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CAS No. : | 42268-88-2 | MDL No. : | MFCD22578671 |
Formula : | C11H11BrO4 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | SVXVCUVXGMLDJC-UHFFFAOYSA-N |
M.W : | 287.11 | Pubchem ID : | 15686242 |
Synonyms : |
|
Num. heavy atoms : | 16 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.27 |
Num. rotatable bonds : | 5 |
Num. H-bond acceptors : | 4.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 61.84 |
TPSA : | 52.6 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.5 cm/s |
Log Po/w (iLOGP) : | 2.79 |
Log Po/w (XLOGP3) : | 2.19 |
Log Po/w (WLOGP) : | 2.0 |
Log Po/w (MLOGP) : | 2.53 |
Log Po/w (SILICOS-IT) : | 2.69 |
Consensus Log Po/w : | 2.44 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.95 |
Solubility : | 0.324 mg/ml ; 0.00113 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.93 |
Solubility : | 0.339 mg/ml ; 0.00118 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -3.8 |
Solubility : | 0.0453 mg/ml ; 0.000158 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 2.0 alert |
Leadlikeness : | 0.0 |
Synthetic accessibility : | 2.12 |
Signal Word: | Danger | Class: | 8 |
Precautionary Statements: | P260-P264-P270-P280-P301+P312-P301+P330+P331-P305+P351+P338-P310-P321-P330-P363-P405-P501 | UN#: | 1759 |
Hazard Statements: | H302-H314 | Packing Group: | Ⅲ |
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 sodium 2.) reflux, 4 h; Yield given. Multistep reaction; | ||
With potassium carbonate In tetrahydrofuran at 60℃; for 2h; | 4 5-Methoxymethyl-isophthalic acid dimethyl ester 5-Bromomethyl-isophthalic acid dimethyl ester (44g, 140 mmol), K2CO3 (43g, 308 mmol), MeOH (350 mL) and THF (350 mL) was heated 60 °C for 2h. The mixture was portioned between H20 and EtOAC and the organic phase was washed with brine, dried (Mg04), filtered and concentrated to give 32g of the title compound as a white solid. H NNMR : 3.43 (s, 3 H), 3.96 (s, 6 H), 4.55 (s, 2 H), 8.21 (s, 2 H), 8. 61 (s, 1 H) 13C NMR : 52.8, 58. 9,74. 0, 130. 4,131. 2, 133. 2,140. 0,166. 6 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; for 24.0h;Reflux; | A suspension of 2f (8 g, 0.038 mol), NBS (8.22 g, 0.046 mol) and benzoyl peroxide (0.10 g, 0.48 mmol) in 200 ml CCl4 was refluxed for 24 hrs. The reaction mixture was filtered under hot condition. The mixture was evaporated and washed by ethanol (50 ml×3) to afford the white compound 2g (6.84 g, 62.0 %, Mp: 132-134 ºC). 1H NMR (500 MHz, CDCl3) δ 8.62 (s, 1H); 8.26 (s, 2H); 4.55 (s, 2H); 3.96 (s, 6H). |
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane;Reflux; | 4.02g (0.014mol) of <strong>[17649-58-0]dimethyl 5-methylisophthalate</strong>, 2.67g (0.015mol) of N-bromosuccinimide, added to 250mL three flask containing 100mL of carbon tetrachloride solution , Further weighed 22.3 mg (0.0014 mol) of azobisisobutyronitrile into the above reaction vessel and heated to reflux for 36 ± 2 h. After the reaction was completed, it is cooled to room temperature, and then separately extracted with saturated sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride, and the organic phase is separated and combined, dried and distillation under reduced pressure to obtain a solid; The obtained solid was recrystallized from a mixed solvent of ethyl acetate and n-hexane in a volume ratio of 1:10 to obtain dimethyl 5-benzylbromoisophthalate | |
5.80 g | With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; at 80℃; for 12.75h; | Dimethyl 5-methyl isophthalate (7.904, 38 mmol,) and NBS (7.63 g, 43.1 mmol,) and a small amount of AIBN crystals were added to CCl4 (100 mL), and refluxed at 80 C. for 12 h. After refluxing for 45 minutes, the color of the solution quickly changed from yellow to white and cooled to room temperature.The solid and liquid were separated by filtration, the solid was reserved, and the filtrate was rotary evaporated to dryness. The obtained yellow-white crude product was dissolved in ethyl acetate, and recrystallized by adding n-hexane.Put it in the refrigerator to cool down and recrystallize. After filtration, 5.80 g of dimethyl 5-(bromomethyl)isophthalate was obtained as white crystals. |
With N-Bromosuccinimide; In tetrachloromethane;Reflux; | A compound where R5was a hydrogen atom, and each of R22was an ethyl group, an isopropyl group, or an s-butyl group in the compound (1) was synthesized according to the reaction formula (1).Dicarboxylic acid in 5-methylbenzene-1,3-dicarboxylic acid was reacted with thionyl chloride, and then methanol was reacted in the presence of triethylamine to protect the carboxylic acid. After that, the methyl group was brominated with N-bromosuccinimide (NBS), reacted by triphenylphosphine, before a vinyl group was formed by formaldehyde in the presence of sodium hydroxide. At the same time, deprotection of the dicarboxylic acid protected by the methyl group was performed, to obtain 5-vinylbenzene-1,3-dicarboxylic acid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | In dichloromethane for 2h; Heating; | |
