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CAS No. : | 82-86-0 | MDL No. : | MFCD00003805 |
Formula : | C12H6O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | AFPRJLBZLPBTPZ-UHFFFAOYSA-N |
M.W : | 182.18 | Pubchem ID : | 6724 |
Synonyms : |
|
Num. heavy atoms : | 14 |
Num. arom. heavy atoms : | 10 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 52.61 |
TPSA : | 34.14 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) : | -6.03 cm/s |
Log Po/w (iLOGP) : | 1.48 |
Log Po/w (XLOGP3) : | 1.95 |
Log Po/w (WLOGP) : | 2.22 |
Log Po/w (MLOGP) : | 1.37 |
Log Po/w (SILICOS-IT) : | 3.26 |
Consensus Log Po/w : | 2.05 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.73 |
Solubility : | 0.342 mg/ml ; 0.00188 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.29 |
Solubility : | 0.931 mg/ml ; 0.00511 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -4.4 |
Solubility : | 0.00724 mg/ml ; 0.0000397 mol/l |
Class : | Moderately soluble |
PAINS : | 1.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.5 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P264-P271-P280-P302+P352-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | 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 |
---|---|---|
75% | With oxygen In acetonitrile at 20℃; for 24 h; | The electron transfer reaction from the cyanide anion to1,2-dicarbonyl compounds and their monoimine derivatives1a–f was performed under stirring conditions in dryacetonitrile (40 mL) solutions where the substrate(0,25 mmol) was maintained for 24 h (48 h for 1a and1e) at room temperature and usual laboratory illumina-tion conditions, in the presence of sodium cyanide(10 mmol) over an open-air vessel. The reaction wasfollowed by TLC until complete disappearance of thestarting compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With sulfonated rice husk ash at 20℃; for 0.166667h; Green chemistry; | General procedure for the synthesis of quinoxaline derivatives General procedure: To a mixture of 1,2-diaminobenzene (1 mmol) and 1,2-dicarbonyl compound (1 mmol), RHA-SO3H (15 mg) was added and the mixture was stirred at room temperature for the appropriate time. The progress of the reaction was monitored by TLC (EtOAc: n-hexane 2:8). After completion of the reaction, ethyl acetate (20 mL) was added to the mixture and the solid catalyst was separated. Then the solvent was evaporated and the resulting solid product was recrystallized from ethanol, producing the pure product in high yields. |
97% | With 1-(propyl-3-sulfonate) 3-methylimidazol(3H)-1-ium phosphotungstate In water at 20℃; for 0.183333h; | |
96% | In 1,4-dioxane for 0.5h; Heating; |
96% | With 1-butyl-3-methylimidazolium Tetrafluoroborate at 20℃; for 0.166667h; Green chemistry; | 2.4. General procedure for the synthesis of quinoxalines General procedure: A mixture of aromatic diamine derivatives (2 mmol) and a 1,2-dicarbonyl compound (2 mmol) in ionic liquid (2 mL) was stirred atroom temperature for the appropriate time. The progress of the reaction was monitored by TLC (n-Hexane: EtOAc, 7:3), after completion of the reaction, the reaction mixture was diluted with water and extracted using diethyl ether (30 ml). The combined organic layer was dried over anhydrous sodium sulphate and evaporated under reduced pressure to afford the corresponding product. The residual ionic liquid was dried under vacuum and reused. The same procedure was repeated for the reaction of aromatic anilines with isatin and acenaphthoquinone and phenaacylbromide. All the products obtained were characetrised by IR,1HNMR, 13CNMR and Mass studies. |
95% | With lithium chloride In ethanol at 20℃; for 0.7h; | |
95% | With 1,1,1,3',3',3'-hexafluoro-propanol at 20℃; for 1h; | |
95% | With chromium(II) chloride hexahydratete In ethanol at 20℃; | |
95% | With lead(II) chloride In ethanol at 20℃; for 0.333333h; | General procedure: A mixture of 1,2- dicarbonyl compound or aryl glyoxal (1 mmol),o-phenylenediamine (1.1 mmol) and lead dichloride( 20 mol%) in ethanol(5 mL) was stirred at room temperature. The progress of the reaction wasmonitored by TLC (hexane/AcOEt, 3:7). After the completion of the reaction,the solid which separated was filtered and then recrystallized from ethanol toafford pure product. |
95% | With PVPP*OTf In water at 20℃; for 1h; | 2.2 Typical experimental procedure General procedure: A mixture of 1,2-dicarbonyl compounds (1 mmol), aryl 1,2-diamines (1 mmol) dissolved in 4 mL water, and PVPP·OTf (30 mg) was stirred for 1 h. The reaction was monitored by TLC. After completion of the reaction, the mixture was washed with chloroform and filtered to recover the catalyst. The filtrate was evaporated and purified by recrystallization from hot ethanol to afford pure products. Products were characterized by comparison of their physical and spectral data with those of authentic samples. Spectroscopic data for selected examples as follows: |
95% | With polyvinylimidazole-based Bronsted acidic ionic liquid grafted silica In ethanol at 20℃; for 0.25h; | 3.3. General procedure for preparation of quinoxaline derivatives General procedure: To a mixture of 1,2-diketone (1 mmol) and 1,2-diamine (1 mmol) in 4 mL of ethanol was added catalyst III (0.006 g, 0.5 mol%) or catalyst IV (0.017 g, 1 mol%). The reaction mixture was stirred at room temperature for the appropriate time. The progress of the reaction was followed by TLC. Upon completion, the product and the catalyst were separated easily from each other by simple ltration. The ltrate was concentrated under reduced pressure and the crude product was puried by silica gel column chromatography with petroleum ether (bp 60 °C) and ethyl acetate (in some cases recrystallization was used). The obtained quinoxalines were identied by their 1H NMR and 13C NMR spectra and comparison of their melting points with those of the authentic samples. |
95% | With 3,5-bis(trifluoromethyl)phenylammonium hexafluorophosphate In water at 20℃; for 2h; Combinatorial reaction / High throughput screening (HTS); | 2.2. General Procedure for the Preparation ofQuinoxaline Derivatives General procedure: A mixture of 1,2-dicarbonyl compounds (1 mmol), aryl1,2-diamines (1 mmol), and BFPHP (10 mol%) in water (3mL) was stirred at room temperature for an appropriate time.Upon completion of the reaction, (monitored by TLC), theresultant was cooled with ice bath, filtered and washed withethanol and purified by recrystallization from hot ethanol toafford pure products. |
93% | With niobium pentachloride In ethanol at 20℃; for 0.0333333h; | |
93% | With magnesium sulfate heptahydrate In ethanol at 20℃; for 0.333333h; | |
91% | With titanium(IV) oxide In 1,2-dichloro-ethane at 25℃; for 0.5h; | |
90% | With (2,3,4,5,6-pentafluorophenyl)ammonium triflate In water at 20℃; for 1h; Green chemistry; | Typical experimental procedure A mixture of 1,2-dicarbonyl compounds (1 mmol), aryl1,2-diamines (1 mmol) dissolved in 4 mL water, and PFPAT(10 mol%) was stirred for the appropriate reaction time. Thereaction was monitored by TLC. After completion of thereaction (monitored by TLC), the resultant was cooled withice-salt bath, filtered and washed with ethanol and purifiedby recrystallization from hot ethanol to afford pure products3a-p, and the filtrate containing PFPAT could be directlyused by adding the reactants. After three recycles, thecatalytic activity of PFPAT remained unchanged. Theproducts were characterized by comparison of their physicaland spectral data with those of authentic samples. |
90% | With propylsulfonic acid functionalized nanozeolite clinoptilolite In water at 25℃; for 0.25h; | 2.3 General procedure for the synthesis of quinoxalines General procedure: A mixture of aromatic o-diamine (1mmol), 1,2-dicarbonyl compounds or phenacyl bromides (1mmol) and NZ-PSA (0.01g) in 5mL of water was stirred at room temperature for an appropriate time (Scheme 2). The progress of the reaction was monitored by TLC. After completion of the reaction, the catalyst was filtered off. The solvent was evaporated under reduced pressure and the pure product was obtained without any further purification and their spectroscopic data are shown in supporting information. |
86% | at 130℃; for 0.5h; Ionic liquid; Microwave irradiation; | |
86% | With tungstate sulfuric acid at 20℃; for 0.333333h; Neat (no solvent); | |
80% | With cobalt(III) 5,10,15,20-tetraarylporphyrin In ethanol; water at 20℃; for 0.166667h; | |
With acetic acid | ||
With ethanol; acetic acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With zirconium oxide salicylaldehyde-(3-aminopropyl)trimethoxysilane imine complex modified SBA-15 In water for 0.5h; Reflux; | |
99% | With mesoporous silica SBA-15 functionalized with Cu(II)-DiAmSar complex In neat (no solvent) at 100℃; for 0.0833333h; | 2.3. General procedure for the synthesis of pyrazine-basedheterocycles under solvent-free conditions General procedure: A round-bottomed flask equipped with a magnet and condenserwas charged with the desired 1,2-diamine (1.0 mmol),1,2-diketone (1.0 mmol), and catalyst (Cu(II)DiAmSar/SBA-15,0.005 g). The resulting mixture was heated at 100 °C for theappropriate time. The course of the reaction was monitoredusing TLC on silica gel. Finally, the reaction mixture was cooled,and the crude mixture was purified by column chromatographyor crystallization to get the desired product. Spectral and physicaldata for all heterocycles were compared with referencesamples and were in accord with previously reported data. |
98% | With Cu(II)-Schiff base/SBA-15 In water for 0.5h; Reflux; | General procedure for the synthesis of pyrido[2,3-b]pyrazines, pyrido[3,4-b]pyrazines and 2,3-disubstituted quinoxalines in water General procedure: A round-bottomed flask equipped with a magnet and condenser was charged with desired 1,2-diamine (1.0 mmol), 1,2-diketone (1.0 mmol), water (2 mL) and catalyst Cu/SBA-15 (0.01 g (0.0014 mmol)). The resulting mixture was stirred at reflux temperature for the appropriate times, and the course of the reaction was monitored using TLC on silica gel. For separation of the catalyst, the reaction mixture (at the end of reaction) was filtered and the precipitates on the filter were dissolved in ethanol or ethyl acetate. These solvents can dissolve the products (and also organic starting materials), but the catalyst was remained insoluble. After filtration of the later solution, the catalyst was recovered |
97% | With SBA-15 mesoporous silica supported Fe(III)-Schiff base In water for 0.5h; Reflux; | |
97% | With polyvinylimidazole-based Bronsted acidic ionic liquid grafted silica In ethanol at 20℃; for 0.25h; | 3.3. General procedure for preparation of quinoxaline derivatives General procedure: To a mixture of 1,2-diketone (1 mmol) and 1,2-diamine (1 mmol) in 4 mL of ethanol was added catalyst III (0.006 g, 0.5 mol%) or catalyst IV (0.017 g, 1 mol%). The reaction mixture was stirred at room temperature for the appropriate time. The progress of the reaction was followed by TLC. Upon completion, the product and the catalyst were separated easily from each other by simple ltration. The ltrate was concentrated under reduced pressure and the crude product was puried by silica gel column chromatography with petroleum ether (bp 60 °C) and ethyl acetate (in some cases recrystallization was used). The obtained quinoxalines were identied by their 1H NMR and 13C NMR spectra and comparison of their melting points with those of the authentic samples. |
91% | With ziconium(IV) oxychloride octahydrate In water at 100℃; for 1h; Green chemistry; | 11 4.2. General procedure for the synthesis of compounds 3a-3p For the synthesis of entitled heterocycles, a roundbottom flask equipped with a stir bar was chargedwith 1,2-phenylenediamine (1.0 mmol), 1,2-diketones(1.0 mmol), water (2 mL) and zirconium(IV) oxide chloride(25 mol%). The resulting mixture was heated in an oil bathat 100 8C for the appropriate time, and the course of the reaction was monitored using TLC on silica gel. Finally, thereaction mixture was cooled and the crude mixture waspurified by column chromatography or crystallization togive the desired product. The authenticity of the productswas established by comparing their melting points withdata of the literature and by analyzing the spectroscopicdata of 1H and 13C NMR and IR [9-16,26,27]. |
75% | With cobalt(III) 5,10,15,20-tetraarylporphyrin In ethanol; water at 20℃; for 1h; | |
74% | With 5-sulfosalicylic acid anchored to silica-modified Fe3O4 nanocomposite In ethanol at 60℃; | General procedure for the synthesis of quinoxaline derivatives General procedure: To a mixture of a 1,2-diketone (1.0 mmol) and 1,2-diaminobenzene (1.0 mmol) in ethanol (2.0 mL), Fe3O4(at)SiO2(at)5-SA (20 mg) was added and the mixture was stirred at 60 °C. The progress of the reaction was monitored by TLC. After completion of the reaction, the magnetic catalyst was separated by an external magnet. The products were purified by recrystallization from ethanol or methanol. |
With acetic acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With 1-(propyl-3-sulfonate) 3-methylimidazol(3H)-1-ium phosphotungstate In water at 20℃; for 0.116667h; | |
98% | With sulfonated rice husk ash at 20℃; for 0.25h; Green chemistry; | General procedure for the synthesis of quinoxaline derivatives General procedure: To a mixture of 1,2-diaminobenzene (1 mmol) and 1,2-dicarbonyl compound (1 mmol), RHA-SO3H (15 mg) was added and the mixture was stirred at room temperature for the appropriate time. The progress of the reaction was monitored by TLC (EtOAc: n-hexane 2:8). After completion of the reaction, ethyl acetate (20 mL) was added to the mixture and the solid catalyst was separated. Then the solvent was evaporated and the resulting solid product was recrystallized from ethanol, producing the pure product in high yields. |
91% | With rice husk In water; acetonitrile at 50℃; for 0.5h; Green chemistry; | General procedure for the synthesis of quinoxaline derivatives General procedure: A mixture of 1,2-dicarbonyl compound (1 mmol), o-phenylenediamine (1 mmol) and RiH (0.35 mol %) in H2O/CH3CN (2 mL/2 mL) was stirred at 50 °C. The progress of the reaction was monitored by TLC. After completion of the reaction, and evaporation of the solvents, the reaction solid product was extracted with Et2O (3 × 15 mL). The catalyst was filtered and reused for further runs. Et2O was evaporated and the solid residue recrystallized with ethanol to afford the pure product. The physical and spectral data of the known compounds were in agreement with those reported in the literature [40,43,58,59]. |
85% | With magnesium sulfate heptahydrate In ethanol at 20℃; for 1.5h; | |
85% | With lead(II) chloride In ethanol at 20℃; for 5.66667h; | General procedure: A mixture of 1,2- dicarbonyl compound or aryl glyoxal (1 mmol),o-phenylenediamine (1.1 mmol) and lead dichloride( 20 mol%) in ethanol(5 mL) was stirred at room temperature. The progress of the reaction wasmonitored by TLC (hexane/AcOEt, 3:7). After the completion of the reaction,the solid which separated was filtered and then recrystallized from ethanol toafford pure product. |
84% | With lithium chloride In ethanol at 20℃; for 6.16667h; | |
82% | With chromium(II) chloride hexahydratete In ethanol at 20℃; | |
80% | In acetic acid for 1h; Heating; | |
80% | With acetic acid for 2h; Reflux; | 1 Example 1: Synthesis of fluorescent probe (synthesis taking AQA-H as an example) Acenaphthenquinone (0.36g, 2mmol) was dissolved in 20mL of glacial acetic acid and stirring was started, then 4-nitro-o-phenylenediamine (0.30g, 2mmol) was added, and the temperature was slowly raised to reflux. After 2 hours of reaction, the raw material spots disappeared, indicating that the reaction was complete. The reaction system was cooled to room temperature, the solid was precipitated and filtered under reduced pressure, and the obtained filter cake was recrystallized in DMF/H2O (yield 80%) for the next reaction. |
