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CAS No. : | 25519-82-8 | MDL No. : | MFCD00114817 |
Formula : | C13H18ClNO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | BBDTWYQCXXFKDH-UHFFFAOYSA-N |
M.W : | 255.74 | Pubchem ID : | 2740587 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338-P310 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H332-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 |
---|---|---|
A. A sample of anisole is treated according to the manipulative procedures described above in Example 1(c) and (d) to produce 4-(4-methoxybenzoyl)piperidine hydrochloride which, when recrystallized from isopropanol, had a mp of 251-256 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With triethylamine; HATU; In N,N-dimethyl-formamide; at 20℃; for 4h; | To a solution of5-(methoxycarbonyl)picolinic acid (319 mg, 1.76 mmol) and 4-(4-methoxybenzoyl) piperidinehydrochloride (300 mg, 1.17 mmol) in dimethylformamide (5 mL) was added triethylamine(0.406 mL), followed by the addition of HATU (669 mg, 2.64 mmol). The reactionmixture was stirred at ambient temperature for 4 hours before 50% aqueous sodiumbicarbonate solution (20 mL) was added. Then the mixture was extracted with ethylacetate (3 5 mL). The organic phasewas washed with saturated aqueous sodium chloride solution (2 5 mL), dried over sodiumsulfate, filtered and concentrated. The residue was purified by columnchromatography (silica gel, petroleum ether/ethyl acetate 1:1) to give the titlecompound (425 mg, 95% yield) as white solid. |
80% | With triethylamine; HATU; In N,N-dimethyl-formamide; at 20℃; for 4h; | To a mixture of <strong>[25519-82-8]4-(4-methoxybenzoyl)piperidine hydrochloride</strong> (2.00 g, 7.82 mmol, 1.0 eq) and 5-(methoxycarbonyl)pyridine-2-carboxylic acid (1.42 g, 7.82 mmol, 1.0 eq) in dimethylformamide (55 mL) was added triethylamine (2.72 mL, 19.55 mmol, 2.5 eq) followed by HATU (2.97 g, 7.82 mmol, 1.0 eq). The reaction was stirred at room temperature for 4 hours before partitioning between EtOAc (250 mL) and water-NaHCO3 (1:1, 200 mL). The organics were further washed with brine (150 mL), water (150 mL) and brine (150 mL), dried (Na2SO4) and concentrated under reduced pressure. Column chromatography (silica, 4-5% MeOH-CH2Cl2) yielded the coupled product (2.39 g, 80%) as a white foam; 1H nmr (CDCl3) delta 9.08 (1H, m, pyH-6), 8.29 (1H, dd, J 8.5, 2.0 Hz, pyH-4), 7.84 (2H, d, J 9.0 Hz, 2H of C6H4OCH3), 7.60 (1H, d, J 8.0 Hz, pyH-3), 6.84 (2H, d, J 9.0 Hz, 2H of C6H4OCH3), 4.60 (1H, m, 1H of BzpipH-2, H-6), 3.87 (3H, s, 1×OCH3), 3.82 (1H, m, 1H of BzpipH-2, H-6), 3.77 (3H, s, 1×OCH3), 3.46 (1H, m, BzpipH-4), 3.19 (1H, ddd, J 14.0, 10.0, 4.0 Hz, 1H of BzpipH-2, H-6), 3.02 (1H, m, 1H of BzpipH-2, H-6), 1.95-1.90 (1H, m, 1H of BzpipH-3, H-5), 1.83-1.79 (3H, m, 3H of BzpipH-3, H-5); 13C nmr (CDCl3) delta 199.9, 166.6, 165.0, 163.5, 157.7, 149.6, 138.1, 130.5, 128.5, 126.3, 123.1, 113.9, 55.4, 52.5, 46.6, 42.6, 41.8, 28.8, 28.4; m/z: 383 [M+H]+ (found [M+H]+, 383.1515, C21H22N2O5 requires [M+H]+ 383.1602). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With triethylamine; In acetonitrile; at 130℃; for 0.2h;Microwave irradiation; | To a solution of 2-(2-bromo-5-oxopyrrolidin-1-yl)acetonitrile (730 mg, 3.6 mmol) and <strong>[25519-82-8](4-methoxyphenyl)(piperidin-4-yl)methanone hydrochloride</strong> (920 mg, 3.6 mmol) in acetonitrile (4 ml) was added triethylamine (1.5 ml, 1 1 mmol). The mixture was microwave at 130C for 12 minutes. The solvent was removed in vacuo and the residue was taken up in methylene chloride and water. The organic layer was purified via flash column chromatography (ethyl acetate:hexane, 10:90 to 100:0) to provide slightly yellow oil (950 mg, 74% yield). 1 H NMR (400 MHz, CDCl3) delta 7.94 (d, J = 8.5 Hz, 2 H), 6.96 (d, J = 8.5 Hz, 2 H), 4.22-4.39 (m, 2 H), 3.90 (s, 3 H), 3.57 (dt, J = 22.6, 9.0 Hz, 2 H), 3.40- 3.51 (m, J = 8.5 Hz, 1 H), 3.23-3.39 (br s, 1 H), 2.93-3.20 (m, 3 H), 2.33-2.61 (m, 2 H), 2.13-2.31 (m, 1 H), 1 .83-2.03 (m, 4 H). HRMS calculated for 342.1818, found (ESI, [M + H]+), 342.1830. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With triethylamine; In acetonitrile; at 20 - 70℃; | (4-Methoxyphenyl)(piperidin-4-yl)methanone hydrochloride (524 mg, 2.05 mmol) was stirred at room temperature with triethylamine (0.657 mL, 477 mg, 4.71 mmol) in acetonitrile (80 mL). A solution of ethyl 2-(3-bromo-2-oxopyrrolidin-1-yl)acetate (513 mg, 2.05 mmol) in acetonitrile (20 mL) was added to the mix. The reaction was stirred 3 hours at 40C and then overnight at 50C. After 24 hours the reaction was not complete and the reaction was stirred an additional 48 hours at 70C then allowed to cool to room temperature. The solvents were removed in vacuo. The crude orange solid was eluted through a silica gel column with a 0 to 10% methanol / dichloromethane gradient to afford the title racemic compound (730 mg, 87% yield, 95% purity) as a thick amber oil. MS (ESI) [m/e, (M+H)] = 389.5. 1H NMR (400 MHz, chloroform-d) delta ppm 7.90 - 7.95 (m, 2 H), 6.91 - 6.96 (m, 2 H), 4.17 - 4.24 (m, 2 H), 3.95 -4.17 (m, 2 H), 3.88 (s, 3 H), 3.56 - 3.64 (m, 1 H), 3.36-3.50 (m, 2 H), 3.18-3.29 (m, 1 H), 3.04-3.13 (m, 1 H), 2.93- 3.04 (m, 2 H), 2.4 1 - 2.56(m, 1 H), 2.20-2.35 (m, 1 H), 2.04-2.19 (m, 1 H), 1.80- 1.95(m, 4 H), 1.26 - 1.32 (m, 3 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 4-methyl-morpholine; benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In N,N-dimethyl-formamide; at 20℃; for 18h; | Example 1 Synthesis of 2-{4-[4-(4-methoxy-benzoyl)-piperidin-1 -yl]-4-oxo-butyl}-3H- quinazolin-4-one ("A1") EDCI NMM HOBt DMF To a solution of 4-(4-oxo-3,4-dihydro-quinazolin-2-yl)-butyric acid (51.0 mg, 0.22 mmol), <strong>[25519-82-8](4-methoxy-phenyl)-piperidin-4-yl-methanone hydrochloride</strong> (84.4 mg, 0.33 mmol) and benzotriazol-1-ol hydrate (50.5 mg, 0.33 mmol) in DMF (0.5 ml_) are added N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (74.8 mg, 0.30 mmol) and 4-methylmorpholine (39.5 mg, 0.39 mmol). The mixture is stirred for 18 hours at room temperature. The reaction mixture is partitioned between water and dichloromethane. The organic phase is dried over sodium sulfate and evaporated. The residue is chromatographed on a silica gel column with methanol/dichloromethane as eluent to afford 2-{4-[4-(4- methoxy-benzoyl)-piperidin-1-yl]-4-oxo-butyl}-3H-quinazolin-4-one as colorless, amorphous solid; HPLC/MS 1.71 min (A), [M+H] 435; 1H NMR (400 MHz, DMSO-d6) delta 12.15 (s, 1 H), 8.08 (dd, J = 8.1 , 1.5 Hz, 1H), 8.04 - 7.95 (m, 2H), 7.76 (ddd, J = 8.5, 7.1 , 1.6 Hz, 1 H), 7.59 (dt, J = 8.1 , 0.8 Hz, 1H), 7.45 (ddd, J = 8.1 , 7.1 , 1.2 Hz, 1 H), 7.12 - 6.99 (m, 2H), 4.40 (d, J = 12.9 Hz, 1H), 3.93 (d, J = 13.7 Hz, 1 H), 3.85 (s, 3H), 3.65 (tt, J = 11.2, 3.6 Hz, 1 H), 3.25 - 3.11 (m, 1 H), 2.73 (td, J = 12.8, 2.8 Hz, 1 H), 2.65 (t, J = 7.4 Hz, 2H), 2.42 (td, J = 7.3, 2.9 Hz, 2H), 1.98 (p, J = 7.2 Hz, 2H), 1.77 (m, 2H), 1.51 (qd, J = 12.1 , 4.0 Hz, 1 H), 1.34 (qd, J = 12.1, 4.1 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; water; In tetrahydrofuran; for 10h;Reflux; | General procedure: To a solution of 1-(4-(2,3-dihydrobenzo[b][1,4] dioxine-6-carbonyl) piperidin-1-yl) ethanone 10a (3.13 g, 10 mmol) in 25 mL of THF was added 40 mL of 3 mol/L HCl. The reaction mixture was refluxed for 10 h. The solution was then concentrated in vacuo. The residue was recrystallized from MeOH/Ether to afford 11a (2.64 g, 93% yieid) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In water; acetonitrile; for 4h;Reflux; | General procedure: To a solution of (2-(4-fluorophenyl)oxazol-4-yl)methanol 6a (1.13 g, 6 mmol) in 30 mL DCM was added SOCl2 (0.58 mL, 8 mmol). The solution was refluxed for 2 h and then poured into 30 mL of ice cold water. The organic layer was concentrated in vacuo to afford crude 7a as a yellow oil without a further purification. To a solution of 7a and 11a (1.70 g, 6 mmol) in 12 mL of 1 mol/L NaOHaq and 15 mL of CH3CN was refluxed for 4 h. Then the solution concentrated in vacuo. The residue extracted with CH2Cl2 (20 mL × 2) and washed with brine, dried over anhydrous sodium sulfate. The solution filtered to remove the precipitate and concentrated in vacuo. The crude product was purified by silica gel chromatography using 40:1 DCM/MeOH as the eluent to afford 1a (1.74 g, 69% yield) as a pale yellow solid. |
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