In acetone | 1-3 Examples 1 to 3 A compound where R5was a hydrogen atom, and each of R22was an ethyl group, an isopropyl group, or an s-butyl group in the compound (1) was synthesized according to the reaction formula (1).Dicarboxylic acid in 5-methylbenzene-1,3-dicarboxylic acid was reacted with thionyl chloride, and then methanol was reacted in the presence of triethylamine to protect the carboxylic acid. After that, the methyl group was brominated with N-bromosuccinimide (NBS), reacted by triphenylphosphine, before a vinyl group was formed by formaldehyde in the presence of sodium hydroxide. At the same time, deprotection of the dicarboxylic acid protected by the methyl group was performed, to obtain 5-vinylbenzene-1,3-dicarboxylic acid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | In chloroform for 2h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 1.) Na / 2.) reflux, 4 h 2: 75.5 percent / LiAlH4 / tetrahydrofuran / 1.) -10 deg C, 1 h, 2.) r.t., 1 h 3: PBr3 / CHCl3 / 2 h / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 1.) Na / 2.) reflux, 4 h 2: 75.5 percent / LiAlH4 / tetrahydrofuran / 1.) -10 deg C, 1 h, 2.) r.t., 1 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 1.) Na / 2.) reflux, 4 h 2: 75.5 percent / LiAlH4 / tetrahydrofuran / 1.) -10 deg C, 1 h, 2.) r.t., 1 h 3: 42.5 percent / PBr3 / CHCl3 / 2 h / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: 1.) Na / 2.) reflux, 4 h 2: 75.5 percent / LiAlH4 / tetrahydrofuran / 1.) -10 deg C, 1 h, 2.) r.t., 1 h 3: 42.5 percent / PBr3 / CHCl3 / 2 h / Ambient temperature 4: 92 percent / K2CO3 / dimethylformamide / 4 h / 80 °C 5: 47.4 percent / 1M BBr3 / CH2Cl2 / 72 h / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 1.) Na / 2.) reflux, 4 h 2: 75.5 percent / LiAlH4 / tetrahydrofuran / 1.) -10 deg C, 1 h, 2.) r.t., 1 h 3: 42.5 percent / PBr3 / CHCl3 / 2 h / Ambient temperature 4: 92 percent / K2CO3 / dimethylformamide / 4 h / 80 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1: 99 percent / CHCl3 / 2 h / Heating 2: 64 percent / MeOLi / tetrahydrofuran / 12 h / 0 °C 3: 99 percent / H2 / 5 percent Pd/C / toluene / 4 h / 50 °C / 2250.2 Torr 4: 1.) LiAlH4 / 1a.) THF, r.t., 2 h, 1b.) reflux, 2 h, 2.) reflux, 4 h 5: 77 percent / 33 percent HBr / ethyl acetate / 1.) r.t., 5 h, 2.) 60 deg C, 3 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 99 percent / CHCl3 / 2 h / Heating 2: 64 percent / MeOLi / tetrahydrofuran / 12 h / 0 °C 3: 99 percent / H2 / 5 percent Pd/C / toluene / 4 h / 50 °C / 2250.2 Torr |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 99 percent / CHCl3 / 2 h / Heating 2: 64 percent / MeOLi / tetrahydrofuran / 12 h / 0 °C 3: 99 percent / H2 / 5 percent Pd/C / toluene / 4 h / 50 °C / 2250.2 Torr 4: 1.) LiAlH4 / 1a.) THF, r.t., 2 h, 1b.) reflux, 2 h, 2.) reflux, 4 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 99 percent / CHCl3 / 2 h / Heating 2: 64 percent / MeOLi / tetrahydrofuran / 12 h / 0 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 6 steps 1: 99 percent / CHCl3 / 2 h / Heating 2: 64 percent / MeOLi / tetrahydrofuran / 12 h / 0 °C 3: 99 percent / H2 / 5 percent Pd/C / toluene / 4 h / 50 °C / 2250.2 Torr 4: 1.) LiAlH4 / 1a.) THF, r.t., 2 h, 1b.) reflux, 2 h, 2.) reflux, 4 h 5: 77 percent / 33 percent HBr / ethyl acetate / 1.) r.t., 5 h, 2.) 60 deg C, 3 h 6: 14 percent / dimethylformamide / 12 h / 80 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86.9% | With carbon tetrabromide; triphenylphosphine In dichloromethane for 3h; Inert atmosphere; | |
With N-Bromosuccinimide; triphenylphosphine In dichloromethane at 0℃; for 1h; | 4 5-Bromomethyl-isophthalic acid dimethyl ester; N-Bromosuccinimide (45g, 238 mmol) and triphenylphosphine (65g, 238 mmol) was added to 5-Hydroxymethyl-isophthalic acid dimethyl ester (40g, 159 mmol) in CH2C12 (700 mL) at 0 °C. The mixture was stirred at 0°C for 1 h and then diluted with CH2C12 (700 mL). The mixture was washed with saturated NaHCO3 followed by brine and the organic phase was dried (Mg04), filtered and concentrated. The crude was purified by flash column chromatography over silica gel, eluting with heptane to heptane/EtOAc (4: 1) to give 44.5 g of the title compound as a white solid. 'H NMR 1.43 (t, 6 H), 4.43 (q, 4 H), 4.56 (s, 2 H), 8. 25 (d, 2 H), 8.61 (t, 1 H) 13C NMR : 14.3, 31.6, 61.6, 130.5, 131.6, 134.0, 138. 7,165. 3 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94.1% | With water; hydrogen bromide; acetic acid for 12h; Reflux; | 5-(bromomethyl)isophthalic acid 2g (3 g, 0.010 mol) was dissolved in acetic acid (50 ml) and aqueous HBr (40 %, 50 ml). The solution was refluxed for 12 hrs and poured into 500 ml ice water slowly. The resulting precipitate was collected by filtration and washed with distilled water (30 ml × 3). The filter cake was dried in vacuum and recrystallized in CH3CN to give the compound 2h (2.55 g, 94.1 %, Mp: 244-246 ºC). 1H NMR (400 MHz, DMSO-d6) δ 13.36 (br s, 2H); 8.39 (t, 1H, J = 1.6 Hz); 8.24 (d, 2H, J = 1.6 Hz); 4.88 (s, 2H); 13C NMR (100 MHz, DMSO-d6) δ 166.13, 139.53, 133.97, 131.74, 129.60, 32.73; HR-ESI (m/z): [M-H]-calcd. for 256.9449; found: 256.9448. |
