosphono-oxy-methyl-pyridin-4-ylmethylene)-amino]-ethyl}-1,4,7,10-tetra-azacyclo-dodecane 4'. The remaining portion was recovered by evaporating the filtrate to dryness. ESI-MS(-): found: 783-785 isotopic distribution in negative mode [M-3H]+; calculated for C36H63N6O11P: m/z 786-788. 1H NMR (250 MHz CDCl3): 1.45 (s, 27H), 2.51 to 3.29 {mixed multiplet, 27H (-CH2-N-CH2-N- 16H ), (-CH2-CO2-8H) and (-CH3-Py-3H)} 3.58 (t, 2H), 3.94 (s, 1 H, -N=CH-Py), 4.53 (d, 2H, CH2OP, JPH = 3.93Hz), 7.42 (s, 1 H, Py-H). Elemental analysis: calculated (found) for C36H63N6O11P: C, 54.95(55.02); H, 8.07(8.11); N, 10.68(10.72); O, 22.37(22.43); P, 3.94(3.72). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; sodium tetrahydroborate; triethylamine; In ethanol; water; | EXAMPLE 3 Synthesis of 3-(N-[5'-phospho]pyridoxylamino)-1-hydroxypropyliden-1,1-bisphosphonic acid: To the solution of 189 mg (1 mmol) 3-amino-1-hydroxy-propylidene-1,1-bisphosphonic acid in water (0.5ml), triethylamine (0.6 ml) and ethanol (2ml), pyridoxal-5'-phosphate (265mg, 1 mmol) was added under stirring. The reaction mixture was stirred one (1) 1 h. at room temperature, then NaBH4 (38mg, 1 mmol) was added. The solution was stirred 1 h. at room temperature. To the solution 6 N HCl (0.9ml) was added. Ethanol was evaporated and the pH of the solution was adjusted to pH 7 with NH40H and chromatographed on DEAE-cellulose (HCO3, 100 ml). The column was washed with water (200ml) and then eluted with the use of a linear gradient NH4HCO3 (0.05-0.3M). The peak elude was evaporated and the residue coevaporated with water (5*10 ml). Lyophilisation of the aqueous solution afforded ammonium salt. Yield 236 mg, 44% Rf 0.05 (B); Rf 0.19 (C); Rf 0.1 (D); Rf 0.03 (E); Rf 0.32 (F); 1H NMR (D2O) delta: 7.65 ('H, 6-H); 4.35 (2H, 5-CH2); 3.4t (2H, CH2); 2.45 (3H, 2-CH3); 2.3m (2H, CH2). | |
With hydrogenchloride; sodium tetrahydroborate; triethylamine; In ethanol; water; | EXAMPLE 3 Synthesis of 3-(N-[5'-phospho]pyridoxylamino)-1-hydroxypropyliden-1,1-bisphosphonic acid: To the solution of 189 mg (1 mmol) 3-amino-1-hydroxy-propylidene-1,1-bisphosphonic acid in water (0.5 ml), triethylamine (0.6 ml) and ethanol (2 ml), pyridoxal-5'-phosphate (265 mg, 1 mmol) was added under stirring. The reaction mixture was stirred one (1) 1 h. at room temperature, then NaBH4 (38 mg, 1 mmol) was added. The solution was stirred 1 h. at room temperature. To the solution 6 N HCl (0.9 ml) was added. Ethanol was evaporated and the pH of the solution was adjusted to pH 7 with NH4OH and chromatographed on DEAE-cellulose (HCO3, 100 ml). The column was washed with water (200 ml) and then eluted with the use of a linear gradient NH4HCO3 (0.05-0.3M). The peak elude was evaporated and the residue coevaporated with water (5*10 ml). Lyophilization of the aqueous solution afforded ammonium salt. Yield 236 mg, 44% Rf 0.05 (B); Rf 0.19 (C); Rf 0.1(D); Rf 0.03(E); Rf 0.32 (F); 1H NMR (D2O) delta: 7.6 5 (1H, 6-H); 4.3 5 (2H, 5-CH2); 3.4t (2H, CH2); 2.4 5 (3H, 2-CH3); 2.3m (2H, CH2). | |
With hydrogenchloride; sodium tetrahydroborate; triethylamine; In ethanol; water; | EXAMPLE 3 Synthesis of 3-(N-[5'-phospho]pyridoxylamino)-1-hydroxypropyliden-1,1-bisphosphonic acid: To the solution of 189 mg (1 mmol) 3-amino-1-hydroxy-propylidene-1,1-bisphosphonic acid in water (0.5 ml), triethylamine (0.6 ml) and ethanol (2 ml), pyridoxal-5'-phosphate (265mg, 1 mmol) was added under stirring. The reaction mixture was stirred one (1) 1 h. at room temperature, then NaBH4 (38 mg, 1 mmol) was added. The solution was stirred 1 h. at room temperature. To the solution 6 N HCl (0.9 ml) was added. Ethanol was evaporated and the pH of the solution was adjusted to pH 7 with NH4OH and chromatographed on DEAE-cellulose (HCO3, 100 ml). The column was washed with water (200 ml) and then eluted with the use of a linear gradient NH4HCO3 (0.05-0.3M). The peak elude was evaporated and the residue coevaporated with water (5*10 ml). Lyophilisation of the aqueous solution afforded ammonium salt. Yield 236 mg, 44% Rf 0.05 (B); Rf0.19 (C); Rf 0.1 (D); Rf 0.03(E);Rf 0.32 (F); 1H NMR (D2O)) delta: 7.6 5 ('H, 6-H); 4.3 5 (2H, 5-CH2); 3.4t (2H, CH2); 2.4 5 (3H, 2-CH3); 2.3m (2H, CH2). |
With hydrogenchloride; sodium tetrahydroborate; triethylamine; In ethanol; water; | EXAMPLE 3 Synthesis of 3-(N-[5'-phospho]pyridoxylamino)-1-hydroxypropyliden-1,1-bisphosphonic acid To the solution of 189 mg (1 mmol) 3-amino-1-hydroxy-propylidene-1,1-bisphosphonic acid in water (0.5 ml), triethylamine (0.6 ml) and ethanol (2 ml), pyridoxal-5'-phosphate (265 mg, 1 mmol) was added under stirring. The reaction mixture was stirred one (1) 1 h. at room temperature, then NaBH4 (38 mg, 1 mmol) was added. The solution was stirred 1 h. at room temperature. To the solution 6 N HCl (0.9 ml) was added. Ethanol was evaporated and the pH of the solution was adjusted to pH 7 with NH4OH and chromatographed on DEAE-cellulose (HCO3, 100 ml). The column was washed with water (200 ml) and then eluted with the use of a linear gradient NH4HCO3 (0.05-0.3M). The peak elude was evaporated and the residue coevaporated with water (5*10 ml). Lyophilization of the aqueous solution afforded ammonium salt. Yield 236 mg, 44% Rf 0.05 (B); Rf 0.19 (C); Rf 0.1(D); Rf 0.03(E); Rf 0.32 (F); 1H NMR (D2O) delta: 7.6 5 (1H, 6-H); 4.3 5 (2H, 5-CH2); 3.4t (2H, CH2); 2.4 5 (3H, 2-CH3); 2.3m (2H, CH2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | 34 Preparation of 6-(3-Chlorophenylazo)-pyridoxal-5-phosphate Example 34 Preparation of 6-(3-Chlorophenylazo)-pyridoxal-5-phosphate This product was obtained from commercially available 3-chlorophenylamine and pyridoxal-5-phosphate as described in general procedure D, method A. The desired material was obtained in 58% yield. 1H NMR (D2O): δ 2.30 (s, 3H), 5.46 (s, 2H), 7.24-7-36 (m, 1H), 7.67 (t, J=5.5, 2H), 7.82 (s, 1H), 10.12 (s, 1H). 31P NMR (D2O): δ 7.04 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21% | Example 40 Preparation of 6-(5-Carboxy-2-chlorophenylazo)-pyridoxal-5-phosphate This product was obtained from commercially available <strong>[2840-28-0]3-amino-4-chlorobenzoic acid</strong> and pyridoxal-5-phosphate as described in general procedure D, method A. The final productproduct was obtained in 21% yield. 1H NMR (D2O): delta 2.30 (s, 3H), 5.65 (s, 2H), 7.56 (s, 1H), 7.88-7.91 (m, 2H), 10.26 (s, 1H). 