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[ CAS No. 1149-23-1 ]

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Chemical Structure| 1149-23-1
Chemical Structure| 1149-23-1
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CAS No. :1149-23-1 MDL No. :MFCD00005951
Formula : C13H19NO4 Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W :253.29 g/mol Pubchem ID :70849
Synonyms :

Safety of [ 1149-23-1 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 1149-23-1 ]

  • Downstream synthetic route of [ 1149-23-1 ]

[ 1149-23-1 ] Synthesis Path-Downstream   1~17

  • 1
  • [ 100-97-0 ]
  • [ 141-97-9 ]
  • [ 1149-23-1 ]
YieldReaction ConditionsOperation in experiment
98% Stage #1: hexamethylenetetramine; ethyl acetoacetate at 15 - 20℃; for 0.5h; Large scale; Stage #2: With ethanolamine at 30 - 70℃; for 2.5h; Large scale; 1-4 Example 4 A method for preparing a dihydropyridine raw material drug, the specific steps are as follows:(1) Put 162.5 kg of ethyl acetoacetate and 140 kg of urotropine into the reaction kettle.Control the temperature at 15 ~ 20 ° C, stir and dissolve for 0.5 hours; raise the temperature to 30 ~ 35 ° C,Slowly add 201.3kg of ethanolamine to control the drop rate, and add it in 1 hour. The temperature is raised to 65-70 ° C, the reaction is kept for 2.5 hours, and the temperature is slowly lowered to 0 to 10 ° C.Insulation crystallization for 3 hours, control temperature 3 ~ 5 ° C when centrifuged to obtain 264 kg crude dihydropyridine;(2) 1056 kg of ethanol was added to the reaction vessel, and 264 kg of crude dihydropyridine was added.Heat and stir to dissolve, add ice vinegar acid to adjust PH=7; add 2.64kg activated carbon,Stir for one hour and then press into the crystallizer.The temperature is controlled to be stirred at 0 to 5 ° C, and the crystals are stirred for 2 hours.When the temperature is controlled at 0 to 3 ° C, the mixture is centrifuged to obtain 267 kg of dihydropyridine wet product;(3) Transfer the dihydropyridine wet product into the drying room, and dry it at 60 ° C in a vacuum dryer.After drying for 8 hours, the raw material drug 246 kg of dihydropyridine product was obtained, and the content was 103.5%.The yield was 98.0%.
85% With diammonium phosphate In ethanol; water at 80℃; Preparation of compound 1 To a stirred solution of ethyl acetoacetate (30.00 g 230.52 mmol) andhexamethylenetetramine (10.76 g, 76.84 mmol) in ethanol (150 mL) at roomtemperature was slowly added the solution of ammonium phosphate (15.24 g115.28mmol) in H2O (30 mL). The mixture was warmed to 80°C until a yellow- orange solidformed, which was filtered and washed with water (50 mL×3) and ethanol (50 mL×3),dried to give desired compound 1(24.80 g, yield 85%).
63% With ammonium acetate for 0.0277778h; microwave irradiation;
With ethanol
With ammonium phosphate; ethanol

  • 2
  • [ 1149-23-1 ]
  • [ 1721-13-7 ]
  • 3
  • [ 1149-23-1 ]
  • [ 2602-36-0 ]
YieldReaction ConditionsOperation in experiment
With potassium hydroxide
Multi-step reaction with 2 steps 1: iron(III) chloride / water / 1 h / Reflux 2: sodium hydroxide / methanol
  • 4
  • [ 1149-23-1 ]
  • [ 1149-24-2 ]
YieldReaction ConditionsOperation in experiment
100% With ruthenium(II) tris(2,2'-bipyridine) hexafluorophosphate; In acetic acid; acetonitrile; at 15℃;Irradiation; General procedure: To a suspension of the dihydropyridine (1.20 mmol) in AcOH (4 mL) was added tris(bipyridine)ruthenium(II) hexafluorophosphate (0.1 mL, 2 mg/mL in MeCN). This mixture was then irradiated with a blue LED light (3 W, Wanhui WH-CS) in a water bath at 15 C until TLC showed that the substrate had been consumed. The solution was then diluted with H2O (20 mL) and extracted with MTBE (3 × 20 mL). The combined organic phase was washed with sat. aq NaHCO3 solution (3 × 10 mL) and brine (10 mL). The dried organic phase was concentrated and subjected to flash chromatography to give the pyridine product.