65% | With cobalt(III) 5,10,15,20-tetraarylporphyrin In ethanol; water for 1h; Reflux; | |
60% | With 5-sulfosalicylic acid anchored to silica-modified Fe3O4 nanocomposite In ethanol at 60℃; | General procedure for the synthesis of quinoxaline derivatives General procedure: To a mixture of a 1,2-diketone (1.0 mmol) and 1,2-diaminobenzene (1.0 mmol) in ethanol (2.0 mL), Fe3O4(at)SiO2(at)5-SA (20 mg) was added and the mixture was stirred at 60 °C. The progress of the reaction was monitored by TLC. After completion of the reaction, the magnetic catalyst was separated by an external magnet. The products were purified by recrystallization from ethanol or methanol. |
With acetic acid | ||
In acetic acid at 155℃; for 4h; | 2.2. Synthesis of compound 1 Acenaphthenequinone (182 mg, 1 mmol) and 4-nitro-o-phenylenediamine(199 mg, 1.3 mmol) were dissolved in acetic acid (90 ml) andheated to 155 C and refluxed for 4 h. After cooled to room temperature,a crude precipitate was precipitated and recovered by suction filtration.The precipitate was washed by water and dried to obtain 1. 1H NMR(400 MHz, CF3COOD) δ 9.24 (d, J = 2.3 Hz, 1H), 8.70 (d, J = 7.3 Hz,1H), 8.67 - 8.63 (m, 2H), 8.45 (d, J = 9.2 Hz, 1H), 8.41 (d, J = 8.2 Hz,1H), 8.33 (d, J = 8.3 Hz, 1H), 7.98 - 7.91 (m, 2H). 13C NMR (101 MHz,CF3COOD) δ 150.04, 146.72, 144.13, 134.81, 131.86, 131.69, 130.07,129.91, 125.67, 125.40, 124.13, 122.98, 121.58, 121.07, 120.38,118.60, 118.48. ESI-MS m/z: [M + H]+ calculated for 300.0768, found300.0764. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With acetic acid at 120℃; for 12h; | I-2 Synthesis Example 3,3-diaminobenzidine (15 g, 70 mmol) and acenaphthoquinone (25.5 g, 140 mmol) were placed in a three-necked reaction flask, 300 ml of acetic acid was added as a reaction solvent, and the reaction was refluxed at 120 ° C. for 12 hours. After the reaction, it was cooled to room temperature and filtered to obtain a dark brown solid. The solid was washed with distilled water and ethanol to remove acetic acid. The solid was dissolved in toluene and purified by column chromatography. Finally, the compound I-2 was obtained. The appearance was a bright yellow powder. The yield is 31.5 g and the yield is 89%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With acetic acid isoliert als Chlorid; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With potassium hydroxide In ethanol; toluene at 78℃; for 1.25h; | I.b Example l.b7,9-Diphenyl-6b,7-dihydrocyclopenta[a]acenaphthylen-8-oneA suspension of 16.2 g (77 mmol) of 1 ,3-diphenylpropan-2-one and 14.2 g of acenaphthoquinone in 8.2 ml of toluene and 82 ml of ethanol was heated under reflux (78°C). Subsequently, a solution of 1.35 g of KOH and 27 ml of ethanol was added dropwise within 15 minutes. The reaction mixture was stirred under reflux for a further 1 h. The reaction mixture was cooled to 0 to 5°C. The precipitated black product was filtered off with suction and washed with 3 x 100 ml of ethanol. This gave 26.2 g (yield: 96%) of the title compound. Rf (in 10:1 toluene:ethyl acetate): 0.8. |
95% | With potassium hydroxide In ethanol Reflux; | |
94% | With potassium hydroxide In ethanol; toluene for 0.0833333h; Heating; |
94.6% | With sodium hydroxide In ethanol at 20℃; for 0.25h; | |
93% | With potassium hydroxide In ethanol Reflux; | |
92.5% | With potassium hydroxide In ethanol; water at 50℃; for 3h; Inert atmosphere; | |
92% | With sodium hydroxide In ethanol; water at 60 - 80℃; for 2h; | 2.1 Example 2[0109] Synthesis of exemplified compound XX- 2[0110][Chem. 13]X9 X10 XX-2 [0111] (1) Synthesis of compound X8Reagents and a solvent described below were placed in a reactor.Compound X7 : 10 g (55 mmol)Compound X2 : 12 g (55 mmol)Ethanol: 200 ml[0112] Next, the reaction solution was heated to 60° C, and then 20 ml of a 6M aqueous sodium hydroxide solution was added dropwise to the solution. After the completion of addition, the reaction solution was heated to 80° C and stirred at this temperature (80° C) for 2 hours. Next, the reaction solution was cooled to produce precipitates which were then filtered off. Next, the resultant precipitates were washed in order with water and ethanol and then dried by heating at 80° C under reduced pressure to produce 18 g of compound X8 as a dark green solid (yield: 92%). |
91% | With potassium hydroxide In ethanol Heating / reflux; | 1 Synthesis of ,f']-4,4'7,7'-tetraphenyl}-diindeno[1,2,3-cd:1',2',3'-lm]perylene Synthesis of ,f']-4,4'7,7'-tetraphenyl}-diindeno[1,2,3-cd:1',2',3'-lm]perylene The scheme of the overall preparation of ,f']-4,4',7,7'-tetraphenyl}-diindeno[1,2,3-cd:1',2',3'-lm]perylene is exemplified in Scheme 1. This invention is directed toward the step where XV (7,12-diphenylbenzo[k]fluoranthene) is converted to XVI and XVII. Synthesis of A: A 3 L round bottom flask was charged with 1,3-diphenylacetone (200 g, 0.95 mol), acenaphthenequinone (173.3 g, 0.95 mol) and 1.4 L of ethanol and heated to near reflux. A solution of potassium hydroxide (29.3 g, 0.52 mol) in 285 ml of ethanol was added slowly to a mechanically stirred solution under nitrogen. After complete addition the reaction (black suspension) was stirred an additional thirty minutes at reflux and then cooled to 15° C. and filtered. The solids collected were washed with another 1 L of ethanol. The solids were resuspended in 1 L of methanol and filtered. Finally, the black solids collected were washed with 1 L of methanol until the filtrate was clear to yield 307.76 g of product (91% yield). Synthesis of XV: A 3 L round bottom flask with a mechanical stirrer and reflux condenser was charged with acecyclone (100 g, 0.281 mol) and 1.2 L of 1,2-dichloroethane. The reaction vessel was affixed with two addition funnels. The first contained a solution of anthranilic acid (40.40 g, 0.295 mol) in 500 ml of 1,2-dichloroethane. The second contained isoamyl nitrite (134.8 ml, 1.003 mol) in 365 ml of 1,2-dichloroethane. After bringing the reaction mixture to reflux the solutions in the two addition funnels were added dropwise and simultaneously in equal volumes to the reaction over a period of approximately 1.4 hours. The reflux condenser must be affixed in such a manner as to return solvent directly back into the reaction mixture and not into either addition funnel solution. It is critical that the addition step be performed with great caution as the reaction is highly exothermic and effervescent. If the addition is conducted to quickly a foaming eruption will occur. It is also critical the reaction temperature be at reflux prior to initiation otherwise a buildup of diazotized anthranilic acid may occur and upon thermal initiation overwhelm the reaction vessel and thermal sink. Shortly after complete addition the bubbling ceased and the reaction color changed from black to dark yellow, indicating consumption of acecyclone. The reaction was refluxed an additional hour, and the reaction mixture solvents were stripped by simple distillation until a thick yellow paste formed. These solids were triturated with 2 L of hot butanol, collected and then triturated from hot methanol and collected, washed with 1 L of methanol and dried to provide 105.42 grams of yellow solid for a 92% yield. Thin layer chromatography, 20% dichloromethane/heptane, Rf=0.8, clean blue spot. Invention, Synthesis of XVII, Version A: A 5 L round bottom flask was fixed with a mechanical stirrer and a nitrogen inlet. |
90% | In ethanol; water at 60 - 80℃; Alkaline aqueous solution; | 1 To 200 ml of ethanol, 9.1 g (50 mmol) E4 and 10.5 g (50 mmol) E5 were added, and the resulting mixture was heated to 60°C. To the resulting mixture, 20 ml of a 5 M aqueous sodium hydroxide solution was added dropwise. Upon completion of the dropwise addition, the mixture was heated to 80°C, stirred for 2 hours, and cooled. Precipitates were filtered, washed with water and ethanol, and vacuum-dried under heating at 80°C. As a result, 16 g (yield: 90%) of dark green solid E6 was obtained. |
90.05% | With potassium hydroxide In ethanol Reflux; | |
90% | With potassium hydroxide In ethanol for 0.0833333h; Reflux; Inert atmosphere; | |
90% | With potassium hydroxide In ethanol at 78℃; for 0.25h; | |
90% | With potassium hydroxide In ethanol for 2h; Reflux; | |
90% | With potassium hydroxide In ethanol for 2h; Reflux; | 2.4. Synthesis of 7,9-diphenyl-8H-cyclopenta[a]acenaphthylen-8-one(DCA) DCA was synthesized through reaction of acenaphthenequinone and1,3-diphenylpropan-2-one according to literature [29]. Acenaphthenequinone(5.47 g, 0.03 mol) and 1,3-diphenylpropan-2-one (6.3 g,0.03 mol) were dissolved in ethanol (60 mL) and placed in three-neck250 mL round-bottom flask equipped with refilux condenser and magneticstirrer. When the mixture solution was heat to refilux, KOH (0.8 g)which dissolved in ethanol (5 mL) solution was dropwise added via adrop funnel. The mixture immediately turned black. After dropwiseaddition of KOH ethanol solution completed, the mixture was kept inrefilux for 2 h and then cooled down to room temperature. After filtered,black precipitate was obtained. The crude product was washed withethanol several times to obtain pure product, which is purple-black solidpowder with yield of 90%. 1H NMR (CDCl3, 300 MHz, ppm): δ 8.08 (d, J= 7.1 Hz, 2H), 7.86 (m, 6H), 7.62 (t, J = 7.5 Hz, 2H), 7.56 (t, J = 7.6 Hz,4H), 7.43 (t, J = 7.0 Hz, 2H). 13C NMR (CDCl3, 100 MHz, ppm): δ 201.7,154.2, 132.1, 131.5, 131.4, 129.0, 128.6, 128.3, 127.8, 121.7, 120.9.HRMS: m/z calcd. for C27H16O, 357.1235 [M + H]+, found: 357.1260[M + H]+. Melting point: 291 C. |
89% | With potassium hydroxide In ethanol for 3h; Reflux; | |
88% | With sodium hydroxide In ethanol; water at 60 - 80℃; | 1 First, 9.1 g (50 mmol) of El and 10.5 g (50 iranol) of E2 were placed in 200 ml of ethanol and heated to 6O0C, and then 20 ml of a 5M aqueous sodium hydroxide solution was added dropwise. After the addition, the resultant mixture was heated to 800C, stirred for 2 hours, and then cooled. Then, the resultant precipitates were filtered off, washed with water and ethanol, and then dried by heating at 800C under reduced pressure to prepare 15.6 g (yield: 88%) of dark green solid E3. Next, 3.56 g (10 mmol) of E3 and 2.59 g (12 mmol) of E4 were placed in 50 ml of toluene and heated to 800C, and then 1.40 g (12 mmol) of isoamyl nitrite was slowly added dropwise, followed by stirring at 1100C for 3 hours. After cooling, the mixture was washed two times with 100 ml of water each time. The resultant organic layer was washed with saturated saline and dried with magnesium sulfate. Then, the solution was filtered, and the filtrate was concentrated to obtain a brownish-red liquid. The liquid was purified by column chromatography(toluene/heptane = 2 : 3) and then recrystallized with chloroform/methanol to obtain 3.96 g (yield: 88%) of an isomer mixture as yellow crystal E5. |
85% | With potassium hydroxide In ethanol for 2h; Reflux; | 2 Preparation of dienone 2a Preparation of dienone 2a [0270] To a solution of compound 8a (l .Og, 4.76 mmol) and acenaphthylene- 1 ,2-dione (0.87g, 1 equiv) in ethanol (20ml), under reflux was added a solution of KOH (0.28g, 1 equiv) in ethanol (5ml). After addition, the reaction mixture was stirred under reflux for additional 2hrs. On cooling, dark precipitate obtained by filtration, was washed with ethanol to afford compound 2a as a dark brown solid (yield: 85%). XH NMR (400 MHz, CDC13): δ 8.09 (d, J= 7.2 Hz, 2H), 7.89 (d, J= 8.0 Hz, 2H), 7.86 (d, J= 7.6 Hz, 4H), 7.61 (t, J= 7.6 Hz, 2H), 7.55 (t, J= 7.6 Hz, 4H), 7.43 (t, J= 7.2 Hz, 2H). |
85% | With potassium hydroxide In ethanol Reflux; | 2 Preparation of dienone 2a To a solution of compound 8a (lOg, 4.76 mmol) and acenaphthylene-1,2-dione (O.87g, 1 equiv) in ethanol (20m1), under reflux was added a solution of KOH (O.28g, 1 equiv) in ethanol (5m1). After addition, the reaction mixture was stirred under reflux for additional 2hrs. On cooling, dark precipitate obtained by filtration, was washed with ethanolto afford compound 2a as a dark brown solid (yield: 85%). ‘H NIVIR (400 MHz, CDC13):8.09 (d, J 7.2 Hz, 2H), 7.89 (d, J 8.0 Hz, 2H), 7.86 (d, J 7.6 Hz, 4H), 7.61 (t, J 7.6 Hz, 2H), 7.55 (t, J= 7.6 Hz, 4H), 7.43 (t, J 7.2 Hz, 2H) |
80% | With potassium hydroxide In methanol at 90℃; for 0.5h; | |
77% | In ethanol at 85℃; for 48h; | (1) Preparation of [compound-A-1] Acenaphthenequinone (30 g, 164 mmol) and 1,3-diphenyl-2-propanone (34 g, 164 mmol) were placed in ethanol (600 mL) and then potassium hydroxide (KOH) (27.6 g, 492 mmol) was added and the mixture was stirred and refluxed at 85 ° C. for 48 hours. After lowering the temperature to ordinary temperature and adding 300 mL of water, the produced solid was filtered and dried to produce [Compound A-1] (45 g, yield 77%). |
72% | Stage #1: acenaphthene quinone; 1,3-Diphenylpropanone In ethanol for 0.25h; Inert atmosphere; Reflux; Stage #2: With potassium hydroxide In ethanol at 0℃; for 0.25h; Inert atmosphere; | |
71.3% | With potassium hydroxide In ethanol Reflux; | 1 Synthesis of 9-Bromo-7,12-Diphenylbenzofluoranthene Exemplary Synthesis 1; Synthesis of Compound 1; Synthesis of 9,10-Diphenylanthracene-2-Boronic Acid; An amount of 6.8 g (23.7 mmol) of 2-bromoanthraquinone was suspended in a mixed solvent of 50 ml of dehydrated toluene and 50 ml of dehydrated ether and cooled to -20° C. An amount of 26.3 ml (50 mmol) of a solution of phenyllithium (1.9 mmol/ml) in butylether was added and allowed to react for six hours. Then, distilled water was added to stop the reaction. Then, the separated organic layer was applied to column chromatography to obtain a diol form. Then, the obtained diol form, 39 g (237 mmol) of potassium iodide, and 41 g (390 mmol) of sodium hypophosphite monohydrate were dissolved in acetic acid and refluxed for six hours. After cooling, the deposit was filtered and purified by column chromatography to obtain 4.68 g (11.4 mmol) of 2-bromo-9,10-diphenylanthracene. The yield was 48.3%.An amount of 4.68 g (11.4 mmol) of 2-bromo-9,10-diphenylanthracene was dissolved in dehydrated THF and cooled to -80° C. An amount of 7.9 ml (12 mmol) of a solution of n butyllithium in n hexane was added dropwise and, 40 minutes later, 3.33 g (22.8 mmol) of triethyl borate was further added. After two-hour reaction, a dilute hydrochloric acid solution was added and the mixture was allowed to stand for 12 hours. Then, the separated organic layer was recrystallized to obtain 3.07 g (8.2 mmol) of 9,10-diphenylanthracene-2-boronic acid. The yield was 72%. Synthesis of 9-Bromo-7,12-Diphenylbenzofluoranthene; An amount of 5.9 g (32.4 mmol) of acenaphthenequinone and 7.5 g (35.7 mmol) of 1,3-diphenyl-2-propanone were suspended in 150 ml of ethanol and a solution of 2 g of potassium hydroxide in ethanol was added. After the mixture was heated to the reflux temperature, the same amount of the solution of potassium hydroxide in ethanol was further added and allowed to react for five minutes. The solid substance deposited after cooled on ice was filtered and washed with ethanol to obtain 8.24 g (23.1 mmol) of 7,9-diphenylcyclopenta[a]acenaphthylene-8-one. The yield was 71.3%.An amount of 8.24 g (23.1 mmol) of 7,9-diphenylcyclopenta[a]acenaphthylene-8-one was dissolved in 300 ml of dichloromethane and held at the reflux temperature. A solution of 5.4 g (46.2 mmol) of isoamyl nitrite in dichloromethane and a solution of 5 g (23.1 mmol) of 2-amino-5-bromobenzoic acid in dichloromethane were simultaneously added dropwise over one hour. After 12-hour reflux, methanol was added and the deposit was filtered. Then, the deposit was dissolved in xylene, refluxed for 12 hours, and purified by column chromatography to obtain 3.96 g (8.2 mmol) of 9-bromo-7,12-diphenylbenzofluoranthene. The yield was 35.5%. (Synthesis of Compound 1); An amount of 1.4 g (3.74 mmol) of 9,10-diphenylanthracene-2-boronic acid, 1.8 g (3.74 mmol) of 9-bromo-7,12-diphenylbenzofluoranthene, and 100 mg of tetrakis triphenylphosphine palladium as catalysis were dissolved in a mixed solvent of 80 ml of toluene and 20 ml of ethanol. Then, 40 ml of 2M sodium carbonate solution was added and allowed to react at 90° C. for 12 hours. After the reaction was completed, the organic layer was separated and purified by column chromatography to obtain 1.83 g (2.5 mmol) of Compound 1. The yield was 66.8%.The obtained Compound 1 was identified by the mass spectrum, infrared absorption spectrum, and NMR. |