31P NMR (D2O): delta 7.02 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21% | Example 39 Preparation of 6-(3-Carboxy-2-chlorophenylazo)-pyridoxal-5-phosphate The title compound was obtained from commercially available <strong>[108679-71-6]3-amino-2-chlorobenzoic acid</strong> and pyridoxal-5-phosphate as described in general procedure D, method A. The final productproduct was obtained in 21% yield. 1H NMR (D2O): delta 2.30 (s, 3H), 5.65 (s, 2H), 7.21 (t, J=5.1, 2H), 7.77 (d, J=5.1, 2H), 10.29 (s, 1H). 31P NMR (D2O): delta 7.00 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | Example 1 Preparation of 6-(3-Carboxy-2-methylphenylazo)-pyridoxal-5-phosphate This product was obtained from commercially available <strong>[52130-17-3]3-amino-2-methyl benzoic acid</strong> and pyridoxal-5-phosphate as described in general procedure D, method A. The final productproduct was obtained in 85% yield. 1H NMR (D2O): delta 2.21 (s, 3H), 2.61 (s, 3H), 5.45 (s, 2H), 7.02 (t, J=6.5, 1H), 7.36 (d, J=6.0 1H), 7.52 (d, J=6.0, 1H), 10.06 (s, 1H). 31P NMR (D2O): delta 6.88 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | 7.B Step B. Step B. Preparation of 6-[4-(1-Piperidinesulfonyl)phenylazo]-pyridoxal-5-phosphate This derivative was prepared from 4-(piperidine-1-sulfonyl)-phenylamine (step A) and pyridoxal-5-phosphate as described in general procedure D, method A. The final productproduct was obtained in 56% yield. 1H NMR (D2O): δ 1.45 (s, 2H), 1.66 (s, 4H), 1.88 (s, 3H), 2.33 (s, 3H), 3.00 (s, 4H), 5.63 (s, 2H), 7.97 (d, J=8.0, 2H), 8.03 (d, J=8.1, 2H), 10.32 (s, 1H). 31P NMR (D2O): δ 7.02 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | 22 Preparation of 6-(3,5-Dicarboxyphenylazo)-pyridoxal-5-phosphate Example 22 Preparation of 6-(3,5-Dicarboxyphenylazo)-pyridoxal-5-phosphate This product was obtained from commercially available 5-amino-isophthalic acid and pyridoxal-5-phosphate as described in general procedure D, method A. The desired material was obtained in 70% yield. 1H NMR (D2O): δ 2.30 (s, 3H), 5.65 (s, 2H), 8.21 (s, 1H), 8.32 (s, 2H), 10.26 (s, 1H). 31P NMR (D2O): δ 7.02 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | 19.B Step B. Step B. Preparation of 6-[3-(Butylsulfamoyl)phenylazo]-pyridoxal-5-phosphate This derivative was prepared from 3-amino-N-butyl-benzenesulfonamide (step A) and pyridoxal-5-phosphate as described in general procedure D, method A. The final productproduct was obtained in 54% yield. 1H NMR (D2O): δ 0.85 (t, J=7.4, 3H), 1.31 (quint, J=7.4, 2H), 1.54 (quint, J=7.3, 2H), 2.31 (s, 3H), 3.34 (t, J=7.1, 2H), 5.55 (s, 2H), 7.58 (t, J=8.0, 1H), 7.74 (d, J=7.4, 1H), 8.02 (d, J=8.1, 1H), 8.14 (s, 1H), 10.28 (s, 1H). 31P NMR (D2O): δ 7.04 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | 6.B Step B. Step B. Preparation of 6-[3-(1-Piperidinesulfonyl)phenylazo]-pyridoxal-5-phosphate The title material was prepared from 3-(piperidine-1-sulfonyl)-phenylamine (step A) and pyridoxal-5-phosphate as described in general procedure D, method A. The final productproduct was obtained in 88% yield. 1H NMR (D2O): δ 1.45 (s, 2H), 1.66 (s, 4H), 1.88 (s, 3H), 2.33 (s, 3H), 3.00 (s, 4H), 5.63 (s, 2H), 7.67 (t, J=8.0, 1H), 7.72 (d, J=7.0, 1H), 8.05 (t, J=8.1, 2H), 10.32 (s, 1H). 31P NMR (D2O): δ 7.03 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | 3.B Step B. Step B. Preparation of 6-[4-(N-(1-Adamantyl)sulfamoyl)phenylazo]-pyridoxal-5-phosphate Hydrochloride The title compound was prepared from N-adamantan-1-yl-4-aminobenzenesulfonamide (step A) and pyridoxal-5-phosphate as described in general procedure D, method A. The final productproduct was obtained in 84% yield. 1H NM (D2O): δ 1.45 (s, 6H), 1.66 (s, 6H), 1.88 (s, 3H), 2.33 (s, 3H), 5.63 (s, 2H), 7.97 (d, J=8.0, 2H), 8.03 (d, J=8.1, 2H), 10.32 (s, 1H). 31P NMR (D2O): δ 7.00 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | 9.B Step B. Step B. Preparation of 6-[3-(tert-Butylsulfamoyl)phenylazo]-pyridoxal-5-phosphate The title material was prepared from 3-amino-N-tert-butyl-benzenesulfonamide (step A) and pyridoxal-5-phosphate as described in general procedure D, method A. The final productproduct was obtained in 75% yield. 1H NMR (D2O): δ 1.00 (5, 9H), 2.33 (s, 3H), 5.63 (s, 2H), 7.45 (t, J=8.0, 1H), 7.72 (d, J=7.0, 1H), 7.99 (t, J=8.1, 1H), 8.11 (s, 1H), 10.32 (s, 1H). 31P NMR (D2O): δ 7.02 (s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Step B. Preparation of 6-[4-(tert-Butylsulfamoyl)phenylazo]-pyridoxal-5-phosphate The title material was prepared from <strong>[209917-48-6]4-amino-N-tert-butyl-benzenesulfonamide</strong> (step A) and pyridoxal-5-phosphate as described in general procedure D, method A. The final productproduct was obtained in 82% yield. 1H NMR (D2O): delta 1.00 (s, 9H), 2.33 (s, 3H), 5.63 (s, 2H), 7.72 (d, J=7.0, 2H), 7.99 (d, J=8.1, 2H), 10.32 (s, 1H). 31P NMR (D2O): delta 7.04 (s). |
Yield | Reaction Conditions | Operation in experiment |
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53% | 31.B Step B. Step B. Preparation of 6-[3-(5-Isoquinolylcarbamoyl)phenylazo]-pyridoxal-5-phosphate This derivative was prepared from 3-amino-N-isoquinolin-5-yl-benzamide (step A) and pyridoxal-5-phosphate as described in general procedure D, method A. The final productproduct was obtained in 53% yield. 1H NMR (D2O): δ 2.31 (s, 3H), 5.55 (s, 2H), 7.32 (d, J=7.7, 1H), 7.57 (d, J=8.0, 2H), 7.75 (d, J=7.8, 2H), 7.98 (d, J=7.5, 1H), 8.04 (d, J=7.2, 1H), 8.23 (d, J=7.1, 1H), 8.42 (s, 1H), 9.10 (s, 1H), 10.26 (s, 1H). 31P NMR (D2O): δ 7.05 (s). |
Yield | Reaction Conditions | Operation in experiment |
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48% | 14.B Step B. Step B. Preparation of 6-[4-(Cyclohexylcarbamoyl)phenylazo]-pyridoxal-5-phosphate This compound was prepared from 4-amino-N-cyclohexyl-benzamide (step A) and pyridoxal-5-phosphate as described in general procedure D, method A. The final productproduct was obtained in 48% yield. 1H NMR (D2O): δ 1.04 (m, 5H), 1.41 (d, J=11.0, 1H), 1.54 (d, J=18.3, 4H), 2.31 (s, 3H), 2.70 (m, 1H), 5.58 (s, 2H), 7.6 (d, J=7.0, 2H), 7.73 (d, J=7.2, 2H), 10.27 (s, 1H). 31P NMR (D2O): δ 7.03 (s). |
Yield | Reaction Conditions | Operation in experiment |