99% With copper(ll) bromide; In chloroform; ethyl acetate; for 1.0h;Reflux; General procedure: Equivalent amounts of 1,4-dihydropyridine (1, 3 mmol) and cupricbromide (3 mmol) were taken in a dry round-bottomed flask (25 mL) and ethylacetate-chloroform mixture (10 ml, v/v 1:1) was added to it. The flask wasfitted with a Liebig condenser fitted with a calcium chloride guard tube andwas refluxed for 1 h. The reaction was monitored by TLC after an interval of10 min. After completion, the reaction mixture was filtered through a flutedfilter paper, washed thoroughly with chloroform in order to remove theadhering cuprous bromide from the product and dried over anhydrous Na2SO4.Solvent was removed in vacuo and purified by column filtration to get pureproduct.
98% With oxygen; In water; at 80℃; for 4.0h; General procedure: A 20 mL two-necked flask was evacuated and backfilled with molecular oxygen. Then, substrate (1 mmol) and 5 mL of PMAS/Au NPs solution (Au: 0.05 mmol, 5 mol %) were added at room temperature. The mixture was stirred at 80 C under molecular oxygen for 4 h. The reaction mixture was extracted with ethyl acetate. The organic layer was evaporated and examined by 1H NMR analysis (JEOL ECS-400, 400 MHz) with 1,3,5-trimethoxybenzene as an internal standard.
98% With tris(p-bromophenylammoniumyl) hexachloroantimonate; In acetonitrile; at 60℃; for 6.0h; General procedure: A solution of 1a (0.5mmol) in CH3CN (5ml) at 60 was mixed fully and flushed with air (keep flushing until the reaction completed), then TBPA+. (0.025mmol, dissolved in CH3CN 5ml ) was added .After completion monitored by TLC, the reaction was quenched with water. The mixture was poured into a separator funnel with the addition of excess DCM, and then the crude organic solution was extracted three times with water to remove inorganic salts. The organic phase was then dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure and the products were separated by silica gel column chromatography eluted with petroleum ether/acetone (v/v 10:1) to afford the products.
98% With oxygen; toluene-4-sulfonic acid; acetic acid; at 20℃; for 2.0h; General procedure: Diethyl 2,6-dimethyl-4-phenylpyridine-3,5-dicarboxylate (329 mg,1 mmol) and p-TSA (170 mg, 1 mmol) were dissolved in acetic acid(2 mL). The mixture was stirred at room temperature until thestarting material was completely consumed. Then, 10% Na2CO3solution (25 mL) was added to precipitate the crude product, whichwas collected by filtration and recrystallised from ethanol. Likewise,the product was extracted with ethyl acetate (3 × 15 mL) and washedwith water (2 × 10 mL). The crude product was purified by columnchromatography on silica gel (petroleum ether:EtOAc = 7:1) to yieldthe pure product as a pale yellow solid (312 mg, 95% yield).Diethyl 2,6-dimethylpyridine-3,5-dicarboxylate (5): M.p 69-70 C(lit.18 70-71 C); 1H NMR (500 MHz, CDCl3): 1.44 (t, 6H, J = 7.3,CH2CH3), 2.87 (s, 6H, CH3), 4.42 (q, 4H, J = 7.3, CH2CH3), 8.70 (s, 1H,pyridine).
97% With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; iron(III) chloride hexahydrate; oxygen; sodium nitrite; In acetic acid; acetonitrile; at 20℃; for 0.5h; General procedure: 1,4-DHPs (1 mmol, dissolved in 10 mL acetonitrile), TEMPO(0.05 mmol), FeCl3·6H2O (0.05 mmol), NaNO2 (0.05 mmol) and CH3COOH (1 mL) were added successively to a 25 mL three-neckedround-bottom flask equipped with a magnetic stirrer and a thermometer. The resulting mixture was stirred at room temperature and ambient pressure with an oxygen balloon until the reaction was completed as monitored by TLC (5:1 ethyl acetate/petroleum ether as eluent). Saturated aqueous NaHCO3 solution was added to make it neutral. The mixture was extracted with ethyl acetate three times. The combined organic extracts were washed with saturated aqueous NaCl solution, dried over MgSO4 and filtered. After removal of the solvent under reduced pressure, the residue was purified by columnchromatography (10:1 ethyl acetate/petroleum ether as eluent). Diethyl 2,6-dimethyl-3,5-pyridinedicarboxylate (2b): Pale yellow solid, m.p. 69-70 C (lit.[19] 69-70 C). 1H NMR (500 MHz, CDCl3):delta 8.68 (s, 1H), 4.41 (q, J = 7 Hz, 4H), 2.86 (s, 6H), 1.42 (t, J = 7 Hz,6H).