82% | With boron tribromide In dichloromethane at 50℃; | |
59.13% | With hydrogen bromide; acetic acid for 12h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75.7% | In acetonitrile at 80℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: acetonitrile / 24 h / 80 °C 2: N,N-dimethyl-formamide / 6 h / 90 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | In acetonitrile at 100℃; for 24h; | |
65.9% | In acetonitrile at 80℃; for 24h; | |
In acetonitrile for 24h; Reflux; | 4,4'-Bipyridine (1.00 g, 6.40 mmol) and dimethyl 5-(bromomethyl)isophthalate (3.67 g, 12.8 mmol) were refluxed in a solution of acetonitrile (15 mL) for 1 day. After cooling, the yellow solid formed was collected by filtration, washed with acetonitrile, and then dried under vacuum to obtain [Me4L] Br2 as a pale yellow powder. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61.9% | In N,N-dimethyl-formamide; acetonitrile at 90℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: benzoimidazole; 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate With potassium hydroxide In dimethyl sulfoxide at 20℃; Stage #2: With potassium hydroxide In water at 100℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | In nitromethane at 60℃; for 72h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | Stage #1: dibenzo-24-crown ether; 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate; 1,2-bis(4,4'-dipyridinium)ethane ditrifluoromethanesulfonate In nitromethane at 50℃; for 5h; Microwave irradiation; Stage #2: sodium triflate In nitromethane; water for 5h; Microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | Stage #1: Diethyl iminodiacetate; 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate With potassium carbonate In acetonitrile at 20℃; for 12h; Stage #2: With potassium hydroxide In methanol; water at 20℃; for 12h; Stage #3: With hydrogenchloride In methanol; water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 20h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2-methylimidazole With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 10h; Stage #2: 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate In N,N-dimethyl-formamide at 20℃; for 24h; | 2.2. Preparation of ligand The H2L was synthesized via similar experimental procedure to that reported for preparation of other imidazole substitute isophthalate ligands [7]. Potassium hydroxide (0.56 g, 10 mM) was added to a solution of 2-methyl-1H-imidazole (0.82 g, 10 mM) in 10 mL DMF. The mixture was then stirred for 10 h at room temperature, following which dimethyl 5-(bromomethyl)isophthalate (1.44 g, 5 mM) was added and the solution was stirred further at room temperature for 24 h. Then, 200 mL water and potassium hydroxide (1.12 g, 20 mM) were added into the resulting mixture. The reaction mixture was refluxed for 10 h, and then poured into ice water, acidified with acetic acid to pH 5-6. After filtration, the product was dried at 100 °C under vacuum and obtained as a pale yellow solid (1.06 g, 82%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: tetrahydrofuran / 0.5 h / 20 °C 2: lithium borohydride; ethanol / tetrahydrofuran / 0 - 20 °C / Inert atmosphere 3: diphenylphosphoranyl azide; 1,8-diazabicyclo[5.4.0]undec-7-ene / tetrahydrofuran / 0 - 20 °C / Inert atmosphere 4: water / tetrahydrofuran / 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1.1: tetrahydrofuran / 0.5 h / 20 °C 2.1: lithium borohydride; ethanol / tetrahydrofuran / 0 - 20 °C / Inert atmosphere 3.1: diphenylphosphoranyl azide; 1,8-diazabicyclo[5.4.0]undec-7-ene / tetrahydrofuran / 0 - 20 °C / Inert atmosphere 4.1: water / tetrahydrofuran / 20 °C / Inert atmosphere 5.1: manganese (II) sulfate monohydrate / N,N-dimethyl-formamide / 0.33 h / 65 °C / Inert atmosphere 5.2: 48 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: tetrahydrofuran / 0.5 h / 20 °C 2: lithium borohydride; ethanol / tetrahydrofuran / 0 - 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: tetrahydrofuran / 0.5 h / 20 °C 2: lithium borohydride; ethanol / tetrahydrofuran / 0 - 20 °C / Inert atmosphere 3: diphenylphosphoranyl azide; 1,8-diazabicyclo[5.4.0]undec-7-ene / tetrahydrofuran / 0 - 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | In tetrahydrofuran at 20℃; for 0.5h; | Dimethyl 5-(N,N-Dimethyl)aminoisophthalate (15). A solution of dimethyl 5-(bromomethyl)isophthalate[29] (890 mg, 3.11 mmol) in anhydrous THF (15 mL) was treated at room temperature withdimethylamine (10 mL, 20 mmol, 2M in THF). This was stirred for 30 min during which time a whitesolid precipitated. The mixture was poured into 1N NaOH and extracted with EtOAc. The organiclayer were washed with brine and dried over Na2SO4. Concentration under reduced pressure gave 15 asa yellow oil; 761 mg, 97%; 1H-NMR δ 8.59 (s, 1H), 8.19 (s, 2H), 3.95 (s, 6H), 3.51 (s, 2H), 2.26 (s,6H); 13C-NMR δ 166.3, 140.2, 134.4, 134.3, 130.7, 129.6, 128.8, 63.5, 52.3, 45.4; IR 3434, 2951,2856, 2820, 2776, 2256, 1728, 1640, 1606, 1456, 1435, 1366, 1329, 1244, 1205, 1148, 1122, 1107,1043, 1008, 913, 873, 842, 790, 755, 733, 647 cm-1; HRMS (ESI) m/z calcd for C13H17NO4 (M+H):252.1230; found: 252.1237. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: potassium carbonate / acetone / 24 h / Inert atmosphere; Schlenk technique; Reflux 2: triphenylphosphine; carbon tetrabromide / tetrahydrofuran / 48.67 h / 20 °C / Inert atmosphere; Schlenk technique |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: potassium carbonate / acetone / 24 h / Inert atmosphere; Schlenk technique; Reflux 2: triphenylphosphine; carbon tetrabromide / tetrahydrofuran / 48.67 h / 20 °C / Inert atmosphere; Schlenk technique 3: potassium carbonate / acetone / 6 h / Inert atmosphere; Schlenk technique; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.602 g | With potassium carbonate In N,N-dimethyl-formamide at 60℃; for 8h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium carbonate In acetone for 24h; Inert atmosphere; Schlenk technique; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With tetra(n-butyl)ammonium hydroxide; sodium hydroxide; In water; benzene; at 80℃; | <strong>[75415-03-1]2-(1H-pyrazol-3-yl)pyridine</strong> (0.500 g, 3.45 mmol) and 1,3-dimethyl-5-(bromomethyl)benzene-1,3-dicarboxylate (0.990 g, 3.45 mmol) were added to a solution of 40% aqueous NaOH (5 mL), benzene (15 mL), and Bu4NOH (5 drops), and the resulting solution was refluxed at 80 C overnight. After cooling to room temperature, the colourless organic layer was separated from the yellow aqueous layer. The aqueous layer was then washed with ethyl acetate (2 * 10 mL) before being acidified to pH 3 using aqueous HCl (6 M), at which point a white precipitate formed. The solvents were then removed in vacuo and the residue dissolved in ca. 1 mL of dmf. Addition of ethyl acetate gave a pale yellow solid, which was filtered off, washed with ethyl acetate and diethyl ether and dried (0.354 g, 32%). Anal. Calc. for C17H13N3O4·2H2O: C, 56.83; H, 4.77; N, 11.69. Found: C, 56.78; H, 3.82; N, 11.55%. 1H NMR (400 MHz, dmf-d7): delta (ppm) = 5.71 (2H, s, Hg), 6.96 (1H, d, J = 2.3 Hz, He), 7.30 (1H, ddd, J = 7.5, 4.9, 1.2 Hz, Hb), 7.83 (1H, td, J = 7.7, 1.8 Hz, Hc), 7.97 (1H, dt, J = 7.7, 1.8 Hz, Hd), 8.12 (1H, d, J = 2.3 Hz, Hf), 8.21 (2H, m, Hh), 8.63-8.56 (2H, m, Ha, Hi). HRESI-MS (dmf/MeOH): m/z calcd for C17H12N3O4-: 322.0833 [L3-H]-; found: 322.0826 (100%). Selected IR numax/cm-1: 2415, 1703, 1599, 1463, 1278, 766. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: sodium hydroxide; tetra(n-butyl)ammonium hydroxide / benzene; water / 80 °C 2: methanol / 0.5 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64.7% | With 18-crown-6 ether; potassium carbonate In N,N-dimethyl-formamide for 40h; Inert atmosphere; Reflux; | 3. General Procedure for the Synthesis of 7 and 8 General procedure: Under an atmosphere of nitrogen, 6 (120 mg, 0.33 mmol), [G-n]-Br (for [G-1]-Br, 282.7 mg, 0.98 mmol; for [G-2]-Br, 605.0 mg, 0.98 mmol), K2CO3 (453.0 mg, 3.3 mmol) and 18-crown-6 (11 mg, 0.04 mmol) were dissolved in DMF (6 mL). The mixture was heated at reflux for 40 h and then cooled to room temperature. Solvent was distilled and the resulting mixture was poured into water and extracted with methylene chloride (3×40 mL). The methylene chloride solution was washed with water, dried over anhydrous magnesium sulfate, and filtered. The crude products were purified by column chromatography on silica gel (dichloromethane/ethyl acetate = 20/1) to give compounds 7 or 8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 254 mg | In acetonitrile at 60℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | Stage #1: 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate With ethyl acetate In toluene for 0.5h; Reflux; Stage #2: triethyl phosphite In toluene for 48h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 90℃; for 36h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / 1,4-dioxane; water / 36 h / 90 °C / Inert atmosphere 2: hydrazine hydrate / 12 h / 85 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / 1,4-dioxane; water / 36 h / 90 °C / Inert atmosphere 2: hydrazine hydrate / 12 h / 85 °C 3: acetic acid / ethanol / 12 h / 85 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Stage #1: nicotinic acid; 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate In acetonitrile for 24h; Reflux; Stage #2: With hydrogen bromide In water; acetic acid for 12h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | In acetonitrile for 24h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | Stage #1: methyl 4-hydroxylbenzoate; 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 24h; Stage #2: With water; sodium hydroxide In ethanol at 80℃; for 24h; | |