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With sodium acetate; In water; water-d2; at 25 - 80℃;Reactivity; | Example 4; Interaction between active aldehydes or ketones and a guanosine-5'-hydrazide based gel and formation of the most stable hydrogelsTo investigate the evolution of the system toward the "best fit" dynamic hydrogel, the hydrazides guanosine-5'-hydrazide (1) and N-(l-hydrazinocarbonyl-2-hydroxy-ethyl)- acetamide (serine hydrazide) (2) and the aldehydes <strong>[1008-72-6]<strong>[1008-72-6]2-formylbenzenesulfonic acid sodium</strong> salt</strong> (3) and phosphoric acid mono-(4-formyl-5-hydroxy-6-methyl-pyridin-3-ylmethyl) EPO <DP n="21"/>ester (pyridoxal monophosphate) (4) were selected. The dynamic library was generated at 15 mM concentration for each compound, at pD 6 in sodium acetate buffer, consists of four possible acylhydrazones A-D (A: 1+3, B: 1+4, C: 2+3, D: 2+4), each presenting two configurational isomers, undergoing continuously interchange by acylhydrazone bond formation and cleavage in aqueous medium. Stock solutions (150 mM) of hydrazide 2 and aldehydes 3 and 4 were prepared by dissolving a given compound in D2O or deuterated buffer solution. (0.5 M sodium acetate or potassium acetate, pD 6.0). Guanosine-5'-hydrazide (1, 2.3 mg) was dissolved in 500 muL buffer in a NMR tube to make up a 15 mM solution. Then, were added 50 muL of hydrazide 2 solutions, and 50 muL of aldehyde (3, 4) solutions from the stock solutions. The NMR tube was gently heated to 50-600C for 5-6 h to reach equilibrium. Then, it was cooled to room temperature and the 1H-NMR spectrum (400 MHz) was recorded once the solution was fully gelated. The CH=N imine proton signals of free (non gelated) acylhydrozones, which although broadened, could be clearly identified for each constituent of the mixture. The anti and syn isomers of each acylhydrazone (with respect to the amide bond conformation, about 75% anti and 25% syn + 10% depending on the compound) were integrated, giving the fraction of the library constituents present free in solution. The fraction of guanosine-5'- acylhydrazone in the gel was obtained by difference. Although the acylhydrazone A (1+3) does not give a gel when taken alone, a small amount (? 3%) of it could be trapped in the gel formed by the acylhydrazone B (1+4) in the mixtures of (1+2) with (3+4). The spectra of the individual acylhydrazones (15 mM) showed a weak signal (< 5%) of unreacted aldehyde proton. On heating, the CH=N signals broadened both for the individual compounds and for the mixtures. A markedly uneven distribution was obtained (Figure 1). The guanosine-5'-hydrazide 1 gave 8% and 39% of the acylhydrazones A and B, resulting from its reaction with aldehyde 3 and 4, respectively. Similarly, the serine hydrazide 2 reacted with aldehydes 3 and 4 to give about 42% of C as well as 11% of D. When the 1H NMR spectra were measured at 55C, the distribution of acylhydrazones was found be become less uneven. On further temperature increase up to 80C, the gel was completely melted and the distribution of acylhydrazones was close to equal (Figure 1). Cooling the reaction mixture slowly over a period of 60 min back to 25C restored the initial distribution, indicating EPO <DP n="22"/>that a selection process occurred, by which the mixture evolved to favor the constituent B forming a thermodynamically stable dynamic hydrogel, over constituents A, C and D that do not give such an organized phase. As indicated by the 1H-NMR data, two hydrazones B (in the gel) and C (free in solution) clearly dominate in the constitutional dynamic library at equilibrium. The latter is expressed as "image" of B, as a consequence of D being depressed by the trapping of pyridoxal monophosphate 4 in B in the gel. The dynamic selection is reversible and depends on the temperature: at high temperature when the gel has melted the selection disappears, while it operates at 250C where the medium is gelated. Thus, there is strong selection when the gel is formed, wherein the guanosine derivative interacts, or reacts with the aldehyde which allow the formation of the most stable product. This principle is confirmed by the replacement of serine hydrazide 2 by the corresponding alanine hydrazide, which results in almost the same distribution of acylhydrazones. Several control experiments were performed. Equimolar amounts of hydrazide 2 and aldehydes 3 and 4 (1:1:1) gave 15% of acylhydrazone C and 85% of hydrazone D, indicating that hydrazide 2 forms preferentially acylhydrazone D with aldehyde 4. As expected, hydrazide 2 and aldehydes 3 and 4 in a 2:1:1 ratio generate equal amounts of acylhydrazones C and D at equilibrium. Aldehyde 4 and hydrazides 1 and 2 in 1:1:1 molar ratio resulted in gel formation giving 87% acylhydrazone B and 13% of D at equilibrium. Taken together these results stress the ability of gelation to redirect the acylhydrazone distribution, as hydrazide 1 is able to scavenge 4 from 2 in D despite the strong preference of 2 for 4. Reacting 1, 2 with 3 (1:1:1) gave almost equal distribution of imines, as no gelation occurs to drive a selection. These experiments highlig... |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78.8% | With aq. NaOH In nitric acid aq. HNO3; aq. phosphate soln. was added to dissolved tyrosine at room temp.; heated at 65°C for 20 min; pH adjusted to ca. 6 (aq. NaOH); addn. of aq. Cu-compound; stirred at 55-60°C til completely dissoln.; evapn.; crystn.; elem. anal.; XRD; UV; IR; |
Yield | Reaction Conditions | Operation in experiment |
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28% | In benzene for 4h; Reflux; | 4.4 General method for the preparation of calix-like complexes 1-7 General procedure: Compounds 1-7 were synthesized from the equimolecular reaction of the corresponding salicylaldehyde derivative with 3-aminophenylboronic acid monohydrate using 10mL of benzene as solvent and 2mL of the corresponding alcohol (methanol or ethanol). The reaction mixtures were stirred for 4h under reflux. After that, part of the solvent and the water formed through the triple condensation reaction were removed using a Dean-Stark trap. The final products were recovered by filtration and purified by recrystallization in a solvent mixture MeOH/CHCl3 (1:3 ratio). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | In benzene for 4h; Reflux; | 4.4 General method for the preparation of calix-like complexes 1-7 General procedure: Compounds 1-7 were synthesized from the equimolecular reaction of the corresponding salicylaldehyde derivative with 3-aminophenylboronic acid monohydrate using 10mL of benzene as solvent and 2mL of the corresponding alcohol (methanol or ethanol). The reaction mixtures were stirred for 4h under reflux. After that, part of the solvent and the water formed through the triple condensation reaction were removed using a Dean-Stark trap. The final products were recovered by filtration and purified by recrystallization in a solvent mixture MeOH/CHCl3 (1:3 ratio). |