96% With N-acetylcysteine methyl ester-derived polysulfide; In ethanol; at 37℃; for 20.0h;Darkness; Inert atmosphere; General procedure: To the solution of HEH or BNAH (0.1 mmol) in ethanol or acetonitrile (2 mL) wasadded polysulfide 1 (0.2 mmol). The solution was incubated at r.t. or 37 C for 20 h(for HEH) or 5 h (for BNAH) under dark. After removing the solvent under reducedpressure, the yield of product 2 or 3 were determined by 1H-NMR.
95% With sulfur; zinc(II) oxide; In acetonitrile; at 50℃; for 24.0h;Inert atmosphere; Irradiation; A mixture of 31 diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (62.4mg, 0.25mmol), PHIK-BM (20mg), elemental 32 sulfur (48mg, 1.5mmol), and 28 ZnO (81mg, 1mmol) in 27 MeCN (6mL) was stirred at +50C under N2 and blue LED (40W, 465nm) irradiation for 24h. The catalyst was separated by centrifugation (12,000min-1, 1min) and washed with MeCN (3×2mL). Acetonitrile washings were combined and concentrated under vacuum, affording a white 33 solid. Yield: 59mg, 95%. 1H NMR (400MHz, CDCl3): delta=8.68 (s, 1H; CH), 4.40ppm (q, J(H,H)=5.4Hz, 4H; CH2), 2.85ppm (s, 6H; CH3), 1.42ppm (t, J(H,H)=5.4Hz, 6H; CH3).
95% With sulfur; zinc(II) oxide; In acetonitrile; at 50℃; for 24.0h;Inert atmosphere; Irradiation; A mixture of diethyl 2,6-dimethyl-1 ,4-dihydropyridine-3,5-dicarboxylate (62.4 mg, 0.25 mmol), potassium poly(heptazine imide) obtained according to example 2 (20 mg), elemental sulfur (48 mg, 1 .5 mmol), ZnO (81 mg, 1 mmol) in MeON (6 mL) was stirred at +50O under N2 and blue LED (40W, 465nm) irradiation for 24h. Oatalyst wasseparated by centrifugation (12000 min1, 1 mm) and washed with MeON (3x2 mL). Acetonitrile washings were combined and concentrated in vacuum affording white solid. Yield: 59 mg, 95%. 1H NMR (400 MHz, 0D013, 6): 8.68 (s, 1H, OH), 4.40 (q, J = 5.4Hz, 4H, OH2), 2.85 (s, 6H, OH3), 1.42 (t, J = 5.4Hz, 6H, OH3).

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  • 5
  • [ 50-00-0 ]
  • [ 141-97-9 ]
  • [ 1149-23-1 ]
YieldReaction ConditionsOperation in experiment
98% With ammonium acetate In lithium hydroxide monohydrate at 86℃; for 3h; Schlenk technique; Inert atmosphere;
97% With ammonium acetate at 20℃; for 0.25h; Neat (no solvent);
97% With ammonium acetate; alginic acid In ethanol Reflux; Green chemistry;
97% With ammonium acetate In neat (no solvent) at 20℃; for 0.25h; General procedure: In a general experimental procedure for the synthesis ofDHPs, a mixture of ethyl acetoacetate (10 mmol), aldehydes (5mmol), ammonium acetate (5 mmol), and silica sulfuric acid(0.1 g, 0.26 mmol of H+) [27] were mixed in a round-bottomflask and stirred at room temperature (for a stipulated time asindicated in Table 1) under solvent-free condition. After completionof the reaction (detected by TLC), ethyl acetate (5 ml)was added to the reaction mixture and the catalyst was filtered,washed with warm ethanol for reuse. The filtrate was thenwashed with water (5 ml) followed by brine solution (10 ml)and dried over MgSO4. The solution was concentrated invacuum to afford the crude product. Then, the crude productwas further purified by silica gel column chromatography.Yields of all the products prepared by this procedure are presentedin Table 1
96% With anhydrous ammonium acetate In ethanol for 0.0125h; microwave irradiation;
95% With ammonium acetate; sodium lauryl sulfate; toluene-4-sulfonic acid for 1h; ultrasonic irradiation;
95% With bismuth(III) chloride; ammonium acetate at 60℃; for 0.216667h; Neat (no solvent);
95% With ammonium acetate; β‐cyclodextrin at 80℃; for 0.166667h; Neat (no solvent);
95% With ammonium acetate In lithium hydroxide monohydrate at 25℃; for 2h;
95% With bismuth tungstate; ammonium acetate In lithium hydroxide monohydrate at 20℃; for 0.75h;
94% With gallium(III) trichloride; ammonium acetate at 60℃; for 0.2h; Neat (no solvent);
94.07% With ammonium acetate; toluene-4-sulfonic acid In methanol; lithium hydroxide monohydrate at 20℃; for 4h;
94% With ammonium acetate; toluene-4-sulfonic acid In ethanol at 20℃; for 4h; Synthetic procedure for synthesis of Hantzsch esters General procedure: All the three derivatives were synthesized via well known multicomponent Hantzsch reaction. Alkyl acetoacetate, formaldehyde and ammonium acetate were mixed in ethanol in eqimolar ratio and stirred at room temperature in 50 mL ethanol for 4 h. White precipitate formed was filtered off and recrystallized in ethanol to get the pure product.