54% | Stage #1: methyl 4-hydroxylbenzoate; 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate With sodium hydroxide In N,N-dimethyl-formamide for 8h; Heating; Stage #2: With water; sodium hydroxide In methanol for 8h; | 2.2.1. Synthesis of H3L Dimethyl 5-(bromomethyl)benzene-1,3-dioate (5.7 g, 0.02 mol), methyl 4-hydroxybenzoate (3.0 g, 0.02 mol) and NaOH (0.8 g, 0.02 mol) were mixed in DMF (50 mL). The mixture was heated for 8 h, and the solid was obtained after removing the solvent by reduced pressure distillation. Then the solid, aqueous NaOH solution and methanol (200 mL) were added to the container to perform hydrolysis for 8 h. After cooling to room temperature, the pH value was adjusted to ca. 3 with diluted hydrochloric acid.The solid H3L was filtered off, washed with water and air-dried. Yield: 3.4 g, 54%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Stage #1: 1H-imidazole; 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate In methanol at 20 - 80℃; for 24h; Stage #2: With water; potassium hydroxide for 10h; Reflux; | Synthesis of H2L H2L was prepared by reaction of dimethyl 5-(bromomethyl)isophthalate with imidazole following the procedures used for synthesis of a-imidazolyl-m-toluic acid hydrochloride.[18,19,22] Amixture of dimethyl 5-(bromomethyl)isophthalate (1.28 g,5 mmol) and imidazole (1.7 g, 25 mmol) in methanol (75 mL)was cooled to room temperature after stirring at 80 °C for 24 h.The methanol was moved by evaporation to give a white solid;the solid was dissolved in CH2Cl2 (150 ml) and then washedwith water. The CH2Cl2 solution was then dried over Na2CO3.The Na2CO3 was filtered off. Then, 200-mL water and KOH(1.12 g, 20 mmol) were added into the resulting mixture. Thereaction mixture was refluxed for 10 h, and then poured intoice water, acidified with acetic acid to pH 3-4. After filtration,the product was obtained as pale-yellow solid (1.08 g, 88%). 1HNMR (300 MHz, DMSO-d6, 25 °C): 8.39 (s, 1H); 8.03 (s, 2H);7.86 (s, 1H); 7.26 (s, 1H); 6.96 (s, 1H); 5.37 (s, 2H). Anal. calcdfor C12H10N2O4: C, 58.54; H, 4.09; N, 11.38%. Found: C, 58.62;H, 4.28; N, 11.56%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: silver(l) oxide / dichloromethane / 48 h / Inert atmosphere 2: sodium hydroxide / methanol; water / 12 h / 55 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With silver(l) oxide In dichloromethane for 48h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With silver(l) oxide In dichloromethane for 48h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | Stage #1: 2,8,14,20-tetra-ethyl-4,10,16,22-tetra-hydroxy-6,12,18,24-tetra-methoxy-resorcin[4]arene; 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate With potassium carbonate; potassium iodide In acetonitrile for 12h; Heating; Stage #2: With sodium hydroxide In tetrahydrofuran; water for 10h; Reflux; | 2.3.1. Synthesis of H8L1 and H4L2 Typically, a solution of 3-methoxyphenol (4.96 g, 40 mmol) andpropylaldehyde (2.32 g, 40 mmol) in anhydrous dichloromethane(200 mL) was cooled in ice bath. Boron trifluoride etherate(11.36 g, 80 mmol) was added dropwise to the solution and themixture was stirred at rt. overnight. Then the reaction mixturewas washed using water (100 mL), and the organic layer was driedwith anhydrous sodium sulfate. The solvent was removed byrotary evaporation to obtain red oil residue. The oil was dissolvedin a minimum amount of hot ethanol. Upon cooling, the intermediatecompound 2,8,14,20-tetra-ethyl-4,10,16,22-tetra-hydroxy-6,12,18,24-tetra-methoxy-resorcin[4]arene (L) was achieved in58% yield (Scheme 2).A mixture of L (1.968 g, 3 mmol), dimethyl 5-bromomethyl-1,3-benzene-dicarboxylate (3.444 g, 12 mmol), anhydrous K2CO3(8.28 g, 60 mmol), KI (0.1992 g, 1.2 mmol) and CH3CN (100 mL)was heated in a water bath for 12 h. Then remove the solvent bywater bath. After that, tetrahydrofuran (150 mL), water (20 mL),and NaOH (1.92 g, 48 mmol) were put in the isolated productsand refluxed for 10 h. The solvent was removed by the water bathagain, and added 500 mL water. The pH value of the mixture wasadjusted to 1-2 with HCl (1.0 molL1). Finally, pale yellow solidof H8L1 was obtained. The solid product was filtered, washed bywater, and dried (yield = 76%). The preparation of H4L2 was similarto that of H8L1 except that methyl 3-(chloromethyl)benzoate(2.215 g, 12 mmol) was used instead of dimethyl-5-bromomethyl-1,3-benzene-dicarboxylate (yield = 64%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | The ligand of 1-(3,5-dicarboxybenzyl)-1H-pyrazole-3,5-dicarboxylic acid(H4dpb) was synthesized according to the following procedure [26]. Potassium hydroxide (KOH) (0.28g, 5mmol) was added to a solution of <strong>[4077-76-3]dimethyl 1H-pyrazole-3,5-dicarboxylate</strong> (0.46g, 2.5mmol) in 20mL DMF. The mixture was then stirred for 30min at 80C, following which dimethyl 5-(bromomethyl)isophthalate (0.71g, 2.5mmol) was added and the solution was stirred further for 2h at 80C, then 5mL water and KOH (1.12g, 20mmol) were added into the resulting mixture, the reaction mixture was refluxed for 3h. The solution was cooled down to room temperature and then poured into water of 2C approximately (300mL), acidified with HCl (6.0mol/L) to pH 5-6, the numerous white solid of H4dpb was collected by filtration and washed by water with a yield of 0.71g (85.0%). ESI-MS: m/z (100%) 333.06 [M-1]+. The IR spectra of H4dpb is given in the Supporting Information (Fig. S1). IR (KBr, cm-1): 3487(m), 3151(s), 1707(s), 1533(w), 1471(w), 1458(m), 1383(w), 1228(s), 1107(m), 1006(w), 912(w), 804(s), 770(s). 