Yield | Reaction Conditions | Operation in experiment |
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81% | In ethanol for 4h; Reflux; | 2.4.1 General synthesis General procedure: 7-Amino-4-methyl-coumarin (B) (0.040g, 2.28×10-4mol) or 6-Aminofluorescein (C) (0.080g, 2.30×10-4mol) was dissolved in absolute ethanol, followed by the addition of pyridoxal-5′-phosphate (A) (0.056g, 2.28×10-4mol; 0.057g, 2.30×10-4mol). The solution was stirred and kept under refluxing for 4h. At the end, light orange (compound 1) and orange (compound 2) powders were obtained, and were washed several times with cold ethanol, diethylether and dried under vacuum. |
Yield | Reaction Conditions | Operation in experiment |
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88% | In ethanol for 4h; Reflux; | 2.4.1 General synthesis General procedure: 7-Amino-4-methyl-coumarin (B) (0.040g, 2.28×10-4mol) or 6-Aminofluorescein (C) (0.080g, 2.30×10-4mol) was dissolved in absolute ethanol, followed by the addition of pyridoxal-5′-phosphate (A) (0.056g, 2.28×10-4mol; 0.057g, 2.30×10-4mol). The solution was stirred and kept under refluxing for 4h. At the end, light orange (compound 1) and orange (compound 2) powders were obtained, and were washed several times with cold ethanol, diethylether and dried under vacuum. |
Yield | Reaction Conditions | Operation in experiment |
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80% | Stage #1: crystal violet perchlorate With triethylamine In ethanol for 0.5h; Stage #2: pyridoxal 5'-phosphate In ethanol for 4h; Reflux; | 2.4.1 General synthesis General procedure: Cresyl violet 670 perchlorate (D) (0.067g, 1.85×10-4mol) or nile blue 690 perchlorate (E) (0.070g, 1.67×10-4mol) was dissolved in absolute ethanol followed by the addition of 1 equivalent of triethylamine and kept under stirring for 30min. Thereafter, pyridoxal-5′-phosphate (0.042g, 1.85×10-4mol; 0.046g, 1.67×10-4mol) was added. The solution was stirred and kept under refluxing for 4h. At the end the mixture was evaporated under reduce pressure, and further purified by precipitation with cold ethanol, diethylether, whereas at the end a green (compound 3) and a dark blue powder (compound 4) were obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | Stage #1: nile blue 690 perchlorate With triethylamine In ethanol for 0.5h; Stage #2: pyridoxal 5'-phosphate In ethanol for 4h; Reflux; | 2.4.1 General synthesis General procedure: Cresyl violet 670 perchlorate (D) (0.067g, 1.85×10-4mol) or nile blue 690 perchlorate (E) (0.070g, 1.67×10-4mol) was dissolved in absolute ethanol followed by the addition of 1 equivalent of triethylamine and kept under stirring for 30min. Thereafter, pyridoxal-5′-phosphate (0.042g, 1.85×10-4mol; 0.046g, 1.67×10-4mol) was added. The solution was stirred and kept under refluxing for 4h. At the end the mixture was evaporated under reduce pressure, and further purified by precipitation with cold ethanol, diethylether, whereas at the end a green (compound 3) and a dark blue powder (compound 4) were obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With ammonium acetate; <i>L</i>-proline In methanol at 60℃; for 6h; | 2.1.1. Synthesis of ligand HMHPIP A mixture of 1,10-phenanthroline-5,6-dione (0.315 g,1.5 mmol) [31], pyridoxal-5-phosphate monohydrate (0.398 g,1.5 mmol), ammonium acetate (2.31 g, 30 mmol) and L-proline (0.176 g) in methanol (180 mL) was heated at 60 °C with stirring for 6 h. After completion of the reaction, the yellow-green precipitate was collected and washed with methanol and dried in vacuo. Yield: 78%. Anal. Calcd. For C20H16N5PO5: C, 54.93; H, 3.69; N,16.01; Found: C, 54.78; H, 3.47; N, 16.21%. IR (KBr): 3777.0 (OH,NH), 3065.9 (CAH), 1608.6 (phenyl ring), 1568.1 (phenyl ring),1541.1 (phenyl ring), 1484.5 (phenyl ring), 1403.2, 1320.6,1280.5, 1242.5, 1225.5, 1149.3 (P=O), 1077.4, 1026.6 (P-O),942.3 (. ES-MS m/z: 438 [M + 1]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In methanol | 2.2 Synthesis of L Receptor L was prepared by stirring equimolar amount of 2-aminothiophenol (0.1gm, 0.0008mmol) and pyridoxal phosphate (0.2gm, 0.0008mmol) in methanol (10mL). The yellow color precipitates were separated out in quantitative yield. The precipitates were filtered and dried. Yield: 85%. Mp. 180°C, FTIR (KBr pellete, υmax, cm-1): 3403, 3082, 2933, 2677, 2362, 2339, 2087, 1638, 1541, 1461, 1384, 1314, 1229, 1176, 1078, 1038, 983, 939, 831, 751, 723, 644, 497; 1H NMR: (400MHz, DMSO-d6, Me4Si, δ, ppm): 13.50 (1H, s, -OH), 8.20 (1H, s, -CH2=N), 8.10-6.72 (5H, Ar-H), 5.50 (1H, b, -SH), 5.00 (2H, d, -CH2), 2.38 (3H, s, -CH3); LC-MS (m/z) for C14H15N2O5PS: calculated 354.32 and found 355.14. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | In methanol; water at 70℃; for 5h; | Synthesis of N,N'-bis(pyridoxal phosphate)-o-phenylenediamine Pyridoxal 5-phosphate (2.48 g, 10 mmol) dissolved in 250 mL of methanol/water (1:1, v/v) was added into a 500 mL three-necked flask. Then 1,2-phenylenediamine (0.54 g, 5 mmol) in 50 mL of methanol/water (1:1, v/v) was dropped into the flask. The mixture was stirred at 70 °C for 5 h for the Schiff base condensation reaction of pyridoxal 5-phosphate with 1,2-phenylenediamine. After that the solution was concentrated through the evaporation of solvent and the reaction mixture was cooled to room temperature. The resulting yellow solid mass, N,N'-bis(pyridoxal phosphate)-o-phenylenediamine (BPPP), was filtered, then recrystallized from methanol and dried under vacuum. The yield is 2.07 g (69.0%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | In methanol at 24.84℃; | 2.2 Synthesis of L1 Receptor L1 was prepared by stirring 2-aminophenol (0.087g, 0.0008mol) and pyridoxal-5-phosphate (0.2g, 0.0008mol) in 25mL methanol. The yellow colour precipitates were filtered and dried. Yield: 75%; M.P.: 210°C; FTIR (KBr, υmax, cm-1): 2949, 2904, 2829, 2825, 2719, 2599, 2401, 2359, 2325, 2142, 2065, 1892, 1868, 1804, 1775, 1747, 1713, 1700, 1650, 1601, 1541, 1433, 1381, 1336, 1304, 1272, 1242, 1216, 1178, 1017, 988, 946, 886, 864, 828, 778, 761, 707, 640, 532, 519, 485, 449. 