53.8% | In ethanol at 75℃; for 2h; | 1 1.82 g (10.0 mmol) of Compound 8, 2.62 g (12.5 mmol) of Compound 9, and 50 ml of ethanol were loaded into a 100-ml three-necked flask. In a nitrogen atmosphere, the mixture was heated to 750C, and was stirred for 2 hours . The resultant solution was cooled, and was then filtrated. The resultant black solid was washed with 10 ml..of methanol, whereby 1.91 g (53.8% yield) of Compound 10 as a blackish green solid' were obtained. |
With potassium hydroxide | ||
With potassium hydroxide; sulfuric acid 1) ethanol, reflux, 2 h, 2) acetic anhydride, reflux; Multistep reaction; | ||
With potassium hydroxide In methanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With bromine for 2h; Reflux; | |
90% | With bromine at 60 - 70℃; for 2h; | |
90% | With bromine at 0 - 70℃; for 2h; |
90% | With bromine at 65℃; for 3h; Inert atmosphere; | 10.1 (1) The synthesis of intermediate 1 33 mmol of acenaphthequinone and 180 mmol of liquid bromine were stirred and slowly heat up to 650 and reacted for 3 h at 650. The reaction solution was poured to 300ml of cooled water containg a little H2SO4, a yellow solid was generated and the solution was showed deep yellow color. The reaction mixture was heated to dislodge liquid bromine and HBr untile the solution changed into colorless from deep yellow color, then the solution was filtrated and the filter cake was washed until the filtrate was neutral and dried to obtain the intermediate 1 in a yield of 90%. M.p.236-238□. |
88.12% | With bromine at 70℃; for 2h; | 1 Example 1, Synthesis of Intermediate 1: Among them, the preparation method of the raw material A (5-bromoacenaphthequinone) is: Into a 250mL two-necked flask, add 21.86 g (120mmol) of acenaphthequinone and 27mL (480mmol) of liquid bromine, stir and warm at 70 °C, stop reaction after 2h, add saturated aqueous sodium hydrogen sulfite solution, the reaction solution was colorless. Dilute with water, filter under reduced pressure, and wash with plenty of water until the filtrate is getting neutral. The filter cake is dried and then used in dichloromethane: Separation and purification of petroleum ether = 2:1 (volume ratio) eluent on silica gel column, obtained 27.6 g of 5-bromoacenaphthequinone, which is yellowish brown, Yield 88.12%. |
88.12% | With bromine at 70℃; for 2h; | 1 Wherein raw materials A (5 - bromo acenaphthoquinone) preparation method is as follows In a 250 mL two-necked flask, 21.86 g (120 mmol) of acenaphthenequinone and 27 mL (480 mL) of liquid bromine were added, stirred and heated to 70 ° C. After 2 h, the reaction was stopped, and a saturated aqueous solution of sodium hydrogen sulfite was added until the reaction mixture was colorless. . Dilute with water, filter under reduced pressure, and wash with plenty of water until the filtrate is neutral. The filter cake was dried and separated and purified on a silica gel column using dichloromethane: petroleum ether = 2:1 (volume ratio) eluent to obtain a yellow-brown 5-bromoacenaphthenequinone 27.6 g, yield 88·12 c/o. |
86% | With bromine; sodium hydroxide at 65℃; for 2h; | 1.1 (1) Synthesis of 5-Bromoacenaphthenequinone (Compound 1) The 10.02g (55mmol) acenaphthenequinone added 250mL bottle after three 12mL syringe amount of liquid bromine was added thereto,Saturated NaOH solution to absorb exhaust,Heated slowly to 65 ,The reaction conditions for two hours under stirring.The reaction was stopped,The mixture was cooled to room temperature,Adding an appropriate amount of saturated Na2SO3 solution to remove excess bromine and hydrogen bromide to a colorless liquid.Filtration,Washed until the filtrate was neutral.The crude product was dried and recrystallized with glacial acetic acid,Yellow solid 12.34g,Yield 86%. |
86% | With bromine; sodium hydroxide at 65℃; for 2h; | 1.1 (1) 4-bromoacenaphthoquinone(Compound 1) 10.02 g (55 mmol) of acenaphthoquinone was added to a 250 mL three-necked flask and 12 mL of liquid bromine was added thereto with a syringe.Saturated NaOH solution to absorb the exhaust gas, slowly heated to 65 ° C, stirring conditions for two hours. Stop the reaction,The mixture was cooled to room temperature,Add the appropriate amount of saturated Na2SO3 solution to remove excess bromine and hydrogen bromide to the liquid as colorless. Filter,Washed to the filtrate was neutral. The crude product was dried and recrystallized from glacial acetic acid,10.34 g of a yellow solid,Yield 86%. |
86% | With bromine; sodium hydroxide at 65℃; for 2h; | 1.3 (3) Synthesis of 4-bromoacenoquinone (Compound 3) 10.02 g (55 mmol) of acenaphthoquinone was added to a 250 mL three-necked flask and 12 mL of liquid bromine was added thereto with a syringe. Saturated NaOH solution to absorb the exhaust gas, slowly heated to 65 ,The reaction was carried out under stirring for two hours. The reaction was stopped and the mixture was cooled to room temperature and an appropriate amount of saturated Na2SO3 solution was added to remove excess bromine and hydrogen bromide until the liquid was colorless. Filter,Washed to the filtrate was neutral. The crude product was dried and recrystallized from glacial acetic acid,To give 12.34 g of a yellow solid in 86% yield. |
82% | With bromine at 65℃; for 2h; | 1.1 In a 250mL three-necked flask, 10.04g of acenaphthoquinone and 17mL of liquid bromine were added and heated to 65 ° C. The exhaust gas was absorbed with saturated Na2S03 solution, stirred for 2 hours and cooled to room temperature. Saturated Na2SO3 solution was slowly added to the flask. Bromine, precipitated a yellow solid, filtered, washed to the filtrate was neutral, dry, glacial acetic acid recrystallization, drying, compound b yellow-orange product 11.79g, yield 82%. |
80% | With bromine at 60℃; for 2h; | |
75% | With bromine Inert atmosphere; Reflux; | |
74% | With bromine at 75℃; for 2h; Inert atmosphere; Reflux; | |
72% | With bromine at 70℃; for 2h; | |
With bromine at 60 - 70℃; | ||
With bromine at 60℃; | ||
With bromine at 60℃; | ||
With bromine at 60 - 70℃; | ||
With bromine at 60℃; | ||
With bromine for 2h; Reflux; | ||
With bromine | ||
With bromine at 70℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With hydroxyamino hydrochloride; anhydrous sodium carbonate In ethanol for 0.75h; Reflux; | |
With ethanol; hydroxyamino hydrochloride | ||
With hydroxyamino hydrochloride; sodium hydroxide |
With hydroxyamino hydrochloride; anhydrous sodium carbonate In ethanol for 0.75h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With hydroxylamine hydrochloride; sodium acetate In ethanol at 20℃; for 24h; | Acenaphthylene-1,2-dione di-oxime 9 A literature procedure was followed but the work-up wasdifferent.15 Acenaphthenequinone (5.0 g, 27.5 mmol), hydroxylamine hydrochloride (4.2 g, 60.4 mmol) andsodium acetate (5.0 g, 61 mmol) were stirred at room temperature(rt) in EtOH (150 mL) for 24 h. The mixture wasgently refluxed for 2 h and then cooled. The mixture waspoured into water (400 mL) and left to stand for 2 h as theproduct precipitated. This was filtered with a large sinter,washed with water (100 mL) and air dried to give the titlecompound (5.2 g, 98%) as an off-white solid, m.p. > 220 °C (from DCM/light petroleum ether 40-60). λmax (EtOH)/nm325 (log ε 3.2), 232 (4.6) and 212 (4.5); νmax (Diamond)3453w, 3018w, 2837w, 1489w, 1418w, 1347w, 1289w,1228w, 1185w, 1146w, 1016m, 1000m, 937m, 854s, 825s,773s, 611m, 539m and 443s; δH (600 MHz; CDCl3) 7.69(2H, m), 7.97 (2H, d, J = 6.0) and 8.43 (2H, d, J = 6.0); δC(150 MHz; CDCl3) 125.5, 127.1, 127.8, 129.0, 130.6, 136.9and 149.6; m/z (Orbitrap ASAP) 213.0659 (M+ + H, 100%)C12H9N2O2 requires 213.0659. |
36% | With hydroxylamine hydrochloride; sodium acetate In ethanol; water Reflux; | |
With ethanol; hydroxylamine hydrochloride |
With hydroxylamine hydrochloride | ||
With hydroxylamine hydrochloride; sodium carbonate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With sodium hypochlorite for 0.2h; Irradiation; | |
92% | Stage #1: acenaphthene quinone With 4,4'-dichlorobenzophenone; oxygen; sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 0.166667h; Stage #2: With hydrogenchloride In tetrahydrofuran; water; mineral oil | General procedure for the oxidative cleavage of cyclic 1,2-diketones 1 to dicarboxylic acids 3: General procedure: To a solution of cyclic 1,2-diketones 1 (0.5 mmol) and 4,4′-dichlorobenzhydrol (1.0 mmol) in distilled THF (10 mL) was added NaH (60% in mineral oil, 1.5 mmol) at 0 °C. While stirring, the dark-blue solution was allowed to warm to room temperature. After stirring under O2 (1 atm), until TLC analysis indicated a complete consumption of the starting material, the reaction mixture was quenched by adding 0.1 N HCl to a final pH of 1-2 and extracted with CH2Cl2. The combined organic layers were dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography (preequilibrated with EtOAc/n-hexane/TFA = 1:20:0.1) to give 3. |
80% | With sodium hypochlorite for 2h; Irradiation; |
With potassium hydroxide | ||
With dihydrogen peroxide; acetic acid | ||
Multi-step reaction with 2 steps 1: benzene 2: aq. H2O2, NaOH / dioxane | ||
With 4-ethyl-1-methyl-4H-[1,2,4]-triazol-1-ium iodide; water; 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at 20℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With triethylamine; In tetrahydrofuran; methanol; at 20℃; | Preparation of dienone 2b [0271] A solution of compound 8b (l .Og, 5.2 mmol) and acenaphthylene- 1 ,2-dione (0.95g, 1 equiv) in THF/MeOH (30/10ml) was treated with Et3N (0.79g, 1.5 equiv), and the reaction mixture was stirred overnight at room temperature. Thus formed dark green precipitate was filtered, and washed with methanol to give compound 2b as dark green solid (yield: 80%). lU NMR (400 MHz, CDC13) delta 8.79 (d, J= 7.2 Hz, 1H), 8.15 - 8.03 (m, 2H), 7.95 (d, J= 8.0 Hz, 1H), 7.84 (d, J= 7.2 Hz, 2H), 7.80 (d, J= 7.6 Hz, 1H), 7.64 (t, J= 8.0 Hz, 1H), 7.55 (t, J = 8.0 Hz, 2H), 7.47 (t, J= 7.6 Hz, 1H), 4.03 (s, 3H). |
80% | With triethylamine; In tetrahydrofuran; methanol; at 20℃; | 102951 A solution of compound 8b (lOg, 5.2 mmol) and acenaphthylene-1,2-dione (O.95g,1 equiv) in THF/MeOH (3 0/1 Oml) was treated with Et3N (O.79g, 1.5 equiv), and the reaction mixture was stirred overnight at room temperature. Thus formed dark green precipitate was filtered, and washed with methanol to give compound 2b as dark green solid (yield: 80%). ?H NMR (400 MHz, CDCl3) 8.79 (d,J= 7.2 Hz, 1H), 8.15-8.03 (m, 2H), 7.95 (d,J= 8.0 Hz, 1H), 7.84 (d, J 7.2 Hz, 2H), 7.80 (d, J 7.6 Hz, 1H), 7.64 (t, J 8.0 Hz, 1H), 7.55 (t, J8.0 Hz, 2H), 7.47 (t, J= 7.6 Hz, 1H), 4.03 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | In water at 20℃; for 0.166667h; Green chemistry; | 2.1.1. Synthesis of 2-benzylidenemalononitrile and of 2-(2-oxo-indolin-3-ylidene) malononitrile derivatives General procedure: Malononitrile (66 mg, 1 mmol) and 2,4-dichlorobenzaldehyde (223 mg, 1 mmol) were taken in pestle-mortar and mixed in 1:1 molar ratio in PEG-400/water as a solvent. After 10 minutes of grinding yellowish solid was obtained which was washed with wa- ter/ethanol (2 ×10 mL) and the reaction was monitored by TLC us- ing hexane and acetyl acetate (8:2) as the eluent and silica gel as stationary phase. TLC plates were visualized in an iodine chamber. After air drying and recrystallization in ethanol for 24 h, a white crystalline solid was obtained with high yield (96-99%) and char- acterized (Supplementary information) Scheme 1 and Table 1 . |
98% | In water at 80℃; for 0.25h; | 4.3.9. (2-Oxoacenaphthylen-1(2H)-ylidene)malononitrile (4) A mixture of acenaphthenequinone 1 (5 mmol), malononitrile (5 mmol), and water (3 mL) was stirred at 80 °C for 15 min. Then the reaction mixture was cooled, the precipitate was filtered, washed with ethanol (5 mL) and dried under reduced pressure to afford the product 4 as orange solid. Yield 1.13 g (98%); mp 245-246 °C (lit. mp11 244-246 °C); 1H NMR (300 MHz, DMSO-d6) δ 7.90-8.04 (m, 2H), 8.17 (d, J 7.0 Hz, 1H), 8.34-8.49 (m, 3H) ppm. |
97.3% | In dichloromethane at 20℃; |
97% | In dichloromethane | 16.1 (1) The synthesis of intermediate 1 0.5 g of acenaphthequinone and 0.2 g of malononitrile were dissolved in 50 ml of CH2Cl2, and was directly purified by silica gel column chromatography using a CH2Cl2 as the eluent. The fraction with an Rf value of 0.8 was collected and evaporated to remove the CH2Cl2, affording intermediate 1 as orange red solid in a yield of 97 %. |
95% | In acetonitrile Heating; | |
95% | With silica gel In dichloromethane at 20℃; | |
91% | In acetonitrile for 3h; Heating; | |
91% | In acetonitrile for 2h; Reflux; | General Procedure for the Preparation of 6, 6a-6d General procedure: Acenaphthenequinone or 4b-4e (10 mmol) and malononitrile (660 mg, 10 mmol) in CH3CN (30 mL) were refluxed for 2 hour. After cooling, the precipitate was filtrated and purified by recrystallization from CH3CN to yield an orange needle solid. |
88% | In ethanol at 20℃; for 0.5h; Sonication; | 18 A mixture of acenapthalenequinone (10 mmol) and malononitrile (10 mmol) in absolute ethanol (20 mL) were taken in a conical flask and immersed in water bath of an ultrasonic cleaner. The flask was positioned 0.5 cm above the bottom of the bath at room temperature for 30 min. The resulting orange precipitate was then filtered and washed from ethanol to afford Knoevenagel adduct (yield 88%, mp: 244-246 °C). |
85% | In ethanol for 0.5h; Reflux; | |
82% | In acetonitrile for 3h; Inert atmosphere; Reflux; | |
81.7% | In acetonitrile for 3h; Reflux; | |
80% | In acetonitrile for 3h; Reflux; | |
78% | In acetonitrile for 2h; Reflux; | Using acenaphthylene-1,2-dione (5.46 g, 1 equiv, 30.00 mmol) and malononitrile (1.98 g, 1 equiv, 30 mmol) as the starting materials, then dissolved in acetonitrile (80 mL) and refluxed for 2 hour. Then mixture was cooled to 0 °C and filtered to give a green dark powder. The precipitate was washed several times with cold acetonitrile and purified by silica gel column chromatography (100% DCM) to afford a bright orange powder 2-(2-oxo-2H-acenaphthylene-1-ylidene)-malononitrile (5.38 g, yield =78%). |
In ethanol Heating; | ||
In acetonitrile for 4h; Reflux; | 1 Example 1: Synthesis and Characterization of 8-oxo-8H-acenaphtho[1,2-b] pyrrole-9-carbonitrile 0.1mol of acenaphthene quinone, 0.11mol of malononitrile and 150mL of acetonitrile were added into a 500mL single neck flask in sequence. The reaction mixture was heated under reflux for 4 hours until the color turned into transparent orange red from cloudy pale yellow. After that, the reaction mixture was cooled to room temperature, filtered, and the orange red filter cake was collected to obtain 1-dicyanomethylene-2-oxo-acenaphthene. 0.05 mol of 1-dicyanomethylene-2-oxo-acenaphthene, 1g of K2CO3, and 200mL of acetonitrile were added into a 500mL single neck flask in sequence, the reaction mixture was heated under reflux for 4 hours. A large amount of earth yellow solid separated out. Filtered and the filter case was collected and washed with a large quantity of warm water, and then dried and weighed; the yield was 95%. M.p. 275-277°C; 1H NMR (400M, DMSO): δ 8.705(d, J=8.0Hz , 1H), 8.662 (d, J=8.8Hz, 1H), 8.631 (d, J=8.0Hz, 1H), 8.411 (d, J=8.0Hz, 1H), 8.06 (t, J=8.0Hz, 1H), 7.984 (t,J=8.0Hz, 1H). | |