92% With anhydrous ammonium acetate; tetrabutylammonium bromide In lithium hydroxide monohydrate for 0.05h; microwave irradiation;
92% With ammonium acetate In polyethylene glycol-400 at 90℃; for 4h;
92% With ammonium hydroxide In ethanol; lithium hydroxide monohydrate for 0.166667h; Irradiation; Method General procedure: Different aliphatic or aromatic aldehydes (1a-o) (10 mmol), ethyl acetoacetate (20 mmol), and ammonium hydroxide solution (25%) were taken in aqueous-ethanol mixture (20 mL, 1:1 proportion) and irradiated with a 150 W tungsten lamp (Philips India Ltd). The reaction time varied from 5-15 min (monitored by TLC after 5 min. interval). Upon completion of the reaction, the reaction mixture was cooled and the crystalline product (4a-o) so obtained was filtered, washed with water and dried in vacuo. The Hantzsch dihydropyridines were isolated in high yields in essentially pure form.
91% With ammonium acetate at 60℃; for 1h;
90% With ruthenium (III) chloride; ammonium acetate at 60℃; for 0.1h;
90% With ammonium acetate In lithium hydroxide monohydrate for 2h; Reflux;
90.7% With ammonium acetate; 1-n-butyl-3-methylimidazolium acetate In N,N-dimethyl-formamide for 2h; Reflux;
90% With tetraethylammonium 2-(carbamoyl)benzoate; ammonium acetate In ethanol at 80℃; for 1.25h; Green chemistry; General procedure for the synthesis of DHP and PHQ derivatives General procedure: A mixture of aldehyde (1 mmol), ethyl acetoacetate (2 mmol for DHP or 1 mmol for PHQ), dimedone/1.3-cyclohexanedione (1 mmol for PHQ), and ammonium acetate (1.2 mmol) and TEACB (10 mol%) in 2 cm3 absolute ethanol was heated at 80 C for the time indicated in Tables 2 and 3 into a 10 cm3 round-bottomed flask equipped with a magnetic stirrer until products were formed completely. The reaction progress was monitored by TLC. After completion of the reaction, the solvent was evaporated under vacuum to furnish a solid which was recrystallized from ethyl acetate-hexane.
89% With ammonium bicarbonate In neat (no solvent) at 90℃; for 0.25h; Green chemistry; General procedure for the synthesis of 1,4-dihydropyridines General procedure: A mixture of β-ketoester (4 mmol), aldehyde (2 mmol), ammonium carbonate (1.2 mmol) and sulfated polyborate (5 wt%) was heated at 90 °C. The reaction was monitored by thin layer chromatography. After completion of the reaction, reaction mixture was cooled to room temperature and quenched by water; solid precipitated was filtered at vacuum pump, washed with water (3 x 5 mL), dried under vacuum and recrystallized from ethanol to afford the pure product.
87% With ammonium acetate In lithium hydroxide monohydrate for 2h; Inert atmosphere; Reflux;
86.3% With ammonium hydrogen carbonate In methanol; lithium hydroxide monohydrate for 0.5h; Heating;
85% With ammonium acetate; toluene-4-sulfonic acid In methanol; lithium hydroxide monohydrate for 12h;
84% With anhydrous ammonium acetate In lithium hydroxide monohydrate for 2h; Heating;
84% With 1-methylimidazolium trifluoroacetate; ammonium acetate In ethanol for 0.0166667h; Microwave irradiation;
84% With 1-methyl-3-(3-sulfopropyl)imidazolium phosphotungstate; ammonium acetate; 1-n-butyl-3-methylimidazolium bistrifluoromethylsulfonylamide at 90℃; for 4h; Schlenk technique; Sealed tube; 3 1,4-Dihydro-4-(3-hydroxyphenyl)-2,6-dimethyl-,3,5-diethyl ester-3,5-pyridinedicarboxylic acid-DHP(b) General procedure: A sealed Schlenk tube containing 0.5 mL of BMI·NTf2, 1.00 mmol of the aldehyde, 2.00 mmol of the 1,3-dicarbonyl compound, 1.00 of NH4OAc, and MSI3PW (5 mol %) was allowed to react at 90 °C for 4 h. Substrates were purified by chromatographic column eluted with mixtures of hexane/ethyl acetate or, whether the product precipitates in the reaction medium, it is filtered and washed with cold ethanol. 3.3.3. 1,4-Dihydro-2,6-dimethyl-,3,5-diethyl ester,3,5-pyridinedicarboxylic acid-DHP(c). 1H NMR (300 MHz DMSO-d6 and δ in ppm) 1.16 (6H, t, J 7.0 Hz, OCH2Me), 2.08 (6H, s, Me), 3.33 (1H, s, CHaHb), 3.05 (1H, s, CHaHb), 4.03 (4H, q, J 7.0 Hz, OCH2Me) and 8.25 (1H, s, NH). 13C NMR (75 MHz, DMSO-d6) 167.5, 146.9, 97.4, 59.3, 18.4, 14.8, and 7.2.