742(m) (see Scheme1 ). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: L-alanine methyl ester hydrochloride With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 1h; Inert atmosphere; Stage #2: 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate In N,N-dimethyl-formamide at 50℃; for 32h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Stage #1: 5-(2,8-dimethyl-5H-dibenzo[a,d]cyclohepten-5-yl)-2,4(1H,3H)-pyrimidinedione With N,O-Bis(trimethylsilyl)trifluoroacetamide In 1,2-dichloro-ethane for 1.5h; Inert atmosphere; Reflux; Stage #2: 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate In 1,2-dichloro-ethane for 16h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: N,O-Bis(trimethylsilyl)trifluoroacetamide / 1,2-dichloro-ethane / 1.5 h / Inert atmosphere; Reflux 1.2: 16 h / Reflux 2.1: Lawessons reagent / 1,4-dioxane / 16 h / Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1.1: N,O-Bis(trimethylsilyl)trifluoroacetamide / 1,2-dichloro-ethane / 1.5 h / Inert atmosphere; Reflux 1.2: 16 h / Reflux 2.1: Lawessons reagent / 1,4-dioxane / 16 h / Inert atmosphere; Reflux 3.1: sodium hydroxide / methanol; water; toluene / 4 h 4.1: triethylamine / N,N-dimethyl-formamide / 0.5 h 5.1: lithium hydroxide / methanol; water / 16 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1.1: N,O-Bis(trimethylsilyl)trifluoroacetamide / 1,2-dichloro-ethane / 1.5 h / Inert atmosphere; Reflux 1.2: 16 h / Reflux 2.1: Lawessons reagent / 1,4-dioxane / 16 h / Inert atmosphere; Reflux 3.1: sodium hydroxide / methanol; water; toluene / 4 h 4.1: triethylamine / N,N-dimethyl-formamide / 0.5 h 5.1: lithium hydroxide / methanol; water / 16 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: N,O-Bis(trimethylsilyl)trifluoroacetamide / 1,2-dichloro-ethane / 1.5 h / Inert atmosphere; Reflux 1.2: 16 h / Reflux 2.1: Lawessons reagent / 1,4-dioxane / 16 h / Inert atmosphere; Reflux 3.1: sodium hydroxide / methanol; water; toluene / 4 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: N,O-Bis(trimethylsilyl)trifluoroacetamide / 1,2-dichloro-ethane / 1.5 h / Inert atmosphere; Reflux 1.2: 16 h / Reflux 2.1: Lawessons reagent / 1,4-dioxane / 16 h / Inert atmosphere; Reflux 3.1: sodium hydroxide / methanol; water; toluene / 4 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1.1: N,O-Bis(trimethylsilyl)trifluoroacetamide / 1,2-dichloro-ethane / 1.5 h / Inert atmosphere; Reflux 1.2: 16 h / Reflux 2.1: Lawessons reagent / 1,4-dioxane / 16 h / Inert atmosphere; Reflux 3.1: sodium hydroxide / methanol; water; toluene / 4 h 4.1: triethylamine / N,N-dimethyl-formamide / 0.5 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1.1: N,O-Bis(trimethylsilyl)trifluoroacetamide / 1,2-dichloro-ethane / 1.5 h / Inert atmosphere; Reflux 1.2: 16 h / Reflux 2.1: Lawessons reagent / 1,4-dioxane / 16 h / Inert atmosphere; Reflux 3.1: sodium hydroxide / methanol; water; toluene / 4 h 4.1: triethylamine / N,N-dimethyl-formamide / 0.5 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 6 steps 1.1: N,O-Bis(trimethylsilyl)trifluoroacetamide / 1,2-dichloro-ethane / 1.5 h / Inert atmosphere; Reflux 1.2: 16 h / Reflux 2.1: Lawessons reagent / 1,4-dioxane / 16 h / Inert atmosphere; Reflux 3.1: sodium hydroxide / methanol; water; toluene / 4 h 4.1: triethylamine / N,N-dimethyl-formamide / 0.5 h 5.1: lithium hydroxide / methanol; water / 16 h 6.1: bromo-tris(1-pyrrolidinyl)phosphonium hexafluorophosphate; triethylamine / N,N-dimethyl-formamide / 0.5 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 6 steps 1.1: N,O-Bis(trimethylsilyl)trifluoroacetamide / 1,2-dichloro-ethane / 1.5 h / Inert atmosphere; Reflux 1.2: 16 h / Reflux 2.1: Lawessons reagent / 1,4-dioxane / 16 h / Inert atmosphere; Reflux 3.1: sodium hydroxide / methanol; water; toluene / 4 h 4.1: triethylamine / N,N-dimethyl-formamide / 0.5 h 5.1: lithium hydroxide / methanol; water / 16 h 6.1: bromo-tris(1-pyrrolidinyl)phosphonium hexafluorophosphate; triethylamine / N,N-dimethyl-formamide / 0.5 h |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 7 steps 1.1: N,O-Bis(trimethylsilyl)trifluoroacetamide / 1,2-dichloro-ethane / 1.5 h / Inert atmosphere; Reflux 1.2: 16 h / Reflux 2.1: Lawessons reagent / 1,4-dioxane / 16 h / Inert atmosphere; Reflux 3.1: sodium hydroxide / methanol; water; toluene / 4 h 4.1: triethylamine / N,N-dimethyl-formamide / 0.5 h 5.1: lithium hydroxide / methanol; water / 16 h 6.1: bromo-tris(1-pyrrolidinyl)phosphonium hexafluorophosphate; triethylamine / N,N-dimethyl-formamide / 0.5 h 7.1: trifluoroacetic acid / dichloromethane / 0.5 h / 20 °C 7.2: 20 °C / Darkness |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 7 steps 1.1: N,O-Bis(trimethylsilyl)trifluoroacetamide / 1,2-dichloro-ethane / 1.5 h / Inert atmosphere; Reflux 