In acetonitrile for 4h; Reflux; | 1 Example 1 Synthesis and Characterization of 8-oxo-8H-acenaphtho[1,2-b]pyrrole-9-carbonitrile 0.1 mol of acenaphthene quinone, 0.11 mol of malononitrile and 150 mL of acetonitrile were added into a 500 mL single neck flask in sequence. The reaction mixture was heated under reflux for 4 hours until the color turned into transparent orange red from cloudy pale yellow. After the reaction mixture was cooled to room temperature, filtered, and the orange red filter cake was collected to obtain 1-dicyanomethylene-2-oxo-acenaphthene. | |
With triethylamine In ethanol for 0.166667h; | Experimental procedure for the synthesis of spirodihydropyridine 7a (Table 4, entry 1): A mixture of acenaphthenequinone 6 (1 mmol), malononitrile 2a (1 mmol), and Et3N (1 mmol) were stirred in ethanol for 10 min followed by the addition of 3-methyl aniline 3a (1 mmol) and DMAD 4a (1 mmol) after 10 min. The reaction mixture was stirred for 40 min. After the completion of the reaction as indicated by TLC, the solid formed in the reaction mixture was filtered, dried, and recrystallized from ethanol to obtain the pure product 7a in good yield (80%). | |
In acetonitrile Reflux; | ||
With 1,8-diazabicyclo[5.4.0]undec-7-ene In water | ||
In dichloromethane | ||
With triethylamine In ethanol at 20℃; for 0.166667h; | ||
In ethanol for 1h; Reflux; | General procedure for synthesis of Knoevenagel adducts (1 and 2) General procedure: A mixture of acenaphthylene-1,2-dione (1.820 g, 10 mmol) and malononitrile (0.600g, 10 mmol) and or ethyl cyanoacetate (1.131 g, 10 mmol) in absolute ethanol (20mL) was refluxed for 1 h. The cooled mixture was filtered and the precipitate waswashed with cold ethanol (10 mL) to afford compound 1 and or 2. | |
With BuSO3H functionalized silica-coated Fe3O4 nanocatalyst In neat (no solvent) at 60℃; for 0.166667h; | 2.2 General procedure for the synthesis of [3.3.3] propellane For the synthesis of [3,3,3] propylene, initially, acenaphtoqinone (1.0mmol, 0.16 gr) and malononitrile (1mmol, 0.66g) in the presence of Fe3O4SiO2(BuSO3H)3 (0.01g) under solvent-free conditions were stirred at 60°C for ten minutes. Afterward, 4-Cl-aniline (1mmol, 0.12g) and β-ketoester (1mmol, 0.12ml) were added the mixture reaction and the reaction continued under solvent-free conditions at 60°C. The progression of the reaction was followed by TLC using ethyl acetate: hexane (8:2) ratio as solvent. After completion of the reaction, the reaction mixture was dissolved in hot ethanol, and then the nano magnetic catalyst separated using an external magnet from the aqueous solution, and then, The pure sediment of the product was obtained. The obtained products were characterized using melting point and FT-IR spectra and the new compounds were charecterizied by the 1H and 13C NMR spectra. | |
In acetonitrile Reflux; | ||
In acetonitrile at 65℃; for 3h; | 4.2. General procedure for the synthesis of compounds S1-S1i In a round-bottom flask, a mixture of acenaphthequinone (1.0equiv) and malononitrile (1.1 equiv) were stirred in CH3CN at 65 Cfor 3 h. The resulting mixture was cooled to rt, and then filtered togive the desired product 1. The crude product was used for next step without further purification |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethanol for 0.333333h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56.4% | With sulfonamide; toluene-4-sulfonic acid In ethanol at 80℃; for 72h; | 6 2.6. Synthesis of acenaphtho[1,2-c][1,2,5]thiadiazole 8,8-dioxide, 1 Sulfamide (15.8 g, 161 mmol) and p-toluenesulfonic acid monohydrate (1.36 g, 7.14 mmol) were added to acenaphthenequinone (10.0 g, 53.8 mmol) in absolute ethanol (400 mL), and the mixture was heated at 80°C for 3 days. After cooling to room temperature, the solvent was removed by rotary evaporation. The residue was then extracted with methylene chloride (2 * 350 mL) from water (350 mL), and a light brown precipitate formed above the organic layer. The precipitate was collected, and the combined organic layers were dried with magnesium sulfate, filtered, and concentrated. The concentrate was combined with the precipitate and recrystallized from boiling pyridine (200 mL) to give the product as a light brown powder (7.35 g, 56.4% yield). 1H NMR (DMSO-d6, 499.74 MHz): δ 8.49 (d, J = 7.8 Hz, 2H), 8.45 (d, J = 7.8 Hz, 2H), 8.01 (t, J = 7.7 Hz, 2H). 13C NMR (DMSO-d6, 125.67 MHz): δ 166.24, 148.57, 133.26, 130.77, 129.71, 126.80, 123.13. IR (neat): 1630, 1581, 1485, 1415, 1355, 1170, 1091, 1070, 1038, 986, 942, 920, 831, 776, 738, 694, 663 cm-1. HR-DART/MS (m/z): [M+H]+ 243.0219 (found); C12H7N2O2S 243.0228 (calcd). |
With hydrogenchloride; SULFAMIDE In ethanol | ||
With hydrogenchloride; SULFAMIDE at 40℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | In acetic acid for 2h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With niobium pentachloride In ethanol at 20℃; for 0.0666667h; | |
93% | With polyvinylimidazole-based Bronsted acidic ionic liquid grafted silica In ethanol at 20℃; for 0.75h; | 3.3. General procedure for preparation of quinoxaline derivatives General procedure: To a mixture of 1,2-diketone (1 mmol) and 1,2-diamine (1 mmol) in 4 mL of ethanol was added catalyst III (0.006 g, 0.5 mol%) or catalyst IV (0.017 g, 1 mol%). The reaction mixture was stirred at room temperature for the appropriate time. The progress of the reaction was followed by TLC. Upon completion, the product and the catalyst were separated easily from each other by simple ltration. The ltrate was concentrated under reduced pressure and the crude product was puried by silica gel column chromatography with petroleum ether (bp 60 °C) and ethyl acetate (in some cases recrystallization was used). The obtained quinoxalines were identied by their 1H NMR and 13C NMR spectra and comparison of their melting points with those of the authentic samples. |
93% | With 1-butyl-3-methylimidazolium Tetrafluoroborate at 20℃; for 0.25h; Green chemistry; | 2.4. General procedure for the synthesis of quinoxalines General procedure: A mixture of aromatic diamine derivatives (2 mmol) and a 1,2-dicarbonyl compound (2 mmol) in ionic liquid (2 mL) was stirred atroom temperature for the appropriate time. The progress of the reaction was monitored by TLC (n-Hexane: EtOAc, 7:3), after completion of the reaction, the reaction mixture was diluted with water and extracted using diethyl ether (30 ml). The combined organic layer was dried over anhydrous sodium sulphate and evaporated under reduced pressure to afford the corresponding product. The residual ionic liquid was dried under vacuum and reused. The same procedure was repeated for the reaction of aromatic anilines with isatin and acenaphthoquinone and phenaacylbromide. All the products obtained were characetrised by IR,1HNMR, 13CNMR and Mass studies. |
90% | With lead(II) chloride In ethanol at 20℃; for 0.5h; | General procedure: A mixture of 1,2- dicarbonyl compound or aryl glyoxal (1 mmol),o-phenylenediamine (1.1 mmol) and lead dichloride( 20 mol%) in ethanol(5 mL) was stirred at room temperature. The progress of the reaction wasmonitored by TLC (hexane/AcOEt, 3:7). After the completion of the reaction,the solid which separated was filtered and then recrystallized from ethanol toafford pure product. |
89% | In 1,4-dioxane for 0.5h; Heating; | |
85% | With 1,1,1,3',3',3'-hexafluoro-propanol at 20℃; for 1h; | |
85% | With (2,3,4,5,6-pentafluorophenyl)ammonium triflate In water at 20℃; for 1h; Green chemistry; | Typical experimental procedure A mixture of 1,2-dicarbonyl compounds (1 mmol), aryl1,2-diamines (1 mmol) dissolved in 4 mL water, and PFPAT(10 mol%) was stirred for the appropriate reaction time. Thereaction was monitored by TLC. After completion of thereaction (monitored by TLC), the resultant was cooled withice-salt bath, filtered and washed with ethanol and purifiedby recrystallization from hot ethanol to afford pure products3a-p, and the filtrate containing PFPAT could be directlyused by adding the reactants. After three recycles, thecatalytic activity of PFPAT remained unchanged. Theproducts were characterized by comparison of their physicaland spectral data with those of authentic samples. |
85% | With PVPP*OTf In water at 20℃; for 1h; | 2.2 Typical experimental procedure General procedure: A mixture of 1,2-dicarbonyl compounds (1 mmol), aryl 1,2-diamines (1 mmol) dissolved in 4 mL water, and PVPP·OTf (30 mg) was stirred for 1 h. The reaction was monitored by TLC. After completion of the reaction, the mixture was washed with chloroform and filtered to recover the catalyst. The filtrate was evaporated and purified by recrystallization from hot ethanol to afford pure products. Products were characterized by comparison of their physical and spectral data with those of authentic samples. Spectroscopic data for selected examples as follows: |
82% | With lithium chloride In ethanol at 20℃; for 0.133333h; | |
80% | With 3,5-bis(trifluoromethyl)phenylammonium hexafluorophosphate In water at 20℃; for 2h; Combinatorial reaction / High throughput screening (HTS); | 2.2. General Procedure for the Preparation ofQuinoxaline Derivatives General procedure: A mixture of 1,2-dicarbonyl compounds (1 mmol), aryl1,2-diamines (1 mmol), and BFPHP (10 mol%) in water (3mL) was stirred at room temperature for an appropriate time.Upon completion of the reaction, (monitored by TLC), theresultant was cooled with ice bath, filtered and washed withethanol and purified by recrystallization from hot ethanol toafford pure products. |
75% | In acetic acid for 20h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With sulfonated rice husk ash at 20℃; for 0.0833333h; Green chemistry; | General procedure for the synthesis of quinoxaline derivatives General procedure: To a mixture of 1,2-diaminobenzene (1 mmol) and 1,2-dicarbonyl compound (1 mmol), RHA-SO3H (15 mg) was added and the mixture was stirred at room temperature for the appropriate time. The progress of the reaction was monitored by TLC (EtOAc: n-hexane 2:8). After completion of the reaction, ethyl acetate (20 mL) was added to the mixture and the solid catalyst was separated. Then the solvent was evaporated and the resulting solid product was recrystallized from ethanol, producing the pure product in high yields. |
97% | With polyvinylimidazole-based Bronsted acidic ionic liquid grafted silica In ethanol at 20℃; for 0.25h; | 3.3. General procedure for preparation of quinoxaline derivatives General procedure: To a mixture of 1,2-diketone (1 mmol) and 1,2-diamine (1 mmol) in 4 mL of ethanol was added catalyst III (0.006 g, 0.5 mol%) or catalyst IV (0.017 g, 1 mol%). The reaction mixture was stirred at room temperature for the appropriate time. The progress of the reaction was followed by TLC. Upon completion, the product and the catalyst were separated easily from each other by simple ltration. The ltrate was concentrated under reduced pressure and the crude product was puried by silica gel column chromatography with petroleum ether (bp 60 °C) and ethyl acetate (in some cases recrystallization was used). The obtained quinoxalines were identied by their 1H NMR and 13C NMR spectra and comparison of their melting points with those of the authentic samples. |
96% | With rice husk In water; acetonitrile at 50℃; for 0.166667h; Green chemistry; | General procedure for the synthesis of quinoxaline derivatives General procedure: A mixture of 1,2-dicarbonyl compound (1 mmol), o-phenylenediamine (1 mmol) and RiH (0.35 mol %) in H2O/CH3CN (2 mL/2 mL) was stirred at 50 °C. The progress of the reaction was monitored by TLC. After completion of the reaction, and evaporation of the solvents, the reaction solid product was extracted with Et2O (3 × 15 mL). The catalyst was filtered and reused for further runs. Et2O was evaporated and the solid residue recrystallized with ethanol to afford the pure product. The physical and spectral data of the known compounds were in agreement with those reported in the literature [40,43,58,59]. |
95% | With iron(II,III) oxide In water at 20℃; for 3h; | |
95% | With titanium(IV) oxide In 1,2-dichloro-ethane at 25℃; for 0.5h; | |
95% | With 1,1,1,3',3',3'-hexafluoro-propanol at 20℃; for 1h; | |
95% | With 1-(propyl-3-sulfonate) 3-methylimidazol(3H)-1-ium phosphotungstate In water at 20℃; for 0.333333h; | |
95% | With 1-butyl-3-methylimidazolium Tetrafluoroborate at 20℃; for 0.25h; Green chemistry; | 2.4. General procedure for the synthesis of quinoxalines General procedure: A mixture of aromatic diamine derivatives (2 mmol) and a 1,2-dicarbonyl compound (2 mmol) in ionic liquid (2 mL) was stirred atroom temperature for the appropriate time. The progress of the reaction was monitored by TLC (n-Hexane: EtOAc, 7:3), after completion of the reaction, the reaction mixture was diluted with water and extracted using diethyl ether (30 ml). The combined organic layer was dried over anhydrous sodium sulphate and evaporated under reduced pressure to afford the corresponding product. The residual ionic liquid was dried under vacuum and reused. The same procedure was repeated for the reaction of aromatic anilines with isatin and acenaphthoquinone and phenaacylbromide. All the products obtained were characetrised by IR,1HNMR, 13CNMR and Mass studies. |
94% | With lead(II) bromide In ethanol at 20℃; | |
94% | With camphor sulfonic acid In ethanol; water at 28 - 32℃; for 0.75h; Green chemistry; | Synthesis of dibenzo[a,c]phenazine (3a) General procedure: In an oven dried clean reaction tube o-phenylenediamine (1; 0.5 mmol), phenanthrene-9,10-dione (2; 0.5 mmol) and a catalytic amount of camphor sulfonic acid (20 mol%) were taken sequentially. The reaction mixture was then stirred vigorously in aqueous ethanol as solvent at room temperature. Progress of the reaction was monitored byTLC. After completion of the reaction, synthesized dibenzo[a,c]phenazine (3a) was isolated pure with 92% yield just by simple filtration and subsequent washing with aqueous ethanol (EtOH:H2O 1:1). The structure of the synthesized compound was determinedby the detail spectral analysis including 1H NMR, 13C NMR and HRMS spectroscopy. |
93% | With niobium pentachloride In ethanol at 20℃; for 0.0333333h; | |
93% | With lead(II) chloride In ethanol at 20℃; for 0.333333h; | General procedure: A mixture of 1,2- dicarbonyl compound or aryl glyoxal (1 mmol),o-phenylenediamine (1.1 mmol) and lead dichloride( 20 mol%) in ethanol(5 mL) was stirred at room temperature. The progress of the reaction wasmonitored by TLC (hexane/AcOEt, 3:7). After the completion of the reaction,the solid which separated was filtered and then recrystallized from ethanol toafford pure product. |
92% | In 1,4-dioxane for 0.5h; Heating; | |
92% | With niobium pentachloride In acetonitrile at 80 - 85℃; for 4.5h; | |
92% | With cerium(III) chloride heptahydrate In glycerol at 75℃; for 4.5h; | |
92% | With propylsulfonic acid functionalized nanozeolite clinoptilolite In water at 25℃; for 0.333333h; | 2.3 General procedure for the synthesis of quinoxalines General procedure: A mixture of aromatic o-diamine (1mmol), 1,2-dicarbonyl compounds or phenacyl bromides (1mmol) and NZ-PSA (0.01g) in 5mL of water was stirred at room temperature for an appropriate time (Scheme 2). The progress of the reaction was monitored by TLC. After completion of the reaction, the catalyst was filtered off. The solvent was evaporated under reduced pressure and the pure product was obtained without any further purification and their spectroscopic data are shown in supporting information. |