83% Stage #1: formalin; ethyl acetoacetate With 1-butyl-3-methylimidazolium dimethylphosphate; ammonium acetate at 80℃; for 3h; Stage #2:
83% With ammonium acetate In ethanol at 60℃; for 8h;
80% With ammonia In methanol; lithium hydroxide monohydrate at 50℃; for 0.25h; Reflux; Microwave irradiation; 3.2. Chemistry The following general procedure was used to perform reactions in the batch mode: a mixture ofaqueous formaldehyde (37% in water and 10%-15% of methanol; 0.7 mL; 9.35 mmol), a β-ketoester(19.53 mmol), and a methanolic solution of ammonia (15.5% in methanol; 3.0 mL; 21.02 mmol) inmethanol (4.0 mL) was heated at 50 °C for the appropriate period of time (see text). After cooling theprecipitate was filtered, rinsed with well-chilled ethanol (0-5 °C; 5-10 mL) and recrystallized fromethanol. Acetonitrile was used as the sovent (instead of methanol) in one experiment (see Section 2.5.2).Yields: 75%-90%.
79% With ammonium acetate In ethanol at 80℃; for 0.25h; Inert atmosphere;
79% With ammonium acetate at 80℃; for 0.25h;
78% With ammonium acetate; toluene-4-sulfonic acid In ethanol at 80℃; for 3h;
72% With anhydrous ammonium acetate at 70℃; for 0.2h;
71% With ammonium acetate In lithium hydroxide monohydrate for 3h; Reflux;
68% With ammonium acetate In lithium hydroxide monohydrate at 20℃; for 0.166667h; Sonication; 3.2.5. General procedure for co-catalyzed synthesis of 1,4-DHP derivatives(5ar, 6ae) by Fe3O4/SiO2-PDA NPs and USW General procedure: Of each component, aldehyde 1 (1.0 mmol), ammonium acetate 2(1.0 mmol), and β-keto ester 3 or dimedone 4 (2.0 mmol), in deionizedwater (2.0 mL) and in the presence of the fabricated Fe3O4/SiO2-PDANPs (50 mg) were ultrasonicated (50 KHz) for 10 min, at room temperature.After completion of the reaction, the NPs were magneticallyseparated, and the residual product was collected by filtration andwashed with ethanol and recrystallized to yield the pure product.
64% With ammonium acetate at 70℃; for 0.166667h;
63% Stage #1: formalin; ethyl acetoacetate With diethylamine In lithium hydroxide monohydrate at 0 - 20℃; for 46h; Stage #2: With ammonia In ethanol at 0 - 20℃; for 40h;
57% With ammonium acetate In lithium hydroxide monohydrate at 110℃; for 2h; Schlenk technique; Inert atmosphere;
43% With ammonium hydroxide In methanol for 1h; Heating;
38% Stage #1: formalin; ethyl acetoacetate With ammonium acetate at 70℃; for 0.166667h; Stage #2: With lithium hydroxide monohydrate for 0.166667h; Cooling;
17% With ammonium acetate; triethylamine at 80℃; Neat (no solvent);
With hydrogenchloride; ammonia
With ammonia; lithium hydroxide monohydrate
With diethylamine Behandlung des Reaktionsprodukts mit Ammoniak in Alkohol;
With ammonia In methanol
With anhydrous ammonium acetate at 80℃; for 0.75h;
With ammonium acetate In lithium hydroxide monohydrate for 0.666667h; Heating;
With ammonia In ethanol; lithium hydroxide monohydrate for 3h; Reflux;
With ammonium acetate Neat (no solvent);
With ammonium acetate Reflux;
With ammonium acetate In lithium hydroxide monohydrate for 2h; Reflux;
38 g With ammonium acetate In ethanol Reflux; Preparation of Hantzsch 1,4-dihydropyridine ester. Formaldehyde solution (57.51g), ethyl acetoacetate (52g)and ammonium acetate (15.4g) was dissolved in ethanol (75 mL). The mixture wasstirred and refluxed then before the reactants disappeared monitored by TLC.The mixture was cooled in the refrigerator at -24°C and yellow precipitation was obtained. The mixture was then filtered before being heated again. The residue was washed with ethanol for 2-3 times. The crude product was recrystallized with ethanol to yield 38g of Hantzsch 1,4-dihydropyridineester.