1H NMR (400MHz, DMSO-d6, δ, ppm): 15.01 (s, 1H, -OH), 9.29 (s, 1H, -CH=N), 8.00 (s, 1H, Ar-H), 7.58 (d, 1H, -OH), 7.57-6.91 (m, 4H), 5.17 (d, 1H, -CH2); LC-MS (m/z,) for [C14H15N2O6P+H+]: calculated 339.26 and found 339.14; Anal. Calc for C14H15N2O6P: C 49.71, H 4.47, N 8.28. found: C 49.65, H 4.48, N 8.20. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In methanol at 20℃; for 24h; | 2.4.1. Synthesis of L1 Pyridoxal-5-phosphate (0.4 g, 1.6 mmol) was added to a solution ofaniline (0.15 g, 1.6 mmol) in methanol. The mixture was stirred at roomtemperature for 24 h. The orange precipitate was removed by filtrationand washed with cold methanol and then n-hexane. Re-crystallizationfrom ethanol solution (20 mL) at 0 C yielded analytically pure orangesolid. 2.4.2. Spectroscopic data L1: 1H NMR (DMSO-d6, 400 MHz): 9.47 (s, 1 H), 7.95 (s, 1 H), 7.62(d, 2H, 3J =8.0 Hz), 7.47 (t, 2H, 3J =8.0 Hz), 7.36 (t, 1H, 3J =8.0 Hz),4.96, 4.95 (d, 2JHH =4.0 Hz), 2.44 (s, 3 H). 13C (100 MHz, DMSO-d6) 161.7, 154.0, 149.5, 147.0, 139.2, 131.2, 130.0, 128.5, 122.5, 120.5,61.5, 19.3. 31P (DMSO-d6, 162 MHz) 0.11. FT-IR (KBr, cm 1): (=C-H)3064 (w), (C H) 2931 (w), (C H) 2884 (w), (C=C) 1380 (m). Yield:0.46 g, 88 %, Mp: 212 C. |
70% | In methanol at 24.84℃; | 2.3 Synthesis of L2 Receptor L2 was prepared by stirring aniline (0.075g, 0.0008mol) and pyridoxal-5-phosphate (0.2g, 0.0008mol) in 25mL methanol. The yellow colour precipitates were filtered and dried. Yield: 70%; M.P.: 187°C; FTIR (KBr, υmax, cm-1): 3424, 3089, 3079, 2910, 2659, 1751, 1685, 1605, 1581, 1524, 1484, 1449, 1386, 1329, 1240, 1180, 1080, 1041, 1023, 985, 949, 923, 833, 797, 776, 750, 714, 686, 649, 615, 571, 529, 497. 1H NMR (400MHz, DMSO-d6, δ ppm): 14.16 (1H, s, -OH), 9.25 (1H, s, -CH=N), 8.05 (1H, s, Ar-H), 7.58-7.39 (5H, Ar-H), 5.19 (2H, d, -CH2), 2.08 (3H, s, -CH3); LC-MS (m/z) for [C14H15N2O5P+H+]: calculated 323.26 and found 323.00; Anal. Calc for C14H15N2O5P: C 52.18, H 4.69, N 8.69. found: C 51.98, H 4.63, N 8.63. |
44% | In methanol for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium formate; potassium carbonate In water; ethyl acetate | 2 Synthesis of (3R,4S)-4-Aminotetrahydro-2H-pyran-3-ol To a solution of L-Alanine (200 g, 2.24 mol), sodium formate (76.0 g, 1.12 mmol), and sodium phosphate dibasic (28.7 g, 202 mmol) in 2.25 L of water adjusted to pH 7.5 was added NAD (2.2 g, 3.21 mmol), pyridoxal-5-phosphate (2.2 g, 8.90 mmol), LDH (0.45 g, 0.22 mol), FDH (4.5 g, 0.20 mol), and TA P1G5 (4.5 g, 0.22 mol). After all the components were completely dissolved, (3S)-3-(benzyloxy)tetrahydro-4H-pyran-4-one (45 g, 0.22 mol) was added and the pH was adjusted to pH 7.25 with 6 N HCl and aged at 30° C. After 15 h, potassium carbonate (700 g, 5.06 mol) was added slowly, followed by ethyl acetate (2.2 L). The mixture was filtered through a bed of Solka Floc and the cake was washed with ethyl acetate (250 mL). The combined filtrates were separated and the aqueous layer was extracted a second time with ethyl acetate (2 L). The combined organic extracts were concentrated in vacuo to provide crude (3R,4S)-3-(benzyloxy)tetrahydro-2H-pyran-4-amine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | Stage #1: sphinganine-1-phosphate With potassium <i>tert</i>-butylate In methanol at 20℃; for 0.5h; Cooling with ice; Inert atmosphere; Stage #2: pyridoxal 5'-phosphate With potassium <i>tert</i>-butylate In methanol at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #3: With sodium tetrahydroborate In methanol at 0℃; for 4h; Reflux; Darkness; Inert atmosphere; | 2 4.2.1. General procedure 1: reductive amination between PLP and selected amines General procedure: To an ice cooled solution of the selected amine (0.1 mmol) in dry CH3OH (3 mL) was added KOtBu (2 equiv) and the mixture was stirred at rt for 30 min (Solution A). Simultaneously, KOt-Bu (2 equiv/mol of PLP) was added to a solution of PLP (1.3 eq.) in CH3OH (3 mL) at 0°C and the mixture was stirred at rt for 30 min(Solution B). Solution A was then added dropwise to solution B at 0°C and the mixturewas refluxed in the dark for 3 h, cooled to 0°C and treated with NaBH4 (1.3 equiv). After stirring at rt for 1 h, the reaction mixture was acidified by dropwise addition of 6 M aq. HCl and the solvent was evaporated to dryness to give a residue, which was purified as indicated below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | Stage #1: Sphingosine-1-phosphate With potassium <i>tert</i>-butylate In methanol at 20℃; for 0.5h; Cooling with ice; Inert atmosphere; Stage #2: pyridoxal 5'-phosphate With potassium <i>tert</i>-butylate In methanol at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #3: With sodium tetrahydroborate In methanol at 0℃; for 4h; Reflux; Darkness; Inert atmosphere; | 3 4.2.1. General procedure 1: reductive amination between PLP and selected amines General procedure: To an ice cooled solution of the selected amine (0.1 mmol) in dry CH3OH (3 mL) was added KOtBu (2 equiv) and the mixture was stirred at rt for 30 min (Solution A). Simultaneously, KOt-Bu (2 equiv/mol of PLP) was added to a solution of PLP (1.3 eq.) in CH3OH (3 mL) at 0°C and the mixture was stirred at rt for 30 min(Solution B). Solution A was then added dropwise to solution B at 0°C and the mixturewas refluxed in the dark for 3 h, cooled to 0°C and treated with NaBH4 (1.3 equiv). After stirring at rt for 1 h, the reaction mixture was acidified by dropwise addition of 6 M aq. HCl and the solvent was evaporated to dryness to give a residue, which was purified as indicated below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | Stage #1: 2-aminoethyl dihydrogen phosphate With potassium <i>tert</i>-butylate In methanol at 20℃; for 0.5h; Cooling with ice; Inert atmosphere; Stage #2: pyridoxal 5'-phosphate With potassium <i>tert</i>-butylate In methanol at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #3: With sodium tetrahydroborate In methanol at 0℃; for 4h; Reflux; Darkness; Inert atmosphere; | 1 4.2.1. General procedure 1: reductive amination between PLP and selected amines General procedure: To an ice cooled solution of the selected amine (0.1 mmol) in dry CH3OH (3 mL) was added KOtBu (2 equiv) and the mixture was stirred at rt for 30 min (Solution A). Simultaneously, KOt-Bu (2 equiv/mol of PLP) was added to a solution of PLP (1.3 eq.) in CH3OH (3 mL) at 0°C and the mixture was stirred at rt for 30 min(Solution B). Solution A was then added dropwise to solution B at 0°C and the