90% | With bismuth(lll) trifluoromethanesulfonate In water at 20℃; for 0.116667h; | |
90% | With zinc trifluoromethanesulfonate In acetonitrile at 80 - 85℃; for 4.5h; | |
90% | With magnesium sulfate heptahydrate In ethanol at 20℃; for 0.333333h; | |
90% | With lithium chloride In ethanol at 20℃; for 0.533333h; | |
90% | With (2,3,4,5,6-pentafluorophenyl)ammonium triflate In water at 20℃; for 1h; Green chemistry; | 6 Typical experimental procedure A mixture of 1,2-dicarbonyl compounds (1 mmol), aryl1,2-diamines (1 mmol) dissolved in 4 mL water, and PFPAT(10 mol%) was stirred for the appropriate reaction time. Thereaction was monitored by TLC. After completion of thereaction (monitored by TLC), the resultant was cooled withice-salt bath, filtered and washed with ethanol and purifiedby recrystallization from hot ethanol to afford pure products3a-p, and the filtrate containing PFPAT could be directlyused by adding the reactants. After three recycles, thecatalytic activity of PFPAT remained unchanged. Theproducts were characterized by comparison of their physicaland spectral data with those of authentic samples.White solid; mp 242-245 °C. IR (KBr): 3443, 3047, 2922, 2361, 1614, 1481 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.70-7.75 (m, 2 H), 7.98 (t, J = 7.7 Hz, 2 H), 8.15 (d, J = 7.7 Hz, 2 H), 8.18-8.22 (m, 2 H), 8.42 (d, J = 7.7 Hz, 2 H); 13C NMR (100 MHz, CDCl3): δ = 125.7, 126.8, 127.2, 128.2, 128.9, 129.6, 130.1, 133.2, 142.5, 145.3 ( |
90% | With PVPP*OTf In water at 20℃; for 1h; | 2.2 Typical experimental procedure General procedure: A mixture of 1,2-dicarbonyl compounds (1 mmol), aryl 1,2-diamines (1 mmol) dissolved in 4 mL water, and PVPP·OTf (30 mg) was stirred for 1 h. The reaction was monitored by TLC. After completion of the reaction, the mixture was washed with chloroform and filtered to recover the catalyst. The filtrate was evaporated and purified by recrystallization from hot ethanol to afford pure products. Products were characterized by comparison of their physical and spectral data with those of authentic samples. Spectroscopic data for selected examples as follows: |
90% | With 3,5-bis(trifluoromethyl)phenylammonium triflate In water at 20℃; for 1h; | 3.2. General Procedure for the Preparation of QuinoxalineDerivatives 3a-m General procedure: A water solution (3 mL) of 1,2-dicarbonyl compounds 2(1 mmol) and arene-1,2-diamines 1 (1 mmol) was mixedwith BFPAT (4) (10 mol%), and the resulting mixture wasstirred at rt for an appropriate time. Upon completion of thereaction, (monitored by TLC), the resultant was cooled in anice bath, filtered, washed with ethanol, and purified by recrystallizationfrom hot ethanol to afford pure products 3.The products were characterized by comparison of theirphysical and spectral data with those of authentic samples |
89% | With zinc(II) chloride In water; acetonitrile at 20℃; for 2.5h; | Synthesis of quinoxalines General procedure: In a typical reaction, carbonyl compounds (0.4 mmol) and o-phenylenediamine (0.4 mmol) were dissolved in 3 mL of acetonitrile water mixture (1:1). To this solution, clayzic (50 mg) was added and stirred for 2.5 h at room temperature. Then the reaction mixture was extracted with dichloromethane (10 mL) for 6 h, filtered, washed with water and dried with anhydrous sodium sulfate. In some cases, crude product and was recrystallized by ethyl acetate. |
89% | With samarium(III) trifluoromethanesulfonate In acetonitrile for 4.5h; Reflux; | |
88% | With tungstate sulfuric acid at 20℃; for 0.333333h; Neat (no solvent); | |
87% | With acetic acid at 35℃; for 8h; | |
86% | With aminosulfonic acid In ethanol at 20℃; for 1h; | B. Typical procedure: General procedure: To a 25 ml round bottom flask, a mixture of isatin / acenaphthoquinone / 2-hydroxynaphthoquinone/ ninhydrin (1 mmol), o-phenylene diamine (1 mmol) in ethanol (95 %, 10 mL) and sulfamic acid (20 mol %) was added. The reaction mixture was stirred at ambient temperature for time mentioned in Table II, monitored by TLC. After completion of reaction, the mixture was filtered washed with ethanol and dried to furnish the desired pure products in high yields. |
86% | With sodium tosylate; toluene-4-sulfonic acid In water at 20℃; for 2h; | Typical procedure for the synthesis of indoloquinoxalines General procedure: Isatins/ninhydrine/acenaphthoquinone (1.0 mmol), o-phenylene diamine (1.0 mmol) and PTSA (10 mol %) were added in a round bottom flask, containing 40% aq NaPTS (5 mL) and the reaction mixture was stirred at room temperature. The reaction progress was monitored by thin-layer chromatography (TLC). After completion of the reaction, the mixture was diluted with water (20 mL). The filtrate was washed with water and dried affording the corresponding crude products, which on recrystallization using ethanol gave pure products. |
81% | With cobalt(III) 5,10,15,20-tetraarylporphyrin In ethanol; water at 20℃; for 0.166667h; | |
80% | In acetic acid for 20h; Reflux; | |
80% | With 5-sulfosalicylic acid anchored to silica-modified Fe3O4 nanocomposite In ethanol at 60℃; | General procedure for the synthesis of quinoxaline derivatives General procedure: To a mixture of a 1,2-diketone (1.0 mmol) and 1,2-diaminobenzene (1.0 mmol) in ethanol (2.0 mL), Fe3O4(at)SiO2(at)5-SA (20 mg) was added and the mixture was stirred at 60 °C. The progress of the reaction was monitored by TLC. After completion of the reaction, the magnetic catalyst was separated by an external magnet. The products were purified by recrystallization from ethanol or methanol. |
With toluene-4-sulfonic acid for 0.0666667h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With benzeneseleninic anhydride In chlorobenzene at 120℃; for 2h; | |
79% | With N-Bromosuccinimide; water; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In dimethyl sulfoxide at 60 - 70℃; for 3h; | |
36% | With sodium dichromate; cerous nitrate In acetic acid for 19h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With acetic acid In methanol; benzene for 0.5h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In acetic acid; acetonitrile for 5h; Reflux; | |
85% | In acetic acid; acetonitrile for 1.5h; Heating; | |
84% | In acetic acid for 1h; Heating; |
78% | With acetic acid at 20℃; for 14h; Reflux; | 2 Preparation of N-{(1E,2E)-2-[(2,6-Diisopropylphenyl)imino]acenaphthylenylidene}-2,6-diisopropylaniline (L5).; [Show Image] A mixture of 1.82 g (10 mmol) of acenaphtoquinone, 3.54 g (20 mmol) of 2,6-diisopropylaniline, and 40 ml of glacial acetic acid was refluxed for 2 h and then stirred for 12 h at room temperature. The resulting precipitate was separated, washed with 20 ml of cold water, and dried under vacuum. 3.89 g of dark-yellow solid were obtained with a yield of 78%. Anal. for C36H40N2. Calculated: C 86.35, H 8.05. Found: C 86.43, H 8.14. 1H NMR (CDCl3): δ 7.87 (d, J=8.1Hz, 2H), 7.36 (dd, J=8.1Hz, J=7.2 Hz 2H), 7.31-7.20 (m, 6H), 6.64 (d, J=7.2 Hz, 2H), 3.04 (hept, J=6.8 Hz, 4H), 1.24 (d, J=6.9 Hz, 12H), 0.97 (d, J=6.9 Hz, 12H). 13C{1H} NMR (CDCl3): δ 161.0, 147.5, 140.8, 135.4, 131.1, 129.5, 128.8, 127.8, 124.3, 123.4, 123.3, 28.6, 23.4, 23.1. |
78% | With acetic acid at 20℃; for 14h; Reflux; | 2 Preparation of N-{(1E,2E)-2-[(2,6-Diisopropylphenyl)imino]acenaphthylenylidene}-2,6-diisopropylaniline (L5) A mixture of 1.82 g (10 mmol) of acenaphtoquinone, 3.54 g (20 mmol) of 2,6-diisopropylaniline, and 40 ml of glacial acetic acid was refluxed for 2 h and then stirred for 12 h at room temperature. The resulting precipitate was separated, washed with 20 ml of cold water, and dried under vacuum. 3.89 g of dark-yellow solid were obtained with a yield of 78%.Anal. for C36H40N2. Calculated: C, 86.35; H, 8.05. Found: C, 86.43; H, 8.14.1H NMR (CDCl3): δ 7.87 (d, J=8.1 Hz, 2H), 7.36 (dd, J=8.1 Hz, J=7.2 Hz 2H), 7.31-7.20 (m, 6H), 6.64 (d, J=7.2 Hz, 2H), 3.04 (hept, J=6.8 Hz, 4H), 1.24 (d, J=6.9 Hz, 12H), 0.97 (d, J=6.9 Hz, 12H).13C{1H} NMR (CDCl3): δ 161.0, 147.5, 140.8, 135.4, 131.1, 129.5, 128.8, 127.8, 124.3, 123.4, 123.3, 28.6, 23.4, 23.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With n-butyllithium In tetrahydrofuran at 20℃; for 4h; | |
77.4% | With lithium hydroxide In water at 20℃; for 0.333333h; | 1.1 Step 1: Synthesis of intermediate product (L-1) 100mL flask acetoxy naphthoic metallocene quinone 5.0 g (27.45 mmol), benzyl triphenylphosphine bromide and 11.89 g (27.45 mmol), lithium hydroxide 2.88 g (68.62 mmol) and MC 250 mL wamul 150 ml were placed at room temperature for 20 minutes It was stirred. after confirming the completion of the reaction by TLC and extracted with MC. The intermediate L-1 and the solvent to the column to remove MC through the reduced pressure 5.44 g (yield: 77.4%) was obtained. |
(i) NaOEt, EtOH, (ii) /BRN= 879172/; Multistep reaction; |
7.75 g | With lithium hydroxide In dichloromethane; water at 20℃; for 0.25h; Inert atmosphere; | 3 In a nitrogen stream,The above phosphonium salt 15.9g (34.62mmol),Acenaphthenequinone (Intermediate (A1)) 6.307g (34.62mmol) was dissolved in 400ml of methylene chloride.Lithium hydroxide monohydrate * 2.905g (69.24mmol) was dissolved in 120ml of ion-exchanged water,Methylene chloride solution was added,Direct vigorously stirred for 15 minutes at room temperature.To the reaction solution was added ion-exchanged water 500ml,The dichloromethane layer was washed with water,The organic layer was dried over anhydrous magnesium sulfate,The solvent was distilled off under reduced pressure.The residue was purified by silica gel chromatography (developing solvent: ethyl acetate / hexane = 1/9) to giveTo give intermediate (A5).The yield was 7.75g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With sodium acetate In acetone for 4h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.57 g | In acetic acid for 1.5h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzonitrile; chlorobenzene at 84.9℃; for 1.25h; var. oxidants; | ||
With oxygen In benzonitrile; chlorobenzene at 84.85℃; for 2h; | ||
With tetrabutylammonium perchlorate; oxygen In benzonitrile; chlorobenzene at 84.85℃; for 1.5h; |
With N-hydroxyphthalimide; [bis(acetoxy)iodo]benzene; oxygen In chlorobenzene at 75℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 31% 2: 11% 3: 10% 4: 21% | In toluene at 110℃; for 2h; Further byproducts given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With 1-(propyl-3-sulfonate) 3-methylimidazol(3H)-1-ium phosphotungstate In water at 20℃; for 0.15h; | |
96% | With 1-butyl-3-methylimidazolium Tetrafluoroborate at 20℃; for 0.166667h; Green chemistry; | 2.4. General procedure for the synthesis of quinoxalines General procedure: A mixture of aromatic diamine derivatives (2 mmol) and a 1,2-dicarbonyl compound (2 mmol) in ionic liquid (2 mL) was stirred atroom temperature for the appropriate time. The progress of the reaction was monitored by TLC (n-Hexane: EtOAc, 7:3), after completion of the reaction, the reaction mixture was diluted with water and extracted using diethyl ether (30 ml). The combined organic layer was dried over anhydrous sodium sulphate and evaporated under reduced pressure to afford the corresponding product. The residual ionic liquid was dried under vacuum and reused. The same procedure was repeated for the reaction of aromatic anilines with isatin and acenaphthoquinone and phenaacylbromide. All the products obtained were characetrised by IR,1HNMR, 13CNMR and Mass studies. |
94% | With zirconium tetrakis(dodecyl sulfate) In water at 20℃; for 0.25h; |
91% | With niobium pentachloride In acetonitrile at 80 - 85℃; for 5h; | |
91% | at 130℃; for 0.5h; Ionic liquid; Microwave irradiation; | |
91% | With cerium(III) chloride heptahydrate In glycerol at 75℃; for 5h; | |
90% | With samarium(III) trifluoromethanesulfonate In acetonitrile for 4.5h; Reflux; | |
88% | With zinc trifluoromethanesulfonate In acetonitrile at 80 - 85℃; for 5h; | |
78% | With cobalt(III) 5,10,15,20-tetraarylporphyrin In ethanol; water at 20℃; for 0.166667h; | |
60% | In benzene for 8h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
form of mp: 220 degree resp. 230 degree; | ||
form of mp: 220 degree resp. 230 degree; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | Stage #1: acenaphthene quinone With acetic acid In acetonitrile at 80℃; Inert atmosphere; Stage #2: 2,6-diisopropylbenzenamine for 5.5h; Reflux; Inert atmosphere; | |
91% | With formic acid In ethanol at 65℃; for 168h; | 1 4.2.1. Preparation of bis[N,N'-(2,6-diisopropylphenyl)imino]acenaphthene (dppBIAN, 3a) To a slurry of acenaphthenequinone (1) (9.39 g, 51.5 mmol) and formic acid (1.0 mL) in ethanol (700 mL) was added 2,6-diisopropylaniline (2a) (19.8 mL, 105 mmol) in ethanol (200 mL) dropwise over 7 days at 65 °C. The reaction mixture was cooled to ambient temperature and the orange solid was collected by vacuum filtration. The remaining ethanol solution was concentrated in vacuo and cooled to -12 °C to give crystallized 3a (23.4 g, 91%); 1H NMR (400 MHz, CDCl3): δ 7.86 (d, J = 8.3 Hz, 2H, Aracen), 7.36 (t, J = 7.8 Hz, 2H, Aracen), 7.3-7.2 (m, 6H, Ar), 6.64 (d, J = 7.3 Hz, 2H, Ar), 3.03 (sept, J = 6.9 Hz, 4H, CHMe2), 1.24 (d, J = 6.9 Hz, 12H, MeCHMe), 0.98 (d, J = 6.9 Hz, 12H, MeCHMe); 13C{1H} NMR (100 MHz, CDCl3): δ 160.99, 147.51, 140.82, 135.44, 131.12, 129.51, 128.89, 127.89, 124.30, 123.48, 123.36, 28.63 (MeCHMe), 23.44 (MeCHMe), 23.15 (MeCHMe); IR, v/cm-1: 3065, 2961, 2925, 2867, 1668, 1590, 1466, 1455, 1428. |
91% | With acetic acid In acetonitrile for 5h; Inert atmosphere; Reflux; | 2.1.1.1. Bis[N,N′-(2,6-diisopropylphenyl)imino]acenaphthene (BIAN). Acenaphthenequinone (1.35 g, 7.4 mmol) was dispersed in acetonitrile (65 ml) and refluxed for 45 min. Acetic acid (12 ml)was then added and stirring continued until the total dissolution ofacenaphthenequinone. 2,6-Diisopropylaniline (3 ml, 16 mmol) wasadded directly. The solutionwas refluxed for further 5 h and then cooledto room temperature. The formed precipitate was isolated by filtrationand washed with n-hexane. After air drying, bis[N,N′-(2,6-diisopropylphenyl) imino]acenaphthenewas obtained as a bright yellowpowder (3.37 g, 91%).1H NMR (500 MHz, CDCl3, δ): 1.27 (d, 24H), 3.07 (m, 4H), 6.68 (d,4H), 7.3 (t, 2H), 7.42 (t, 2H), 7.92 (d, 4H), UV-Vis (toluene) λmax:427 nm. |
90% | In acetic acid; acetonitrile for 5.5h; Reflux; Inert atmosphere; | |
87% | With acetic acid In acetonitrile at 80℃; for 144h; | |
87% | With acetic acid In acetonitrile at 80℃; for 144h; | |
87% | With formic acid In methanol at 45℃; for 12h; Inert atmosphere; Schlenk technique; | |
85% | With acetic acid In acetonitrile for 1.5h; Heating; | |
85% | Stage #1: 2,6-diisopropylbenzenamine; acenaphthene quinone With acetic acid; zinc(II) chloride Stage #2: With sodium oxalate; potassium carbonate In water | |
83% | Stage #1: acenaphthene quinone With acetic acid In acetonitrile at 92℃; Inert atmosphere; Stage #2: 2,6-diisopropylbenzenamine In acetonitrile at 92℃; Inert atmosphere; | |
82% | With toluene-4-sulfonic acid In ethanol for 12h; Reflux; | 5 mmol of acenaphthequinone, 13 mmol of 2,6-diisopropylaniline, 42 mL of ethanol and 0.1 g of p-toluenesulfonic acid were added to a 100 mL reaction vial and heated to reflux for 12 h to give a acenaphthequinone diimine ligand with a yield of 82%. |
80% | Stage #1: acenaphthene quinone In acetonitrile for 1h; Reflux; Stage #2: 2,6-diisopropylbenzenamine In acetonitrile for 5h; Reflux; | |