With ammonia In methanol Reflux; 5.1.1 General method for the synthesis of dialkyl 2,6-dimethyl-4-substituted-1,4-dihydro-pyridine-3,5-dicarboxylates (6a-6n) General procedure: A solution of aldehyde (0.01mol), methylacetoacetate (0.03mol, 3.2ml) or ethylacetoacetate (0.03mol, 3.8ml) in methanol (20ml) was treated with ammonia solution (0.02mol) and refluxed for 8-16h. After the completion of the reaction, the mixture was cooled and evaporated to separatecompounds 6a-6n. The crude compound was purified by double recrystallization with methanol. The yield obtained was 52-60%.
With ammonium acetate In ethanol at 80℃; for 2h;
With ammonium acetate; toluene-4-sulfonic acid In methanol; lithium hydroxide monohydrate at 20℃; for 4h;
With potassium peroxodisulfate; benzyltrimethylammonium fluoride; ammonium acetate In ethanol at 70℃; Green chemistry;
With ammonium hydroxide In ethanol at 78℃; 2.1 Synthesis of DHP with corresponding aldehyde General procedure: A reaction flask was charged with ethyl acetoacetate (2.6 g, 20 mmol), the aldehyde (10 mmol), ethanol (20 mL). To the above solution, ammonium hydroxide (4 mL, 10 eq.) was added slowly. After addition, the system was heated at 78 °C with stirring. The reaction was monitored by TLC. When the reaction was completed, the crude reaction mixture was allowed to reach room temperature, the solvent was eliminated and a solution of 2 N HCl aqueous solution and dichloromethane were added and the layers were separated. The aqueous phase was extracted three times with dichloromethane. The combined organic layers were washed with two portions of a saturated solution of NaHCO3, brine and then dried over MgSO4 and filtered. Solvent was removed under reduced pressure. If necessary, products were purified by chromatography on silica gel.
With ammonium hydroxide for 2h; Reflux;
With ammonium acetate In lithium hydroxide monohydrate for 2h; Reflux; Ethyl Hantzsch ester (HEH) was synthesized according to literature.1 Briefly,paraformaldehyde (100 mmol), ethyl acetoacetate (400 mmol), and ammoniumacetate (200 mmol) were mixed in 200 mL of water. The reaction was stirred atrefluxing temperature for 2 h. After the reaction was completed, the reaction mixturewas cooled to room temperature. The product was filtrated and washed with 10 mL ofwater twice. The obtained yellow solid product was dried and used without furtherpurification (yield: 90%).
With ammonium acetate at 70℃;
With bismuth tungstate; ammonium acetate In lithium hydroxide monohydrate at 20℃; for 1h;
With ammonium acetate In lithium hydroxide monohydrate for 2h; Reflux;
With NH4HCO3 In ethanol for 20h; Inert atmosphere; Reflux; 1.2 (2) 100 ml with magnetic stirringThree bottles were added NH4HCO3 (7.9g, 0.1mol), 40% aqueous formaldehyde (containing formaldehyde 0.1mol) andEthyl acetoacetate (26 g, 0.2 mol) and 60 ml of a 50%Ethanol solution, under nitrogen, heated to reflux 20h,Until a pale yellow precipitate, the reaction system was cooled to room temperature,The solid was filtered off with suction and washed twice with cold ethanol,Drying afforded compound 7 (where R is hydrogen) as a light yellow solid (20.32 g)Weigh 2.53g (0.01mol) Compound 7 added to 100ml single-port glass bottles,Followed by sequential addition of 30ml of methanol, 4mol / L NaOH aqueous solution 10ml,Heated to reflux about 5h. The reaction solution was poured into 200ml of cold water, filtered under reduced pressure,The filtrate was adjusted to pH = 2.5 with 1 mol / L hydrochloric acid to precipitate a solid,Filter and dry under reduced pressure to give light yellow solid Compound 8 (wherein R is hydrogen) (1.52 g).