1.2: 16 h / Reflux 2.1: Lawessons reagent / 1,4-dioxane / 16 h / Inert atmosphere; Reflux 3.1: sodium hydroxide / methanol; water; toluene / 4 h 4.1: triethylamine / N,N-dimethyl-formamide / 0.5 h 5.1: lithium hydroxide / methanol; water / 16 h 6.1: bromo-tris(1-pyrrolidinyl)phosphonium hexafluorophosphate; triethylamine / N,N-dimethyl-formamide / 0.5 h 7.1: trifluoroacetic acid / dichloromethane / 0.5 h / 20 °C 7.2: 20 °C / Darkness |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 7 steps 1.1: N,O-Bis(trimethylsilyl)trifluoroacetamide / 1,2-dichloro-ethane / 1.5 h / Inert atmosphere; Reflux 1.2: 16 h / Reflux 2.1: Lawessons reagent / 1,4-dioxane / 16 h / Inert atmosphere; Reflux 3.1: sodium hydroxide / methanol; water; toluene / 4 h 4.1: triethylamine / N,N-dimethyl-formamide / 0.5 h 5.1: lithium hydroxide / methanol; water / 16 h 6.1: bromo-tris(1-pyrrolidinyl)phosphonium hexafluorophosphate; triethylamine / N,N-dimethyl-formamide / 0.5 h 7.1: trifluoroacetic acid / dichloromethane / 0.5 h / 20 °C 7.2: 20 °C / Darkness |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 3-[[6-(1H-indol-6-yl)indol-1-yl]methyl]benzoic acid With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 0.5h; Stage #2: 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate In N,N-dimethyl-formamide; mineral oil for 2h; | General procedure iii: Synthesis of 3-[[6-[1-[(3-tert-butoxycarbonylphenyl)methyl]indol-6-yl]indol-1-yl]methyl]benzoic acid (9c) General procedure: To a stirred solution of 8a (232 mg, 0.63 mmol) in DMF (7.0 mL) at 0°C was added NaH (60%in mineral oil, 61.5 mg, 1.54 mmol) and the reaction mixture was allowed to warm up to RT over30 min. 6c (171 mg, 0.63 mmol) was added and the mixture was stirred for 2 hours. The reactionmixture was added dropwise into 2.0 M HCl (20 mL), extracted with DCM (30 mL × 3), and thecombined organic fractions were concentrated. Purification by silica gel chromatography(40%60% EtOAc/hexanes) afforded 9c (266 mg, 76%) as a white powder. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | Stage #1: 4,4'-bipyridine; 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate In acetonitrile at 10℃; for 24h; Stage #2: With hydrogenchloride In water at 100℃; for 12h; | 1.2 step 2: preparation of Ligand 1,1'- bis(3,5-dicarboxybenzyl)- 4,4'- bipyridine chloride H4LCl2 0.32 g (1 mmol) of 4-bipyridine and 1.72 g (3 mmol) of dimethyl 5-benzylbromoisophthalate synthesized in the first step were dissolved in a 100 mL single-necked flask containing 40 mL of acetonitrile solution A, then reacted in an oil bath at 10 ° C for 24 h, after the end of the reaction, cooled to room temperature, and filtered to obtain a precipitate A; The precipitate A was washed with 10 ml of acetonitrile solution B each time, washed a total of 3 times, and then dried in a vacuum oven at 40 ° C to obtain a pale yellow solid powder; The pale yellow solid powder was dissolved in a 50 mL single-mouth bottle containing 15 mL of concentrated hydrochloric acid at a concentration of 12 mol/L, and then reacted in an oil bath at 100 ° C for 12 h. After the reaction was completed, it was cooled to room temperature and filtered to obtain a precipitate B. The precipitate B was washed with 10 mL of distilled water each time, washed a total of 3 times, and then dried in a vacuum oven at 60 ° C to obtain a white solid powder of 0.5 g, yield 86.0%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethyl acetate; toluene Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium carbonate In N,N-dimethyl-formamide at 85℃; for 10h; | Synthesis of dimethyl 5-((4-(4 (ethoxycarbonyl)phenylazo)phenoxy) methyl) isophthalate (1) 5-(Bromomethyl)isophthalic aciddimethyl ester(517 mg, 1.8 mmol), 4-(4-Hydroxy-phenylazo)benzoicacid ethyl ester (270 mg, 1 mmol) and K2CO3 (207 mg, 1.5 mmol) was dissolved in 50 mL DMF in a 100 mL flask. The reaction system was stirred and heated at 85 °C for 10 h to form precipitate. A mass of water was added and filtered to obtain the cuticolor solid product 1 with ayield of 95%. 1H NMR (600 MHz, CDCl3) δ 8.67 (s, 1H), 8.34 (s, 1H),8.18 (d, J=7.9 Hz, 1H), 7.97 (d, J=8.1 Hz, 1H), 7.91 (d, J=7.9 Hz,1H), 7.12 (d, J=8.1 Hz, 1H), 5.24 (s, 1H), 4.41 (q, J=6.7 Hz, 1H),3.97 (s, 2H), 1.43 (t, J=6.8 Hz, 1H). Elemental analysis results found:C, 65.50; H, 5.10; N, 5.84%; C26H24N2O7 requires C, 65.54; H, 5.05; N,5.88%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With potassium carbonate In acetonitrile for 24h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With potassium carbonate In N,N-dimethyl-formamide at 85℃; for 10h; | |