80% | Stage #1: acenaphthene quinone In acetonitrile for 1h; Reflux; Stage #2: 2,6-diisopropylbenzenamine In acetonitrile for 5h; Reflux; | |
69% | With acetic acid In acetonitrile for 1.5h; Reflux; | 3 (Synthesis Example 3:Synthesis of 1,2-Bis [(2,6-diisopropylphenyl) imino] acenaphthene) 1.54 g (182.2 mmol) of acenaphthoquinone was dissolved in 62 mL of acetonitrile under air at room temperature,Stirring was started.The solution was refluxed for 1 hour,14.5 mL (253.6 mmol) of acetic acid was added.After confirming that the reaction solution became uniform,2,6-diisopropylaniline was added dropwise over 30 minutes.The resulting solid was filtered off,After rinsing and washing twice with 30 mL of hexane,By drying under reduced pressure,11.3 g (yield: 69%) of a yellow powder was obtained. |
58% | With formic acid In ethanol for 12h; Inert atmosphere; Reflux; | 3 Example 3 Synthesis of α-Diimine Compound A3 Under nitrogen atmosphere,100mL was added to the acenaphthenequinone branched-necked flask 1.82g (10mmol),2,6-diisopropylaniline4.2g (24mmol),Ethanol 60 mL and formic acid 0.5 mL,The reaction was heated to reflux for 12 hours.2.9 g of a-diimine compound was obtained with a yield of 58%. |
With acetic acid In acetonitrile Reflux; | ||
In acetonitrile Reflux; | ||
In acetonitrile Schlenk technique; | ||
With acetic acid Reflux; | 76 Synthesis of ligand L1s (comparative ligand) In a 100 mL egg-shaped flask, acenaphthoquinone (1.822 g, 10 mmol), 2,6-diisopropylaniline(4.0 mL, 21 mmol) and two drops of anhydrous acetic acid were added. The reaction was heated at reflux and monitored by TLC until ended. After the reaction was completed, the orange red diimine product was obtained by crystallizing from anhydrous methanol.. 1H NMR (300 MHz, CDCl3): δ =7.89 (2 H, d), 7.36 (2 H, t), 7.26 (6 H, s), 6.64 (2 H, d), 3.03 (4 H, m), 1.24 (12 H, d), 0.98 (12 H, d). | |
In acetonitrile | ||
In acetonitrile Reflux; | ||
With acetic acid Reflux; | ||
Inert atmosphere; | ||
Acidic conditions; | ||
With toluene-4-sulfonic acid In toluene at 110℃; | ||
With acetic acid In acetonitrile | ||
With acid In methanol | ||
In acetonitrile Reflux; | ||
In acetonitrile Inert atmosphere; Glovebox; | ||
With acetic acid In acetonitrile Reflux; | ||
With toluene-4-sulfonic acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With toluene-4-sulfonic acid In toluene at 140℃; for 6h; Inert atmosphere; Schlenk technique; | 2.2 Synthesis of bis(arylimino)-acenaphthene (Ar-BIAN) ligands (L1-L3) General procedure: All the ligands were prepared according to the Schiff's base reactions of acenaphthylene-1,2-dione (0.91 g, 5 mmol) with substituted anilines (11 mmol) in the presence of catalytic amount of p-toluene sulfonic acid in toluene. Reaction mixture was refluxed for 6 hours at 140°C. Dean-Stark apparatus was used in order to remove secondary product (H2O) from the reaction environment. After completion of the reaction, the mixture was cooled to room temperature, solvent was removed under vacuum and crude product was recrystallized twice with ethanol.N,N′-bis(4-fluorophenyl)acenaphthene (4-FPh-BIAN) (L1): Obtained as a yellow solid. Yield: 1.41 g, 76 %. 1H NMR (300 MHz, CDCl3) δ (ppm): 7.84 (d, J=8.3 Hz, 2H), 7.35 (dd, J=8.3, 7.2 Hz, 2H), 7.18 - 7.09 (m, 4H), 7.09 - 7.00 (m, 4H), 6.90 (d, J=7.2 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ (ppm): 161.90, 161.89, 161.45, 159.04, 147.67, 147.64, 141.94, 131.39, 129.33, 128.41, 127.77, 123.95, 119.87, 119.80, 116.48, 116.25. 19F NMR (470 MHz, CDCl3) δ (ppm): -119.19. FT-IR (cm-1): 3049 (w), 1658 (m), 1633 (m), 1590 (m), 1496 (s), 1487 (s), 1435 (m), 1419 (m), 1358 (m), 1273 (m), 1211 (s), 1203 (s), 1147 (m), 1090 (m), 1042 (m), 1008 (m), 925 (m), 827 (s), 792 (m), 780 (m), 745 (m), 732 (m), 720 (m). Anal. Calcd. For C24H14F2N2 (368.39): C, 78.25; H, 3.83; N, 7.60%. Found: C, 78.42; H, 3.78; N, 7.64%. |
76% | Stage #1: 4-fluoroaniline; acenaphthene quinone In toluene for 0.5h; Reflux; Stage #2: With toluene-4-sulfonic acid In toluene at 140℃; for 12h; Dean-Stark; | 1 Example 1. Preparation of the ligand represented by formula L1 (N,N'-bis(4-fluorophenyl)acenaphthenequinone) Weigh 0.91g (5mmol) acenaphthenequinone and 1.22g (5.00mmol) 4-fluoroaniline into the reaction flask, add about 20mL of toluene solvent, heat and stir to reflux, and then add a catalytic equivalent (20%, 0.190g) of p-toluenesulfonic acid to the reaction flask after half an hour, the reaction mixture was heated to reflux for 6h. After cooling to room temperature, the reaction mixture was refluxed at 140°C for 6 hours. In order to remove by-products (H2O) from the reaction environment, Dean-Stark equipment was used. After the completion of the reaction, the mixture was cooled to room temperature, the solvent was removed in vacuo, and the crude product was recrystallized twice with ethanol to obtain 1.41 g of yellow powder, namely L1,N,N'-bis(4-fluorophenyl)acenaphthene Quinone, yield: 76%. |
75% |
65% | Stage #1: 4-fluoroaniline; acenaphthene quinone With zinc(II) chloride In acetic acid for 1h; Reflux; Stage #2: With potassium carbonate In water for 2h; Reflux; | |
With acetic acid; zinc(II) chloride In toluene for 1h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 41% 2: 26% 3: 23% | With samarium diiodide; water In tetrahydrofuran at 20℃; for 0.00277778h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With methanesulfonic acid; trifluorormethanesulfonic acid at 20℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methanesulfonic acid; trifluorormethanesulfonic acid at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
toluene-4-sulfonic acid; In benzene;Dean-Stark trap; Heating / reflux; | L3, e.g., 1-(2-methyl-1-naphthylimino)-2-acenaphthenenone, illustrated below, was synthesized by adding 2-Methylnaphthylamine (0.43 g, 2.74 mmol) to a stirred slurry of 1,2-acenaphthenedione (0.50 g, 2.74 mmol) in benzene (90 mL). A catalytic amount of p-toluenesulfonic acid was added to the resulting slurry and the reaction mixture was then refluxed. The water formed was separated via a Dean-Stark trap. The reaction was refluxed for 2 hours and then left to stand overnight under argon. The reaction mixture was obtained as a deep green/brown solution which contained about 20% of the bisimine and 80% of the desired monoimine by G.C. analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In benzene Dean-Stark trap; Heating / reflux; | L4, e.g., 1-(9-phenanthreneimino)-2-acenaphthenenone, illustrated below, was prepared by adding a solution of 9-aminophenanthrene (0.26 g, 1.37 mmol) to a stirred slurry of 1,2-acenaphthenedione (0.50 g, 2.74 mmol) in benzene (90 mL). A catalytic amount of p-toluenesulfonic acid was added to the resulting slurry and the reaction mixture was then refluxed. The water formed was separated via a Dean-Stark trap. The reaction was refluxed for 2 hours and then left to stand overnight under argon. The solvent was removed by rotavap and the remaining solids were recrystallized from methanol. A solid was obtained that contained 74% of the desired monoimine and 26% of 1,2-acenaphthenedione by G.C. analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluorormethanesulfonic acid; trifluoroacetic acid at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With methanesulfonic acid; trifluorormethanesulfonic acid at 20℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 8.5% 2: 30% | With toluene-4-sulfonic acid In water; toluene for 168h; Heating / reflux; | 1 Example 1; To a suspension of 1.00 g acenaphtenequinone (5.48 mmol/1 eq) in 50ml of toluene was added 0.83 g of 2- (4-aminophenyl)ethanol (6.02mmol/1.1 eq), 1.94g of 2,4,6-triphenylaniline (6.02 mmol/1.1 eq) and 0.06 g of p-toluenesulfonic acid monohydrate (0.06 mol%). The reaction mix- ture was refluxed for 7 d. The water was removed by azeotropic distilla- tion. The reaction was followed by thin layer chromatography on silica us- ing Whatman 250 µm Layer, flexible plates for TLC, PE SIL G/UV (Whatman plc, Kent ME16 OLS, UK) to ensure completion of the reaction. The unsymmetrical diimine was purified by flash chromatography (ethyl acetate: hexane / 1:1 volume) and isolated in 30% yield (1.0g), as a deep- red solid. Flash chromatography was carried out under standard condi- tions using procedures described in W. C. Still, et al., J. Org. Chem. , vol. 43, p. 2923-2925 (1978), which is hereby included by reference. A 36 cm long x 4.5 cm diameter column was used and it was about 2/3 filled with silica gel (Scientific Adsorbents No.02826-25, particle size 22-63 µm, pore size 60 Angstroms, Scientific Adsorbents, Inc. , Atlanta, GA 30340, USA). Two products symmetrical diimine 1 containing no hydroxyl groups (Rf = 0.83) and unsymmetrical diimine 2 containing one hydroxyl group (Rf = 0.36) were isolated by flash chromatography. The solvent was removed under vacuum. The diimines 1 and 2 were obtained, as deep-red solids in 8.5% (0.37g) and 30% (1g) yields correspondingly. Diimine 3 containing 2 hydroxyl groups apparently remained on the column and probably could have been eluted with a more polar solvent (mixture). ¹H NMR (300 MHz, CDCI3, 25°C): 2.93 (m, 2 H, CH2), 4.14 (m, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With toluene-4-sulfonic acid In toluene at 140℃; for 6h; Inert atmosphere; Schlenk technique; | 2.2 Synthesis of bis(arylimino)-acenaphthene (Ar-BIAN) ligands (L1-L3) General procedure: All the ligands were prepared according to the Schiff's base reactions of acenaphthylene-1,2-dione (0.91 g, 5 mmol) with substituted anilines (11 mmol) in the presence of catalytic amount of p-toluene sulfonic acid in toluene. Reaction mixture was refluxed for 6 hours at 140°C. Dean-Stark apparatus was used in order to remove secondary product (H2O) from the reaction environment. After completion of the reaction, the mixture was cooled to room temperature, solvent was removed under vacuum and crude product was recrystallized twice with ethanol. |
68% | Stage #1: 4-trifluoromethylphenylamine; acenaphthene quinone In toluene for 0.5h; Reflux; Stage #2: With toluene-4-sulfonic acid In toluene at 140℃; for 12h; Dean-Stark; | 3 Example 3. Preparation of the ligand represented by formula L3 (N, N'-p-3-trifluoromethylphenylacenaphthenequinone) Weigh 0.91g (5mmol) acenaphthenquinone and 1.60g (5.00mmol) p-trifluoromethylaniline into the reaction flask, add about 20mL toluene solvent, heat and stir to reflux, after half an hour, add a catalytic equivalent (20 %, 0.190g) p-toluenesulfonic acid, the reaction mixture was heated to reflux for 6h. After cooling to room temperature, the reaction mixture was refluxed at 140°C for 6 hours. In order to remove by-products (H2O) from the reaction environment, Dean-Stark equipment was used. After the completion of the reaction, the mixture was cooled to room temperature, the solvent was removed in vacuo, and the crude product was recrystallized twice with ethanol to obtain 1.60 g of gray-yellow powder, that is, N,N'-p-trifluoromethylphenylacenaphthenequinone. Yield: 68%. |
58% | Stage #1: 4-trifluoromethylphenylamine; acenaphthene quinone With zinc(II) chloride In acetic acid for 1h; Reflux; Stage #2: With potassium carbonate In water for 2h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | for 0.25h; Microwave irradiation; neat (no solvent); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With polycyclic aromatic carbon sheets with sulfonic acid In ethanol at 80℃; for 3h; | General procedure for the preparation of spiro[4H-pyran-3,30-oxindole]derivatives General procedure: A mixture of isatin (1 mmol), malononitrile or cyanoacetic esters (1 mmol), 1,3-dicarbonyl compounds (1 mmol), and the catalyst (10 wt %) in ethanol (3 ml) was stirred at 80 C for a specified time (see Table 2). After complete conversion, as indicated by TLC, the reaction mixture was cooled to room temperature. The resulting solid precipitate was filtered and dried along with the catalyst. Further purification of the product was performed by recrystallization using ethanol and the catalyst was recovered by filtration. |
90% | With (2-hydroxy-ethyl)ammonium acetate In water at 90℃; for 0.5h; | |
88% | With gold(III) chloride trihydrate In decaethylene glycol at 70℃; for 0.5h; |
88% | With caspian isinglass In water at 60℃; for 0.2h; | General procedure for synthesis of spirooxindoles 4a-4wand spiroacenaphthylene derivatives 6a-6e catalyzed by IG General procedure: A mixture of isatin derivatives (1a-1d, 1 mmol) oracenaphthoquinone (5, 1 mmol), methylene nitriles (2a,2b, 1 mmol), 1,3-dicarbonyl (3, 1 mmol), and 5 mg IG in3 cm3 H2O was stirred at 60 C for the mentioned timeshown in tables. Rapid conversion of reagents can beclearly confirmed by reaction color change. The progress ofthe reaction was monitored by TLC using EtOAc/n-hexane(1:3) as an eluent. Upon completion, the reaction mixturewas allowed to cool to room temperature and the precipitatewas obtained from the reaction mixture by filtration.The product 4a was dissolved in DMSO and the catalystwas separated by simple filtration. Pure products wereafforded by evaporation of the solvent under reduced pressure. |
87% | With ammonium chloride In water at 80℃; for 0.166667h; | |
82% | With 1,8-diazabicyclo[5.4.0]undec-7-ene In water for 0.25h; Reflux; | Typical Procedure for the Synthesis of Ethyl 2’-Amino-7’-methyl-2,5’-dioxo-5’,6’,7’,8’-tetrahydro-2H-spiro[acenaphthylene-1,4’-chromene]-3’-carboxylate (4j) General procedure: In a typical procedure, acenaphthenequinone (1 equiv.), ethyl cyanoacetate (1.2 equiv.), and 10 mL of water were placed in a 50-mL round-bottomed flask mounted over a magnetic stirrer. DBU (10 mol%) was added to the mixture, and the contents were stirred. 5-Methyl-cyclohexane-1,3-dione (1 equiv.) was added to this stirred mixture, and the reaction mixture was refluxed for15 min. The progress of the reaction was monitored by TLC for disappearance of 5-methyl-cyclohexane-1,3-dione. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and water was decanted.Ethanol (3mL) was added to the mixture, and the mixture was stirred. The solid product was collected by Buchner filtration and subsequently washed with ethanol to give the analytically pure spiropyran (4j) without recrystallization. The aqueous filtrate containing DBU was used as such for investigating the recyclability of the catalyst. The product was identified as ethyl 2'-amino-7'-methyl-2,5'-dioxo-5',6',7',8'-tetrahydro-2H-spiro[acenaphthylene-1,4'-chromene]-3'-carboxylate (4j) by spectral data |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With 4,4′-(butane-1,4-diyl)bis(1-sulfo-1,4-diazabicyclo[2.2.2]octane-1,4-diium) tetrachloride In water at 90℃; for 0.25h; | 2.2. General procedure for the synthesis of 2-amino-3-cyano-4H-pyrans derivatives General procedure: A mixture of an isatin (1 mmol), molononitrile (1.1 mmol), C-H activated acid (1 mmol), and C4(DABCO-SO3H)2*4Cl (5 mol%) in water (3 mL) was stirred at 90 °C for an appropriate time. The reaction progress was monitored by TLC and also precipitation of the products from the reaction mixture. After completion of the reaction, the mixture was cooled to room temperature and the solid product was filtered, washed with cold distilled water (2 mL) to obtain essentially pure products. The solid products can be recrystallized from ethanol if necessary. |