With ammonium hydrogen carbonate In ethanol at 80℃; Inert atmosphere;
24 g With ammonium acetate In lithium hydroxide monohydrate for 2h; Schlenk technique; Inert atmosphere; Reflux;
With ammonium acetate
With ammonium acetate In lithium hydroxide monohydrate at 80℃; for 4h;
With ammonium acetate In lithium hydroxide monohydrate for 1h; Reflux;
With ammonium hydroxide In ethanol at 80℃; for 3h; 4.1.1. General procedure A: General procedure: To the solution of various aldehydes (10 mmol), ethyl acetoacetate(22 mmol) and ammonia solution (2 mmol) in the solvent of ethanol (30mL). And the mixture was heated to refluxed for 3 h. After the reaction was completed by TLC detection, it was cooled to room temperature.The mixture was poured into 100 mL of cold water and extracted with ethyl acetate. The organic layers were combined and washed in brine,dried on Na2SO4, and then concentrated under vacuum. The residue was purified by column chromatography using EtOAc/PE (1:2) gradient togive the product.

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  • 6
  • [ 14558-49-7 ]
  • [ 626-34-6 ]
  • [ 1149-23-1 ]
  • 7
  • [ 14558-49-7 ]
  • [ 626-34-6 ]
  • [ 1149-23-1 ]
  • 8
  • [ 1149-23-1 ]
  • [ 74-88-4 ]
  • [ 14258-07-2 ]
YieldReaction ConditionsOperation in experiment
86% Stage #1: diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate With sodium hydride In tetrahydrofuran for 0.5h; Heating; Stage #2: methyl iodide In tetrahydrofuran for 2h; Heating;
86% Stage #1: diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate With sodium hydride In tetrahydrofuran at 0℃; for 0.166667h; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran at 20℃; for 0.25h; Inert atmosphere;
20% Stage #1: diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate With sodium hydride In tetrahydrofuran for 0.5h; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran for 2h; Inert atmosphere; Reflux;
  • 9
  • [ 50-00-0 ]
  • [ 631-61-8 ]
  • [ 141-97-9 ]
  • [ 1149-23-1 ]
YieldReaction ConditionsOperation in experiment
92% Stage #1: formaldehyd; ammonium acetate; ethyl acetoacetate With cellulose sulfuric acid In neat (no solvent) at 80 - 100℃; Stage #2: With cellulose sulfuric acid In neat (no solvent) General procedure for the synthesis of 1,4 dihydropyridines General procedure: aldehyde (0.01 moles), ethyl acetoacetate (0.025 moles) and ammonium acetate (0.02 moles) were refluxed at 100 C under solvent free conditions for 2-5 h employing 0.05 g of cellulose sulfuric acid, the reaction was monitored by TLC. The reaction mixture was poured in to a ice cold water and extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Purified through column chromatography and recrystalized in ethanol
90% With Silica-sulphonic acid-[BMIM][PF6] In neat (no solvent) at 60℃; for 0.166667h; Green chemistry;
  • 10
  • [ 3042-22-6 ]
  • [ 14548-45-9 ]
  • [ 1149-23-1 ]
  • [ 1604834-22-1 ]
  • 11
  • [ 3042-22-6 ]
  • [ 1570-48-5 ]
  • [ 1149-23-1 ]
  • [ 1604834-32-3 ]
  • C18H20N2O [ No CAS ]
  • 12
  • [ 54675-23-9 ]
  • [ 1149-23-1 ]
  • [ 3446-89-7 ]
  • 6-bromo-3-(4-(methylthio)benzyl)quinoline-2,4-diol [ No CAS ]
YieldReaction ConditionsOperation in experiment
With pyridine; at 20 - 80℃; A mixture of 4-(methylthio)benzaldehyde (3.00 g, 19.7 mmol), <strong>[54675-23-9]6-bromo-4-hydroxyquinolin-2(1H)-one</strong> (4.72 g, 19.7 mmol, Intermediate 45: step a), diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (5.23 g, 20.7 mmol), and pyridine (100 mL) was stirred at 80 C. for 4 hours and then at room temperature overnight. The reaction was cooled and the formed precipitate was filtered, washed with Et2O (100 mL), and dried to afford the title compound as a white solid.
  • 13
  • [ 100-42-5 ]
  • [ 1149-23-1 ]
  • diethyl rac-(1R,6S,8S)-1,3-dimethyl-8-phenyl-2-azabicyclo[4.2.0]oct-3-ene-4,6-dicarboxylate [ No CAS ]
  • diethyl rac-(1R,6S,8R)-1,3-dimethyl-8-phenyl-2-azabicyclo[4.2.0]oct-3-ene-4,6-dicarboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 58% 2: 19% With tris[2-phenylpyridinato-C2,N]iridium(III) In acetonitrile at 20℃; for 24h; Inert atmosphere; Irradiation; 1 Example 1: Visible-light promoted [2+2] cycloaddition reaction of 1,4-dihydropyridine and olefins At room temperature, nitrogen was protected and a photosensitizer Ir(ppy)3 (tris(2-phenylpyridine) fluorene) was added to a dry reaction tube. [Preparation method reference Liang, A.; Huang, G.; Chen, S .; Hou, H.RSC Adv., 2015, 5, 49466](0.01 mmoL) 1,4-dihydropyridine (1 mmol) represented by Formula I, olefin (1.0 mmol) represented by Formula II,Acetonitrile (20 mL), freeze-evacuated-recycled to room temperature three times, filled with nitrogen,Then, after column chromatography at room temperature for 24 hours under irradiation of an 8w blue LED lamp, column chromatography (eluting solvent is petroleum ether or a mixture of petroleum ether and ethyl acetate) gives the product.