With potassium carbonate In N,N-dimethyl-formamide at 60℃; for 8h; | 1.1 (1), the starting material 4,4'-dihydroxyazobenzene (1 mmol),Dimethyl 5-(bromomethyl)isophthalate (2.5 mmol) and anhydrous potassium carbonate (2.5 mmol) were dissolved in 80 mL of N'N-dimethylformamide, and stirred at 60 °C for 8 h.After the reaction of the raw materials is completed, cooling, adding a large amount of yellow solid by adding 250 mL of distilled water, and filtering to obtain an intermediate product 1 (dimethyl p-methoxybenzyl azobenzene) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate at 90℃; for 12h; | 1 The synthetic route of the target compound is as follows Synthesis step of the target compound: 5-bromomethylisophthalate (2 mmol) and 4-amino-2,3 dimethylazobenzene (1 mmol),Add potassium carbonate (1 mmol), and stir at 0 °C for 12 h.Cooling filtration,The filtrate is steamed,The obtained crude product was purified by column chromatography (petroleum ether: ethyl acetate = 10:1, ratio) to give the title compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: potassium carbonate; tetrakis(triphenylphosphine) palladium(0) / 1,4-dioxane; water / 24 h / 90 °C / Inert atmosphere 2: hydrazine hydrate / 12 h / 85 °C 3: acetic acid / ethanol / 12 h / 85 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 90℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: acetonitrile / 24 h / Reflux 2: hydrogenchloride / water / 48 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: acetonitrile / 24 h / Reflux 2: hydrogenchloride / water / 48 h / Reflux 3: cobalt(II) chloride hexahydrate; nitric acid / water / 3 h / 80 °C / Sealed tube |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With potassium carbonate In acetonitrile for 24h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | In N,N-dimethyl-formamide at 90℃; for 8h; | 1"-[3,5-bis(methoxycarbonyl)benzyl]-6'-(pyridin-2-yl)-[2,2':4',4"-terpyridin]-1"-ium bromide (2, C31H25N4BrO4) To a stirred solution of 0.75 g 4′-(4-pyridyl)-2,2′:6′,2-terpyridine (2.5 mmol) in 10 cm3 dimethylformamide, 1.15 g 5-(bromomethyl)isophthalic acid dimethyl ester (4 mmol) was added and then the reaction temperature was increased to 90 °C and maintained for 8 h (Scheme 1). The precipitate was isolated by hot filtration and washed with acetone separately, giving L-Br as a white solid (2.53 g, yield: 75%). 1HNMR (400 MHz, DMSO-d6): δ = 9.47 (2H, d, J = 6.4 Hz,Hg),8.89 (2H, s, He),8.82 (2H, d, J = 6.0 Hz, Hf),8.78 (2H,d, J = 4.5 Hz, Ha), 8.72 (2H, d, J = 7.6 Hz, Hd),8.59 (1H,s, Hi),8.51 (2H, s, Hh),8.08 (2H, t, J = 15.6 Hz, Hb),7.58(2H, t, J = 12.0 Hz, Hc), 6.08 (2H, s, -CH2-), 3.92 (6H, s, -OCH3) ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetonitrile for 48h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 4,4'-bipyridine; 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate In acetonitrile for 24h; Reflux; Stage #2: With hydrogen bromide for 48h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: acetic acid; hydrogen bromide / 12 h / Reflux 2: oxalyl dichloride / chloroform / 6 h / 0 °C / Inert atmosphere 3: N,N-dimethyl-formamide / 12 h / 0 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: acetic acid; hydrogen bromide / 12 h / Reflux 2: oxalyl dichloride / chloroform / 6 h / 0 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | Stage #1: L-glutamic dimethyl ester hydrochloride With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: 1,3-dimethyl 5-(bromomethyl)benzene-1,3-dicarboxylate In N,N-dimethyl-formamide at 55℃; for 48h; | 2.2.1. Synthesis of (S)-5-((2-carboxy-5-oxopyrrolidin-1-yl)methyl)isophthalic acid (H3L) The synthesis route of ligand H3L is shown in Scheme 1. A mixture ofL-α-glutamic acid dimethyl ester hydrochloride (6.35 g, 30.00 mmol),anhydrous K2CO3 (4.53 g, 40.00 mmol), and dry DMF (40 mL) wasstirred at room temperature for 1 h, and then a solution of 5-bromomethyl-isophthalic acid dimethyl ester (2.87 g, 10.00 mmol) and dryDMF (20 mL) was added dropwise. The resulting mixture was heated to 55° C and kept at that temperature with continuous stirring for 48 h. All the above processes took place under nitrogen. The mixture was cooled to room temperature and filtered to remove any solids. Pale yellow oil was obtained after removal of the solvent in vacuo. The pale yellow oil was redissolved in dichloromethane and washed with distilled water several times. After evaporation of the solvent, pure pale yellow oil was obtained. A mixture of the resulting pale yellow oil, methanol (15 mL),and an aqueous solution of NaOH (25 mL, 5%) was heated at 70° C withstirring for 36 h. As the pH value of the reaction solution was adjusted to 4, white precipitate appeared. After having been filtered, washed with distilled water, and dried in air, white powder H3L was obtained. Yield:1.32 g, 43% (based on 5-bromomethylisophthalic acid dimethyl ester).Anal. Calcd for C14H13NO7 (%): C, 54.73; H, 4.26; N, 4.56. Found: C,54.85; H, 4.21; N, 4.49. IR (KBr, cm1): 3430 (m), 3075 (w), 2920 (w),2850 (w), 1701 (s), 1623 (s), 1468 (m), 1419 (m), 1257 (s), 1210 (m),739 (w), 711 (w), 685 (w), 533 (w). 1H NMR (300 MHz, DMSO), δ (ppm):2.19 (m, 4 H), 4.10 (m, 1 H), 4.82 (d, 2 H), 8.02 (s, 2 H), 8.37 (s, 1 H),13.24 (s, 3 H). 13C NMR (75 MHz, DMSO), δ (ppm): 22.62, 28.87, 44.54,58.81, 131.50, 132.95, 133.07, 138.11, 166.46, 173.21, 174.81. HRMS:m/z 306.0830 (M H, 306.0614 calculated for C14H12NO7). |
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