95% | With 1,1'-(butane-1,4-diyl)bis(1,4-diazabicyclo[2.2.2]octan-1-ium) hydroxide In water at 80℃; for 0.25h; Green chemistry; | 2.4.6. General procedure for the synthesis of 2-amino-3-cyano-4H-pyrans derivatives General procedure: A mixture of an isatin (1mmol), molononitrile (1mmol), CH activatedacid (1mmol), and [C4(DABCO)2]·2OH(2mol%) inwater (3mL)was stirred at 80 °C. The reaction progress was monitored by TLC [eluent:n-hexane:EtOAc (9:2)] (It is important to that by beginning of thereaction the products were precipitated in the reaction medium).After completion of the reaction, the mixture was cooled to room temperature and the solid product was filtered, washed with cold distilledwater (2 mL) to obtain essentially pure products. The solid productswere recrystallized from ethanol if necessary. |
94% | With 1-butyl-3-methylimidazolium hydroxide In neat (no solvent) at 20℃; for 0.333333h; |
94% | With (2-hydroxy-ethyl)ammonium acetate In water at 90℃; for 0.5h; | |
94% | With 1-deoxy-1-(methylamino)-D-glucitol In ethanol; water at 20℃; for 0.416667h; Green chemistry; | |
94% | In water at 20℃; for 4h; Irradiation; Green chemistry; | 2.2. The overall process of preparing (4a-i) General procedure: Multifarious reagents including acenaphthequinone (1, 1.0 mmol),malononitrile (2, 1.0 mmol) and various reagents including a-methylencarbonylcompounds/enols (3a-i, 1.0 mmol) were reacted opposed toCFL (23 W) irradiation at room temperature in aqueous ethyl lactate(2:1, 3 mL) (Scheme 1). This was observed by TLC that employed (ethyl acetate/n-hexane (1:3)). Afterwards, the filtering of the acquired solidwas conducted, then the solid was rinsed water (2 × 3 mL) and ethanol(2 × 3 mL) and solid composition became recrystallized by EtOH. Theproducts were classified after the comparison of spectroscopic information(1H NMR). Support for this manuscript can be found in the onlineversion. |
93% | In water at 80℃; for 0.25h; | 4.3. General non-catalytic multicomponent procedure General procedure: A mixture of acenaphthenequinone 1 (5 mmol), cyclic CH-acid 2 (5 mmol), malononitrile (5 mmol), and water (3 mL) was stirred at 80 °C for 15 min. Then the reaction mixture was cooled and filtered to isolate the solid product 3, which was washed with ethanol (2×5 mL), and dried under reduced pressure. For 3h, the mixture of acenaphthenequinone 1 (5 mmol), 2h (5 mmol), and malononitrile (5 mmol) was boiled in n-propanol (3 mL); the product was isolated as above. |
93% | With polycyclic aromatic carbon sheets with sulfonic acid In ethanol at 80℃; for 3h; | General procedure for the preparation of spiro[4H-pyran-3,30-oxindole]derivatives General procedure: A mixture of isatin (1 mmol), malononitrile or cyanoacetic esters (1 mmol), 1,3-dicarbonyl compounds (1 mmol), and the catalyst (10 wt %) in ethanol (3 ml) was stirred at 80 C for a specified time (see Table 2). After complete conversion, as indicated by TLC, the reaction mixture was cooled to room temperature. The resulting solid precipitate was filtered and dried along with the catalyst. Further purification of the product was performed by recrystallization using ethanol and the catalyst was recovered by filtration. |
93% | With mesoporous silica SBA-15 supported 1,4-diazabicyclo[2.2.2]octane In water at 50℃; for 0.0666667h; | EXPERIMENTAL General procedure: A mixture of isatins or acenaphthoquinone (1 mmol), activated methylene reagents (1 mmol), 1,3-dicarbonyl compounds (1 mmol) and SBA-15-DABCO (0.085 g, 7 mol%) in water was stirred at 25 or 50 °C. Upon compilation, monitored by TLC (n-hexane / ethyl acetate 2 / 1), the reaction mixture was allowed to cool to room temperature. The precipitate was filtered and dissolved in acetone. The catalyst was separated by filtration of this solution. The solution was concentrated under vaccum to afford the product, which was purified by recrystallization in the ethanol. |
93% | With nickel ferrite(at)SiO2(at)melamine magnetic nanoparticles In ethanol for 0.25h; Reflux; Green chemistry; | 2.4. General procedure for the synthesis of spiropyran derivatives General procedure: The mixture of the ninhydrin or acenaphthenequinone(1 mmol), malononitrile/ethyl cyanoacetate (1 mmol), 1,3-dicarbonyl compounds (1 mmol) and 0.025 g NiFe2O4(at)SiO2(at)Melaminein 5mL of ethanol were added to it. The mixture was run in reflux condition for an appropriate time. Upon completion of the reaction, monitored by TLC (hexane/AcOEt 1:3), the magnetic catalyst was removed by an external magnet and the generated solid product was filtered and recrystallized by EtOH to give pure products. Spectral data of all compounds are available on the supporting information. |
92% | With FeNi3 magnetic nanoparticles supported SiO2 In water at 20℃; Green chemistry; | |
92% | With D-glucose In water at 45℃; for 0.0833333h; Green chemistry; | |
92% | With Eosin Y In water at 20℃; for 3.5h; Irradiation; Green chemistry; | 2.1.1. Overall process of preparing (4a-j) General procedure: To a mixture of malononitrile (2, 1.0 mmol), acenaphthequinone (1,1.0 mmol) and various reagents including a-methylencarbonyl compounds/enols (3a-j, 1.0 mmol) in a EL1/H2O (2:1) (3 mL), was addedNa2 eosin Y (1.5 mol%), under white light emitting diode (LED) (18 W)irradiation (Scheme 3). The mixture was stirred for 4 h at ambient temperature. The reaction progress was monitored by TLC utilizing nhexane/EtOAc (3:1) as an eluent. After completing the reaction, theachieved solid was filtered, rinsed with water and the crude solid was recrystallized from ethanol to provide the pure material without requiring more purification |
91% | With caspian isinglass In water at 60℃; for 0.166667h; | General procedure for synthesis of spirooxindoles 4a-4wand spiroacenaphthylene derivatives 6a-6e catalyzed by IG General procedure: A mixture of isatin derivatives (1a-1d, 1 mmol) oracenaphthoquinone (5, 1 mmol), methylene nitriles (2a,2b, 1 mmol), 1,3-dicarbonyl (3, 1 mmol), and 5 mg IG in3 cm3 H2O was stirred at 60 C for the mentioned timeshown in tables. Rapid conversion of reagents can beclearly confirmed by reaction color change. The progress ofthe reaction was monitored by TLC using EtOAc/n-hexane(1:3) as an eluent. Upon completion, the reaction mixturewas allowed to cool to room temperature and the precipitatewas obtained from the reaction mixture by filtration.The product 4a was dissolved in DMSO and the catalystwas separated by simple filtration. Pure products wereafforded by evaporation of the solvent under reduced pressure. |
90% | With sodium hydrogencarbonate In ethanol for 0.416667h; Reflux; | |
90% | With Mn(II) complex with 2,2'-bipyridine 1,1'-dioxide ligand within nanoreactors of MCM-41 In water for 0.25h; Reflux; Green chemistry; | |
90% | With graphitic carbon nitride nanosheets decorated by Fe3O4 nanoparticles In water at 80℃; for 0.666667h; Green chemistry; | 2.3.1. General procedure for the preparation of spirooxindole derivatives General procedure: A mixture of isatin (1 mmol), malononitrile (1 mmol), C -H ac- tivated acid compound (1 mmol) and Fe 3 O 4 / g -C 3 N 4 (0.025 g) in H 2 O (5 mL) at 80 °C was stirred for the appropriate time [TLC: n - hexane: ethyl acetate (5:4)]. After completion of the reaction, the mixture was cooled to room temperature and filtered off, ethanol (10 mL) was added and the catalyst was removed using an exter- nal magnet. Evaporation of the solvent from mixture gave the solid residue which recrystallized from EtOH to afford the pure product. Finally Fe 3 O 4 / g -C 3 N 4 washed with H 2 O and ethanol and be used for the next run. |
81% | With SBA-Pr-NH2 In ethanol at 20℃; for 0.0833333h; | |
80% | With (benzyl)(2-(N,N-dimethylamino)ethyl)dimethylammonium chloride In water at 80℃; for 1h; | |
80% | With 1,8-diazabicyclo[5.4.0]undec-7-ene In water for 0.25h; Reflux; | Typical Procedure for the Synthesis of Ethyl 2’-Amino-7’-methyl-2,5’-dioxo-5’,6’,7’,8’-tetrahydro-2H-spiro[acenaphthylene-1,4’-chromene]-3’-carboxylate (4j) General procedure: In a typical procedure, acenaphthenequinone (1 equiv.), ethyl cyanoacetate (1.2 equiv.), and 10 mL of water were placed in a 50-mL round-bottomed flask mounted over a magnetic stirrer. DBU (10 mol%) was added to the mixture, and the contents were stirred. 5-Methyl-cyclohexane-1,3-dione (1 equiv.) was added to this stirred mixture, and the reaction mixture was refluxed for15 min. The progress of the reaction was monitored by TLC for disappearance of 5-methyl-cyclohexane-1,3-dione. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and water was decanted.Ethanol (3mL) was added to the mixture, and the mixture was stirred. The solid product was collected by Buchner filtration and subsequently washed with ethanol to give the analytically pure spiropyran (4j) without recrystallization. The aqueous filtrate containing DBU was used as such for investigating the recyclability of the catalyst. The product was identified as ethyl 2'-amino-7'-methyl-2,5'-dioxo-5',6',7',8'-tetrahydro-2H-spiro[acenaphthylene-1,4'-chromene]-3'-carboxylate (4j) by spectral data |
76% | With gold(III) chloride trihydrate In decaethylene glycol at 70℃; for 0.5h; | |
75% | With ammonium chloride In water at 80℃; for 0.166667h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With caspian isinglass In lithium hydroxide monohydrate at 60℃; for 0.25h; | General procedure for synthesis of spirooxindoles 4a-4wand spiroacenaphthylene derivatives 6a-6e catalyzed by IG General procedure: A mixture of isatin derivatives (1a-1d, 1 mmol) oracenaphthoquinone (5, 1 mmol), methylene nitriles (2a,2b, 1 mmol), 1,3-dicarbonyl (3, 1 mmol), and 5 mg IG in3 cm3 H2O was stirred at 60 C for the mentioned timeshown in tables. Rapid conversion of reagents can beclearly confirmed by reaction color change. The progress ofthe reaction was monitored by TLC using EtOAc/n-hexane(1:3) as an eluent. Upon completion, the reaction mixturewas allowed to cool to room temperature and the precipitatewas obtained from the reaction mixture by filtration.The product 4a was dissolved in DMSO and the catalystwas separated by simple filtration. Pure products wereafforded by evaporation of the solvent under reduced pressure. |
90% | With polycyclic aromatic carbon sheets with sulfonic acid In ethanol at 80℃; for 3.5h; | General procedure for the preparation of spiro[4H-pyran-3,30-oxindole]derivatives General procedure: A mixture of isatin (1 mmol), malononitrile or cyanoacetic esters (1 mmol), 1,3-dicarbonyl compounds (1 mmol), and the catalyst (10 wt %) in ethanol (3 ml) was stirred at 80 C for a specified time (see Table 2). After complete conversion, as indicated by TLC, the reaction mixture was cooled to room temperature. The resulting solid precipitate was filtered and dried along with the catalyst. Further purification of the product was performed by recrystallization using ethanol and the catalyst was recovered by filtration. |
90% | With Mn(II) complex with 2,2'-bipyridine 1,1'-dioxide ligand within nanoreactors of MCM-41 In lithium hydroxide monohydrate for 0.25h; Reflux; Green chemistry; |
89% | With 2-hydroxyethylammonium acetate In lithium hydroxide monohydrate at 90℃; for 0.5h; | |
88% | With [Cu(2,2′-bipyridine-1,1′-dioxide)2*2H2O]2+/montmorillonite KSF In ethanol; lithium hydroxide monohydrate for 0.933333h; Reflux; Green chemistry; | Synthesis ofspirochromene (19a) andspiroacenaphthylene (19b-h): general procedure General procedure: A mixture of isatins (18) or acenaphthenequinone (20) (1.0 mmol), malononitrile (8a) or ethyl cyanoacetate (8b) (1.0 mmol) and 1,3-dicarbonyl compounds (dimedone (9), ethyl acetoacetate (11), meldrum′s acid (17)) or activated phenols (α-naphthol (13), 4-hydroxycoumarin (15)) (1.0 mmol), and also [Cu(bpdo)2·2H2O]2+/Mont (0.2mol%) in EtOH/H2O (4mL, 1:1) were placed in a 10mL round-bottomed fask and heated under refux conditions. The progress of the reaction was monitored by TLC (n-hexane/ethyl acetate, (1:1)). Upon completion of the reaction, the mixture was cooled to room temperature, fltered, and washed with EtOH at room temperature. The fltration was evaporated under reduced pressure, and the obtained residue was recrystallized from EtOH to aford the expected products (Table4). |
84% | With mesoporous silica SBA-15 supported 1,4-diazabicyclo[2.2.2]octane In lithium hydroxide monohydrate at 50℃; for 0.25h; | EXPERIMENTAL General procedure: A mixture of isatins or acenaphthoquinone (1 mmol), activated methylene reagents (1 mmol), 1,3-dicarbonyl compounds (1 mmol) and SBA-15-DABCO (0.085 g, 7 mol%) in water was stirred at 25 or 50 °C. Upon compilation, monitored by TLC (n-hexane / ethyl acetate 2 / 1), the reaction mixture was allowed to cool to room temperature. The precipitate was filtered and dissolved in acetone. The catalyst was separated by filtration of this solution. The solution was concentrated under vaccum to afford the product, which was purified by recrystallization in the ethanol. |
83% | With ammonia hydrochloride In lithium hydroxide monohydrate at 80℃; for 0.166667h; | |
83% | With 1,4-diaza-bicyclo[2.2.2]octane In lithium hydroxide monohydrate at 75℃; for 3.5h; Green chemistry; | |
82% | With hydrogen tetrachloroaurate(III) trihydrate In 2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol at 70℃; for 0.5h; | |
80% | With triethylamine In ethanol for 4.5h; Reflux; | |
80% | With 1,8-diazabicyclo[5.4.0]undec-7-ene In lithium hydroxide monohydrate for 0.25h; Reflux; | Typical Procedure for the Synthesis of Ethyl 2’-Amino-7’-methyl-2,5’-dioxo-5’,6’,7’,8’-tetrahydro-2H-spiro[acenaphthylene-1,4’-chromene]-3’-carboxylate (4j) General procedure: In a typical procedure, acenaphthenequinone (1 equiv.), ethyl cyanoacetate (1.2 equiv.), and 10 mL of water were placed in a 50-mL round-bottomed flask mounted over a magnetic stirrer. DBU (10 mol%) was added to the mixture, and the contents were stirred. 5-Methyl-cyclohexane-1,3-dione (1 equiv.) was added to this stirred mixture, and the reaction mixture was refluxed for15 min. The progress of the reaction was monitored by TLC for disappearance of 5-methyl-cyclohexane-1,3-dione. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and water was decanted.Ethanol (3mL) was added to the mixture, and the mixture was stirred. The solid product was collected by Buchner filtration and subsequently washed with ethanol to give the analytically pure spiropyran (4j) without recrystallization. The aqueous filtrate containing DBU was used as such for investigating the recyclability of the catalyst. The product was identified as ethyl 2'-amino-7'-methyl-2,5'-dioxo-5',6',7',8'-tetrahydro-2H-spiro[acenaphthylene-1,4'-chromene]-3'-carboxylate (4j) by spectral data |
75% | With SBA-Pr-NH2 In ethanol at 20℃; for 0.166667h; | |
55 %Spectr. | With choline chloride at 80℃; for 6h; Green chemistry; | General procedure for spiro-2-oxindole preparation General procedure: In the test tube (0.5 mmol) isatin or acenaphthoquinone with 0.5mmol active methylene and 0.5 mmol 1,3-dicarbonyl compounds/4Hcumarin/α naphtol and 0.5 mL urea:ChCl were added. The reaction mixture was stirred and heated to 80 °C. The reaction completion was monitored by TLC. After reaction completion about 5 mL water was added to reaction mixture in the cases that the solid was obtained and the solid was filtered, and in the cases that a viscose liquid was obtained after water addition the ethyl acetate was added to extract the product and the organic layer was removed under vacuum. The products were recrystallized from ethanol to give pure corresponding compounds |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With 4,4′-(butane-1,4-diyl)bis(1-sulfo-1,4-diazabicyclo[2.2.2]octane-1,4-diium) tetrachloride In lithium hydroxide monohydrate at 90℃; for 0.2h; | 2.2. General procedure for the synthesis of 2-amino-3-cyano-4H-pyrans derivatives General procedure: A mixture of an isatin (1 mmol), molononitrile (1.1 mmol), C-H activated acid (1 mmol), and C4(DABCO-SO3H)2*4Cl (5 mol%) in water (3 mL) was stirred at 90 °C for an appropriate time. The reaction progress was monitored by TLC and also precipitation of the products from the reaction mixture. After completion of the reaction, the mixture was cooled to room temperature and the solid product was filtered, washed with cold distilled water (2 mL) to obtain essentially pure products. The solid products can be recrystallized from ethanol if necessary. |