50 % de With tris[2-phenylpyridinato-C2,N]iridium(III) In acetonitrile at 20℃; for 48h; Schlenk technique; Inert atmosphere; Irradiation; Overall yield = 77 %; Overall yield = 0.5506 g; diastereoselective reaction;
  • 14
  • [ 67-56-1 ]
  • [ 1149-23-1 ]
  • [ 603-35-0 ]
  • [ 279673-53-9 ]
  • [ 14243-64-2 ]
  • C13H17NO4*ClH [ No CAS ]
  • C15H13NO2*ClH [ No CAS ]
  • 15
  • C12H8BF4NO3 [ No CAS ]
  • [ 1149-23-1 ]
  • C25H26BF3N2O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
31% With triethylamine In dimethyl sulfoxide at 80℃; for 10h; 2.2. Synthesis. General procedure: Fluoroquinolone-boron complex 2 was synthesized according to Leyva et al. method [24].332.85 μmol of the fluoroquinolone 2 and 0.5 mmol ofthe heterocycle (3,5-diethoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine, uracil, 5,5-diphenylhydantoine, benzimidazole or1,2,3,4-tetrahydrocarbazole) were added in 1.5mLof DMSO (for 3a-d, f ) or CH3CN (for 3e) and 69.4 μL ofTEA solution. .eir action mixture was stirred and heated at 80°C and monitored with thin layer chromatography untilreaction was completed. .en, 1mL of ethanol was added toobtain a solid, which was filtered, washed with cold ethanol,and recrystallized with CH3CN. Difluoroboryl 1-ethyl-7-(3,5-diethoxycarbonyl-2,6-dimethyl-1,4-dihydropyridin-1-yl)-6-fluoro-4-oxo-1,4-dihydroquinoline-3-carboxylate (3a). Reaction time (10 h), yellow pale solid with anmp of 300-301°C and 31% yield. FTIR-ATR (cm-1): 3066 (C-H,aromatic), 1716 (CO, ketone, ester), 1617 y 1485 (CC, Ar),1561 (CC, vinyl), 1448 (CH3, bend), 1360 (C-N, Ar), 1288,1230 (C-O, ester), 1093, 1041 (C-F, Ar). RMN de 1H NMR δ(DMSO-d6, ppm): 9.09 (s, 1H), 8.52 (s, 1H), 8.26 (d, JH-F ortho 10.47 Hz, 1H), 7.41 (s, 6H), 4.34 (q, J 7.30 Hz, 4H), 4.10 (q,J 7.30 Hz, 2H), 3.10 (s, 2H), 1.91 (t, J 7.30 Hz, 6H), 1.34 (t,J 7.30 Hz, 3H).
  • 16
  • [ 1149-23-1 ]
  • [ 17199-29-0 ]
  • C8H8O3*C13H19NO4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% In dichloromethane at 20℃; for 2h; The structure and preparation method of Chiral Catalyst III are as follows: (S)-α-Hydroxyphenylacetic acid (152.1mg, 1mmol) and 2,6-dimethyl-3,5-dioic acid methyl ester-1,4-dihydropyridine (253.3mg, 1mmol) were dissolved in two In methyl chloride, react for 2h at room temperature, remove the solvent under reduced pressure, and quantitatively obtain a white 1,4-dihydropyridine chiral hybrid hydrogenation reagent, that is, chiral catalyst III.
In dichloromethane at 20℃; for 2h; 2 (S)-α-Hydroxyphenylacetic acid (152.1mg, 1mmol) and 2,6-dimethyl-3,5-dioic acid methyl ester-1,4-dihydropyridine (253.3mg, 1mmol) were dissolved in two In methyl chloride, react for 2h at room temperature, remove the solvent under reduced pressure, and quantitatively obtain a white 1,4-dihydropyridine chiral hybrid hydrogenation reagent, that is, chiral catalyst III.
  • 17
  • [ 1149-23-1 ]
  • [ 121138-01-0 ]
  • diethyl 2,6-dimethyl-4-(tetrahydrofuran-3-yl)-1,4-dihydropyridine-3,5-dicarboxylate [ No CAS ]
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