mixturewas refluxed in the dark for 3 h, cooled to 0°C and treated with NaBH4 (1.3 equiv). After stirring at rt for 1 h, the reaction mixture was acidified by dropwise addition of 6 M aq. HCl and the solvent was evaporated to dryness to give a residue, which was purified as indicated below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | In water at 80℃; | Preparation of a Schiff Base from P5P andOxalydihydrazide Pyridoxal 5-phosphate 1 (0.2 mmol, 50mg) was dissolved in distilled water (10 mL) at 80 °C. Theresulting solution was added dropwise while being stirred to a5-fold excess of oxalydihydrazide 2 (1.0 mmol, 118 mg) inwater (15 mL) at 80 °C. After complete addition of pyridoxalphosphate, the reaction mixture was stirred for an additional 30min at 80 °C. The light yellow precipitate was filtered withoutbeing cooled, washed with hot water two or three times, dried(0.1 mmol, 45 mg, 65% yield), and identified as Schiff base 3 byNMR (Supporting Information). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In water at 50℃; | Synthesis of the Schiff bases of pyridoxal-5-phosphate with compounds 1-3. General procedure: A solution of 2.5 mmol of compound 1-3 in 25 mL of water washeated to 50° C and quickly added to a solution of 0.6179 g (2.5 mmol) of PLP preheated to 50°C. Excessof the solvent was distilled off at continuous stirring tothe final volume of 25 mL. The reaction mixture wasleft for 1 h at room temperature. The formed crystalline precipitate was filtered off, washed withacetone, and dried to constant mass at 70° in the air. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In water at 50℃; | Synthesis of the Schiff bases of pyridoxal-5-phosphate with compounds 1-3. General procedure: A solution of 2.5 mmol of compound 1-3 in 25 mL of water washeated to 50° C and quickly added to a solution of 0.6179 g (2.5 mmol) of PLP preheated to 50°C. Excessof the solvent was distilled off at continuous stirring tothe final volume of 25 mL. The reaction mixture wasleft for 1 h at room temperature. The formed crystalline precipitate was filtered off, washed withacetone, and dried to constant mass at 70° in the air. |
Yield | Reaction Conditions | Operation in experiment |
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85% | In water at 50℃; | Synthesis of the Schiff bases of pyridoxal-5-phosphate with compounds 1-3. General procedure: A solution of 2.5 mmol of compound 1-3 in 25 mL of water washeated to 50° C and quickly added to a solution of 0.6179 g (2.5 mmol) of PLP preheated to 50°C. Excessof the solvent was distilled off at continuous stirring tothe final volume of 25 mL. The reaction mixture wasleft for 1 h at room temperature. The formed crystalline precipitate was filtered off, washed withacetone, and dried to constant mass at 70° in the air. |
Yield | Reaction Conditions | Operation in experiment |
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76% | Step 2. Preparation of pyridoxal condensateThe 88 g of <strong>[65-22-5]pyridoxal hydrochloride</strong> and 55 g of N,N-dimethylethylenediamine were added to 880 mL of xylene and stirred to warm upThe reaction was carried out at 90 C. and refluxed for 8 h. After the reaction was complete, the toluene was concentrated in vacuo to give a concentrate 2 which was added to the concentrate 2 .Distilling 200 mL of methylene chloride, heating up to dissolution, then cooling the crystals to obtain 85 g of pyrofalaldehyde condensate;Step 3. Preparation of pyridoxal phosphate85g of pyridoxal condensate and 120g of polyphosphoric acid were added to the reaction flask, and the reaction mixture was stirred and warmed to 70C for 12h to react.Completely, then add 60mL of water and stir evenly. Pass 550mL of 732 resin. The resolution flow rate is 0.2BV/h.In 83% of the analytical solution, concentrated under reduced pressure to give a concentrate 3, to the concentrate 3 was added 340 mL of n-propanol to dissolve, slowly coolingWhite crystals were obtained and dried to give 76 g of the product pyridoxal phosphate. The total mass yield was 76%. | |
With water; trichlorophosphate; In tetrahydrofuran; at 0 - 20℃; for 5h; | 30 grams of phosphorus oxychloride was added to the reaction flask and stirring was started. At 5 C, 3 g of pure water was slowly added dropwise, followed by 15 G of tetrahydrofuran. Stirring was continued for 2 hours. A phosphating agent is obtained and used. 10 g of <strong>[65-22-5]pyridoxal hydrochloride</strong> was added, and 30 G of tetrahydrofuran was added. The configured phosphation reagent is then added in one portion at below 0 C. The reaction was stirred at room temperature for 5 hours. The reaction solution was adjusted to pH = 5.5 with sodium hydroxide under ice water bath. The temperature of the reaction mixture was controlled to be 5 C or less, and the solid initial product was gradually precipitated by stirring. Filtration under reduced pressure and drying gave a solid product (yield: 96%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | at 50℃; | General procedure: An equimolar amounts (2.99 mmol) of pyridoxal (or 2.0 mmol of pyridoxal-5-phosphate) and the corresponding amine were heated with stirring (50C) for 3-12 h (in the case of compound 3b, no heating was performed). The precipitate was separated, washed with ethanol and diethyl ether, then dried in a vacuum. Compounds 3b and 7 were isolated after removal of the solvent from the reaction mixture by recrystallization of a solid residue from ethanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With hydrogenchloride In water at 20℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With acetic acid In methanol for 4h; Reflux; | 2.2. Synthesis of L The starting compound rhodamine 6G hydrazide was synthesized by following the reported literature method [31,32]. The mixture of rhodamine 6G hydrazide (0.20 gm, 0.47 mmol), pyridoxal 5′-phosphate (0.12 gm, 0.48 mmol) and a few drops of acetic acid in 15 mL MeOH was refluxed for 4 h. After cooling to room temperature, the orange precipitate was collected and washed with cold methanol and then dried in a vacuum oven. Yield: 87%; 1H NMR (500 MHz, DMSO-d6):11.17 (s, 1H), 9.15 (s, 1H), 7.93 (m, 2H), 7.69 (m, 2H), 7.12 (s, 1H),6.39 (s, 2H), 6.27 (s, 2H), 4.86 (s, 2H), 3.02 (q, 4H), 2.30 (s, 3H), 1.85(s, 6H), 1.21 (t, 6H); (FT-IR, cm-1): 3351, 1731, 1633, 1616, 1521,1310, 1262, 1218, 1195; Mass (m/z): Calc. 657.235, Expt. 658.245. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With acetic acid; In methanol; at 20℃; | General procedure: To a mixture of 5-aminouracil (127 mg, 1 mmol) with an appropriate aldehyde (241 mg, 1.2 mmol) in methanol (15 mL) were added few drops of glacial acetic acid. The reaction mixture was stirred at room temperature until 5-aminouracil was completely consumed (TLC). The precipitate was filtered off, washed with methanol and air dried to give the corresponding product 1-10 as a yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.6% | In water; at 20 - 80℃; for 1h; | A mixture of a solution of 0.618 g (2.5 mmol) of pyridoxal-5-phosphate 1 in 15 mL of water and a solution of 0.345 g (2.5 mmol) of <strong>[768-05-8]pyrazine-2-carbohydrazide</strong> 2 in 15 mL of water (both solutions heated to 70-80 C) was cooled during 1 h at room temperature. The formed crystalline precipitate was filtered off, washed with small amount of cold distilled water and acetone, and dried in air. Yield 0.815 g (84.6%), light yellow crystals, Rf 0.86 (mobile phase 25% aqueous ammonia, Polygram Sil G/UV254). UV spectrum (pH = 7.4, H2O), lambdamax, nm (log epsilon): 302 (4.29); green luminescence in solid phase at lambdaex = 365 nm. 1H NMR spectrum (D2O, pD ~12), delta, ppm: 8.90 d (1H, H3, 4J = 0.9 Hz), 8.65 s (1H, CH=), 8.47 d. d (1H, H5', 3J = 2.4, 4J = 0.9 Hz), 8.41 d (1H, H6', 3J = 2.4 Hz), 7.51 s (1H, H6), 4.75 d (2H, CH2, 3J = 4.3 Hz), 2.22 s (3H, CH3). 13C NMR spectrum, deltaC, ppm: 166.1 (C=O),158.5 (C3), 151.2 (C2), 149.4 (C2'), 147.7 (CH=), 145.6 (C3'), 144.0 (C5'), 143.5 (C6'), 134 (C6), 130.4 (C5), 120.3 (C4), 61.7 (CH2), 18.2 (CH3). 31P NMR spectrum: deltaP 3.79 ppm. Mass spectrum, m/z: 368.07 [ M + H]+. Found, %: C 42.22; H 4.00; N 18.61. C13H14N5O6P. Calculated, %: C 42.52; H 3.84; N 19.07. M 367.25. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water at 50℃; | 2.2. Synthesis of hydrazones General procedure: Synthesis was performed in accordance with Chart 2, analogouslywith. The preliminarily heated to 50 °C solution of 0.309 g(1.25 mmol) of pyridoxal 5′-phosphate in 25 ml of water was quicklyadded to the solution of 1.25 mmol of 2-furoic or thiophene-2-carboxylichydrazide in the 25 ml of water (at 50 °C). The reaction mixturewas cooled during 1 h at roomtemperature. The precipitated crystallineproducts were then filtrated, washed with small quantities of icy distilledwater and acetone and dried at 90 °C in the air until their weightbecame constant. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68.4% | With sodium hydroxide at 35℃; for 2h; | 1.3; 2.3; 3.3 Synthesis of pyridoxal phosphate In a 100 mL three-neck reaction flask equipped with a stirrer and a thermometer,Will be 5.0g (13.6mmol)The pyridoxal phosphate Schiff base prepared in step 2 is added to27.2mL of 2mol/L sodium hydroxide solution,The temperature was raised to 35.0 ° C for 2.0 h.Cool to room temperature,The reaction mixture was extracted twice with ethyl acetate and then filtered (2.Add 19.6 g of strong acid cation exchange resin to the aqueous phase.Stir for 1.0h,Filtration, and finally lyophilized with a lyophilizer to obtain 2.3 g of pyruvic acid as a white solid.Yield = (2.3 g / (13.6 mmol * 0.001 * 247.1)) * 100% = 68.4%, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | In methanol at 20℃; for 24h; | 2.4.1. Synthesis of L1 General procedure: Pyridoxal-5-phosphate (0.4 g, 1.6 mmol) was added to a solution ofaniline (0.15 g, 1.6 mmol) in methanol. The mixture was stirred at roomtemperature for 24 h. The orange precipitate was removed by filtrationand washed with cold methanol and then n-hexane. Re-crystallizationfrom ethanol solution (20 mL) at 0 C yielded analytically pure orangesolid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | In methanol at 20℃; for 24h; | 2.4.1. Synthesis of L1 General procedure: Pyridoxal-5-phosphate (0.4 g, 1.6 mmol) was added to a solution ofaniline (0.15 g, 1.6 mmol) in methanol. The mixture was stirred at roomtemperature for 24 h. The orange precipitate was removed by filtrationand washed with cold methanol and then n-hexane. Re-crystallizationfrom ethanol solution (20 mL) at 0 C yielded analytically pure orangesolid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | In methanol at 20℃; for 24h; | 2.4.1. Synthesis of L1 General procedure: Pyridoxal-5-phosphate (0.4 g, 1.6 mmol) was added to a solution ofaniline (0.15 g, 1.6 mmol) in methanol. The mixture was stirred at roomtemperature for 24 h. The orange precipitate was removed by filtrationand washed with cold methanol and then n-hexane. Re-crystallizationfrom ethanol solution (20 mL) at 0 C yielded analytically pure orangesolid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | In methanol at 20℃; for 24h; | 2.4.1. Synthesis of L1 General procedure: Pyridoxal-5-phosphate (0.4 g, 1.6 mmol) was added to a solution ofaniline (0.15 g, 1.6 mmol) in methanol. The mixture was stirred at roomtemperature for 24 h. The orange precipitate was removed by filtrationand washed with cold methanol and then n-hexane. Re-crystallizationfrom ethanol solution (20 mL) at 0 C yielded analytically pure orangesolid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | In methanol at 20℃; for 24h; | 2.4.1. Synthesis of L1 General procedure: Pyridoxal-5-phosphate (0.4 g, 1.6 mmol) was added to a solution ofaniline (0.15 g, 1.6 mmol) in methanol. The mixture was stirred at roomtemperature for 24 h. The orange precipitate was removed by filtrationand washed with cold methanol and then n-hexane. Re-crystallizationfrom ethanol solution (20 mL) at 0 C yielded analytically pure orangesolid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | In methanol at 20℃; for 24h; | 2.4.1. Synthesis of L1 General procedure: Pyridoxal-5-phosphate (0.4 g, 1.6 mmol) was added to a solution ofaniline (0.15 g, 1.6 mmol) in methanol. The mixture was stirred at roomtemperature for 24 h. The orange precipitate was removed by filtrationand washed with cold methanol and then n-hexane. Re-crystallizationfrom ethanol solution (20 mL) at 0 C yielded analytically pure orangesolid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In methanol at 20℃; for 24h; | 2.4.1. Synthesis of L1 General procedure: Pyridoxal-5-phosphate (0.4 g, 1.6 mmol) was added to a solution ofaniline (0.15 g, 1.6 mmol) in methanol. The mixture was stirred at roomtemperature for 24 h. The orange precipitate was removed by filtrationand washed with cold methanol and then n-hexane. Re-crystallizationfrom ethanol solution (20 mL) at 0 C yielded analytically pure orangesolid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Acinetobacter baumannii recombinant acid phosphatase; nickel dichloride; bovine serum albumin In water Cooling with ice; Enzymatic reaction; | Acid phosphatase assay General procedure: Unless indicated otherwise, reaction mixtures contained 2.0 mM PNPP (Sigma Chemical Co.)or phosphorylated compounds (Sigma Chemical Co.), 0.20MMES (Sigma Chemical Co.)buffer, pH 6.0, 2.0 mM NiCl2, and 0.080-0.30 μg total Acinetobacter baumannii rAcpA protein,and were brought to a final concentration of 0.186 μg/μL protein with addition of bovineserum albumin (BSA, BioRad Laboratories) in a total reaction volume of 200 μL (determinationof released phosphate) or 300 μL (determination of released paranitrophenol). All incubationswere carried out for 30 minutes at 37 °C after which time reactions were placed in an iceslurry for 3 minutes followed by addition of enzyme to the respective blanks and reactionswere terminated by heating at 65 °C for 10 minutes followed by immersion in an ice slurry for3 minutes. Released phosphate was determined by addition of 1.0 mL BIOMOL GREEN phosphatereagent (Enzo Life Sciences), and monitored at 620 nm using a Genesys 10 UV ScanningSpectrophotometer (Thermo Scientific). Paranitrophenol was monitored at 405 nm followingaddition of 1.7 mL 0.5MGlycine buffer, pH 10. Following subtraction of blank values, paranitrophenoland released phosphate were quantitated using paranitrophenol and phosphatestandard curves, respectively. All reactions, i.e., generation of paranitrophenol and release offree phosphate were linear with both time (30 minutes) and assay protein (0.30 μg, ~ 13.2 nM).Specific activity is expressed as nmoles paranitrophenol or free phosphate liberated mg-1s-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethanol; water at 90℃; | General procedure: A 25-mL volume of an aqueous solution of 1 mmolof pyridoxal 5-phosphate heated to 90° was added to25 mL of a water-ethanol (1 : 1 v/v) solution of thecorresponding hydrazide also heated to 90°. Aninstant formation of a crystalline product wasobserved, which was settled at room temperature for1 h, filtered off, washed with ice water and acetone,and dried in air to constant weight. The yield of productswas 80-85% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethanol; water at 90℃; | General procedure: A 25-mL volume of an aqueous solution of 1 mmolof pyridoxal 5-phosphate heated to 90° was added to25 mL of a water-ethanol (1 : 1 v/v) solution of thecorresponding hydrazide also heated to 90°. Aninstant formation of a crystalline product wasobserved, which was settled at room temperature for1 h, filtered off, washed with ice water and acetone,and dried in air to constant weight. The yield of productswas 80-85% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethanol; water at 90℃; | General procedure: A 25-mL volume of an aqueous solution of 1 mmolof pyridoxal 5-phosphate heated to 90° was added to25 mL of a water-ethanol (1 : 1 v/v) solution of thecorresponding hydrazide also heated to 90°. Aninstant formation of a crystalline product wasobserved, which was settled at room temperature for1 h, filtered off, washed with ice water and acetone,and dried in air to constant weight. The yield of productswas 80-85% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With hydrogenchloride In ethanol; water monomer for 10h; Reflux; | {3-Hydroxy-4-[bis(2,4-dihydroxyphenyl)methyl]-2-methylpyridin-5-yl}methyl dihydrogen phosphate hydrochloride (3a) (general procedure) Resorcinol (0.6 g, 5.46 mmol) was added toa solution of pyridoxal 5-phosphate monohydrate (0.6 g,2.26 mmol) in ethanol (10 mL) and concentrated hydrochloricacid (2 mL). The reaction mixture was refl uxed for 10 h, thesolvent was removed, and the resulting solid foamy mass waswashed twice with anhydrous diethyl ether (25 mL). The yieldof 3a was 1.05 g (96%). IR, ν/cm-1: 845, 954, 1037, 1109, 1156,1217, 1287, 1362, 1458, 1511, 1619, 3249. 1H NMR (DMSO-d6),δ: 2.77 (s, 3 H, CH3); 4.60, 5.08 (both dd, 1 H each, CH2,2J, = 14.0 Hz, 3J, = 8.4 Hz); 5.61 (s, 1 H, CH); 6.11 (dd,1 , Ph, 3J, = 8.3 Hz, 4J, = 2.7 Hz); 6.31 (d, 1 H, Ph,4J, = 1.3 Hz); 6.55 (dd, 1 , Ph, 3J, = 8.3 Hz, 4J, = 1.7 Hz);6.61 (d, 1 H, Ph, 4J, = 1.6 Hz); 6.72, 7.07 (both d, 1 H each,Ph, 3J, = 8.4 Hz); 8.22 (s, 1 H, CHarom). 13C NMR (DMSO-d6),δ: 15.98, 34.06, 61.42, 63.56, 102.96, 103.23, 106.67, 107.39,113.09, 114.26, 121.75, 130.05, 130.14, 133.13, 143.37, 148.16,149.79, 155.13, 157.65, 157.93. 31P NMR (DMSO-d6), δ: -0.30.Found (%): C, 49.65; H, 4.54; Cl, 7.23; N, 2.71; P, 6.58.C20H21ClNO9. Calculated (%): C, 49.45; H, 4.36; Cl, 7.30;N, 2.88; P, 6.38. MS (MALDI-TOF), found m/z: 488.23 [M -- HCl + K]+; calculated for C20H20KNO9P+ 488.45 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With hydrogenchloride In ethanol; water monomer for 10h; Reflux; | {3-Hydroxy-4-[bis(2,4-dihydroxyphenyl)methyl]-2-methylpyridin-5-yl}methyl dihydrogen phosphate hydrochloride (3a) (general procedure) General procedure: Resorcinol (0.6 g, 5.46 mmol) was added toa solution of pyridoxal 5-phosphate monohydrate (0.6 g,2.26 mmol) in ethanol (10 mL) and concentrated hydrochloricacid (2 mL). The reaction mixture was refl uxed for 10 h, thesolvent was removed, and the resulting solid foamy mass waswashed twice with anhydrous diethyl ether (25 mL). The yieldof 3a was 1.05 g (96%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With hydrogenchloride In ethanol; water monomer for 10h; Reflux; | {3-Hydroxy-4-[bis(2,4-dihydroxyphenyl)methyl]-2-methylpyridin-5-yl}methyl dihydrogen phosphate hydrochloride (3a) (general procedure) General procedure: Resorcinol (0.6 g, 5.46 mmol) was added toa solution of pyridoxal 5-phosphate monohydrate (0.6 g,2.26 mmol) in ethanol (10 mL) and concentrated hydrochloricacid (2 mL). The reaction mixture was refl uxed for 10 h, thesolvent was removed, and the resulting solid foamy mass waswashed twice with anhydrous diethyl ether (25 mL). The yieldof 3a was 1.05 g (96%) |
Tags: 54-47-7 synthesis path| 54-47-7 SDS| 54-47-7 COA| 54-47-7 purity| 54-47-7 application| 54-47-7 NMR| 54-47-7 COA| 54-47-7 structure
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H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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