98% | With 1,1'-(butane-1,4-diyl)bis(1,4-diazabicyclo[2.2.2]octan-1-ium) hydroxide In lithium hydroxide monohydrate at 80℃; for 0.2h; Green chemistry; | 2.4.6. General procedure for the synthesis of 2-amino-3-cyano-4H-pyrans derivatives General procedure: A mixture of an isatin (1mmol), molononitrile (1mmol), CH activatedacid (1mmol), and [C4(DABCO)2]·2OH(2mol%) inwater (3mL)was stirred at 80 °C. The reaction progress was monitored by TLC [eluent:n-hexane:EtOAc (9:2)] (It is important to that by beginning of thereaction the products were precipitated in the reaction medium).After completion of the reaction, the mixture was cooled to room temperature and the solid product was filtered, washed with cold distilledwater (2 mL) to obtain essentially pure products. The solid productswere recrystallized from ethanol if necessary. |
93% | With 1-(carboxymethyl)pyridinium iodide In lithium hydroxide monohydrate for 0.5h; Reflux; Green chemistry; |
92% | In lithium hydroxide monohydrate at 80℃; for 0.25h; | 4.3. General non-catalytic multicomponent procedure General procedure: A mixture of acenaphthenequinone 1 (5 mmol), cyclic CH-acid 2 (5 mmol), malononitrile (5 mmol), and water (3 mL) was stirred at 80 °C for 15 min. Then the reaction mixture was cooled and filtered to isolate the solid product 3, which was washed with ethanol (2×5 mL), and dried under reduced pressure. For 3h, the mixture of acenaphthenequinone 1 (5 mmol), 2h (5 mmol), and malononitrile (5 mmol) was boiled in n-propanol (3 mL); the product was isolated as above. |
92% | With [Cu(2,2′-bipyridine-1,1′-dioxide)2*2H2O]2+/montmorillonite KSF In ethanol; lithium hydroxide monohydrate for 0.916667h; Reflux; Green chemistry; | Synthesis ofspirochromene (19a) andspiroacenaphthylene (19b-h): general procedure General procedure: A mixture of isatins (18) or acenaphthenequinone (20) (1.0 mmol), malononitrile (8a) or ethyl cyanoacetate (8b) (1.0 mmol) and 1,3-dicarbonyl compounds (dimedone (9), ethyl acetoacetate (11), meldrum′s acid (17)) or activated phenols (α-naphthol (13), 4-hydroxycoumarin (15)) (1.0 mmol), and also [Cu(bpdo)2·2H2O]2+/Mont (0.2mol%) in EtOH/H2O (4mL, 1:1) were placed in a 10mL round-bottomed fask and heated under refux conditions. The progress of the reaction was monitored by TLC (n-hexane/ethyl acetate, (1:1)). Upon completion of the reaction, the mixture was cooled to room temperature, fltered, and washed with EtOH at room temperature. The fltration was evaporated under reduced pressure, and the obtained residue was recrystallized from EtOH to aford the expected products (Table4). |
91% | With 3-butyl-1-methyl-1H-imidazol-3-ium hydroxide In neat (no solvent) at 20℃; for 0.333333h; | |
90% | With hydrogen tetrachloroaurate(III) trihydrate In 2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol at 70℃; for 0.5h; | |
90% | With (benzyl)(2-(N,N-dimethylamino)ethyl)dimethylammonium chloride In lithium hydroxide monohydrate at 80℃; for 1.5h; | |
90% | With acetic acid functionalized poly(4-vinylpyridinium)bromide In lithium hydroxide monohydrate for 1h; Reflux; | 2.4. general procedure for the synthesis 2'-aminospiro[indoline-3,4'-pyran]-2-one derivatives: General procedure: Isatin (1 mmol), alkylmalonates (1 mmol), malononitril (1 mmol) and APVPB (10 mg) were added in a 25-mL round-bottomed flask contained H2O (15 ml) and connected to a reflux condenser. The reaction mixture was stirred under reflux conditions for the appropriate time. Afterwards, the reaction mixture was cooled to room temperature and was allowed to attain at 25 °C for 1 h. Then, the solvent was removed under vacuum. Then, the prepared solid was collected by filtration and washed with ethanol and diethylether (2 × 15 ml) and dried to remove starting materials. Finally, acetone (10 ml) was added, stirred and refluxed for 3 min. Then, the resulting mixture was centrifuged for the separation of the catalyst from the pure product (the product was soluble in warm acetone and the catalyst was insoluble in this solvent). |
90% | With graphitic carbon nitride nanosheets decorated by Fe3O4 nanoparticles In lithium hydroxide monohydrate at 80℃; for 0.583333h; Green chemistry; | 2.3.1. General procedure for the preparation of spirooxindole derivatives General procedure: A mixture of isatin (1 mmol), malononitrile (1 mmol), C -H ac- tivated acid compound (1 mmol) and Fe 3 O 4 / g -C 3 N 4 (0.025 g) in H 2 O (5 mL) at 80 °C was stirred for the appropriate time [TLC: n - hexane: ethyl acetate (5:4)]. After completion of the reaction, the mixture was cooled to room temperature and filtered off, ethanol (10 mL) was added and the catalyst was removed using an exter- nal magnet. Evaporation of the solvent from mixture gave the solid residue which recrystallized from EtOH to afford the pure product. Finally Fe 3 O 4 / g -C 3 N 4 washed with H 2 O and ethanol and be used for the next run. |
88% | In lithium hydroxide monohydrate at 20℃; for 6.5h; Irradiation; Green chemistry; | 2.2. The overall process of preparing (4a-i) General procedure: Multifarious reagents including acenaphthequinone (1, 1.0 mmol),malononitrile (2, 1.0 mmol) and various reagents including a-methylencarbonylcompounds/enols (3a-i, 1.0 mmol) were reacted opposed toCFL (23 W) irradiation at room temperature in aqueous ethyl lactate(2:1, 3 mL) (Scheme 1). This was observed by TLC that employed (ethyl acetate/n-hexane (1:3)). Afterwards, the filtering of the acquired solidwas conducted, then the solid was rinsed water (2 × 3 mL) and ethanol(2 × 3 mL) and solid composition became recrystallized by EtOH. Theproducts were classified after the comparison of spectroscopic information(1H NMR). Support for this manuscript can be found in the onlineversion. |
85% | With (ethylenedinitrilo)tetraacetic acid disodium salt In neat (no solvent) at 70℃; for 0.2h; Green chemistry; | General procedure for the synthesis of spirooxindoles, spiroacenaphthylenes, and spiro-2-amino-4H-pyrans (4-6) General procedure: A mixture of isatin/acenaphthoquinone/ninhydrin)1 mmol) 1a-c, malononitrile 2 (1 mmol), CH-acid 3a-g (1 mmol),and 15 mol % of Na2EDTAwas heated under solventfreeconditions at 70 °C for the mentioned time shown intables. The progress of the reaction was monitored by TLCusing EtOAc/n-hexane (1:3) as an eluent. Upon completion,the reaction mixture was allowed to cool to roomtemperature. Then, 5 mL of water was then added to thereaction mixture, the resulting solid was collected by filtrationand washed twice with water (2 × 5 mL), and then thepure solid products 4/5/6 were recrystallized from ethanol. |
85% | Stage #1: malononitrile; acenaphthene quinone In ethanol; lithium hydroxide monohydrate at 20℃; for 0.333333h; Green chemistry; Stage #2: 4-hydroxy[1]benzopyran-2-one In ethanol; lithium hydroxide monohydrate at 60℃; for 1h; Green chemistry; | General procedure for the synthesis of 2-amino-3-cyano-7,8-dihydro-4H-chromen-5(6H)-ones 4 and 2-amino-3-cyano-pyrano[3,2-c]chromen-5(4H)-ones General procedure: A mixture of aromatic aldehydes (1.0 mmol), malononitrile (1.0 mmol) was stirred in EtOH/H2O (3 mL) in presence of Ag/TiO2 nanocomposite films which have been deposited inside beakers at RT for about 20 min. After that, C-H activated acid (5) (1.0 mmol) was added to the stirred reaction mixture, and the stirring was continued for the appropriate time at 60°C. The progress of the reaction was monitored by thin layer chromatography (TLC). Finally, the reaction mixture was cooled to RT, and then water and ethanol (5 mL) were added to the mixture of reaction and filtered to separate the product 6. Finally, the crude product was recrystallized from ethanol to afford the pure product. The structure of some purified pyran-annulated heterocyclic scaffold was confirmed by analytical as well as spectral studies including FT-IR and 1H NMR. |
82% | With 1,8-diazabicyclo[5.4.0]undec-7-ene In lithium hydroxide monohydrate for 0.5h; Reflux; | Typical Procedure for the Synthesis of Ethyl 2’-Amino-7’-methyl-2,5’-dioxo-5’,6’,7’,8’-tetrahydro-2H-spiro[acenaphthylene-1,4’-chromene]-3’-carboxylate (4j) General procedure: In a typical procedure, acenaphthenequinone (1 equiv.), ethyl cyanoacetate (1.2 equiv.), and 10 mL of water were placed in a 50-mL round-bottomed flask mounted over a magnetic stirrer. DBU (10 mol%) was added to the mixture, and the contents were stirred. 5-Methyl-cyclohexane-1,3-dione (1 equiv.) was added to this stirred mixture, and the reaction mixture was refluxed for15 min. The progress of the reaction was monitored by TLC for disappearance of 5-methyl-cyclohexane-1,3-dione. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and water was decanted.Ethanol (3mL) was added to the mixture, and the mixture was stirred. The solid product was collected by Buchner filtration and subsequently washed with ethanol to give the analytically pure spiropyran (4j) without recrystallization. The aqueous filtrate containing DBU was used as such for investigating the recyclability of the catalyst. The product was identified as ethyl 2'-amino-7'-methyl-2,5'-dioxo-5',6',7',8'-tetrahydro-2H-spiro[acenaphthylene-1,4'-chromene]-3'-carboxylate (4j) by spectral data |
80% | With Sodium hydrogenocarbonate In ethanol for 0.5h; Reflux; | |
80% | With 1-deoxy-1-(methylamino)-D-glucitol In ethanol; lithium hydroxide monohydrate at 20℃; for 0.5h; Green chemistry; | |
79% | With Cu(OAc)2*H2O In neat (no solvent) at 80℃; for 7h; | General procedure for preparation of spiro-4H-pyran derivatives (4a-f) and (8a-f) General procedure: A mixture of isatin/acenaphthoquinone (1.0 mmol), malononitrile (1.0 mmol) and 1,3-dicarbonyl compounds/4-hydroxycumarin/naphthlol 3 (1.0 mmol) in the presence of copper(II) acetate monohydrate as a mild, environmentally benign and natural catalyst under thermal and solvent-free conditions was heated for the appropriate time. After completion of the reaction [as determined by thin layer chromatography (TLC)], the mixture was cooled to room temperature (rt), the solid products were filtered and then were recrystallized from ethanol to give pure compounds (4a-f) and (7a-f). All products were characterized by comparison of spectroscopic data (1HNMR). Spectra data of selected and known products are represented below: |
71% | With SBA-Pr-NH2 In ethanol at 20℃; for 0.166667h; Green chemistry; | 2.3 General procedure for the preparation of spiroacenaphthylenederivatives (4a-4i) General procedure: The SBA-Pr-NH2 (0.02 g) was activated in vacuum at 100 °C and thenafter cooling to room temperature, acenaphthenequinone 1 (1 mmol), malononitrile2 (1 mmol), and phenol derivatives 3 (1 mmol) were added to it. Themixture was stirred in ethanol at room temperature for an appropriate timeto produce spiroacenaphthylene derivatives 4a-4i. The completion of reactionwas indicated by TLC, the resulting solid product was dissolved in hot acetonitrileand ethyl acetate, filtered for removing the unsolvable catalyst andthen the filtrate was cooled to give the pure orange product. The spectroscopicand analytical data for compounds are presented in the following part. Finally,the recovered catalyst could then be washed sequentially with diluted aqueousEt3N solution, water, and acetone. Following a period of drying, the catalystcould be reused without any noticeable loss in reactivity. |
63% | With aluminium potassium sulfate dodecahydrate In ethanol; lithium hydroxide monohydrate at 60℃; for 5h; | |
60% | With triethylamine In ethanol for 4h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With camphor-10-sulfonic acid In ethanol at 80℃; for 0.25h; | 1 In a 50mL round-bottomed flask was added 91mg acenaphthenequinone (MW = 182,0 · 5mmol), 117mg indole (MW = 117, 1 .Ommol), 11.6mg camphorsulfonic acid (CSA) (MW = 232 , 0.05mmol), 5mL of absolute ethanol, the reaction was refluxed at 80 ° C under stirring for 15 minutes (reaction progress was followed by TLC monitoring, eluent: petroleum ether 60-90: ethyl acetate = 2: 1, volume ratio).After completion of the reaction, the reaction solution was cooled to room temperature, was added 5mL of distilled water, the precipitated yellow solid powder, suction filtered, washed with cold anhydrous ethanol lmL twice, and dried in vacuo to give the product 197.0mg, yield 99%, |
93% | With ammonium cerium (IV) nitrate In ethanol for 2h; Reflux; | |
89% | With toluene-4-sulfonic acid In dichloromethane at 20℃; for 1.33333h; | General procedure: A mixture of the isatin 1 or acenaphthenequinone 4 (1 mmol), indole 2 (2 mmol), p-TSA (10mol %), CH2Cl2 (10 mL) was added to 50 mL flask and stirred at room temperature until the thecompletion of the reaction (Scheme 1, 2). Then the solid was filtered and washed with CH2Cl2 (5mL) and ethanol (5 mL) in turns, affording the product in excellent yields, which wasrecrystallized from ethanol to produce pure crystalline products. The products were identified byelemental analysis, MS, 1H NMR, 13C NMR, and IR spectra. |
88% | With SO42-/TiO2 at 20℃; for 0.5h; Grinding; neat (no solvent); | |
82% | With aminopropyl functionalized nanoporous silica In neat (no solvent) at 100℃; for 0.166667h; Green chemistry; | General procedure for the preparation of compound(5a-5i) General procedure: The SBA-Pr-NH2 (0.02 g) was activated in vacuum at 100 °C and then after cooling to room temperature, acenaphthenequinone 3 (1 mmol) and indoles 4 (2 mmol) were added to it. The mixture was stirred under solvent free condition at 100 °C for an appropriate time to produce 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one derivatives 5a-5i. The completion of reaction was indicated by TLC, the resulting solid product was dissolved in hot ethyl acetate, filtered for removing the unsolvable catalyst and then the filtrate was cooled to give the pure yellow product. The spectroscopic and analytical data for compounds are offered in the following part. Finally,the recovered catalyst could then be reused after washing sequentially with diluted aqueous Et3N solution, water, and acetone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With methanesulfonic acid In ethanol at 80℃; for 0.25h; | 9 In a 50 ml round-bottom flask, add 91 mg Acenaphthoquinone (MW= 182,0.5mmol), 131mg2-methyl indole (MW= 131,1.0mmol), 4.8 mg methyl sulfonic acid (MW= 96,0.05mmol), 5 ml anhydrous ethanol, deposited on 80 °C lower reflux stirring 15 minutes (reaction process TLC tracking, monitoring, developing agent: 60-90 petroleum ether: ethyl acetate = 2:1, volume ratio). After the reaction is complete, the reaction cooling to room temperature, add 5 ml distilled water, precipitated yellow solid powder, filtration, use 1 ml of cold anhydrous ethanol washing 2 times, dried under vacuum to get the product 209.0 mg, yield 98% |
90% | With toluene-4-sulfonic acid In dichloromethane at 20℃; for 1h; | General procedure: A mixture of the isatin 1 or acenaphthenequinone 4 (1 mmol), indole 2 (2 mmol), p-TSA (10mol %), CH2Cl2 (10 mL) was added to 50 mL flask and stirred at room temperature until the thecompletion of the reaction (Scheme 1, 2). Then the solid was filtered and washed with CH2Cl2 (5mL) and ethanol (5 mL) in turns, affording the product in excellent yields, which wasrecrystallized from ethanol to produce pure crystalline products. The products were identified byelemental analysis, MS, 1H NMR, 13C NMR, and IR spectra. |
87% | With ammonium cerium (IV) nitrate In ethanol for 2h; Reflux; |
87% | With SO42-/TiO2 at 20℃; for 0.5h; Grinding; neat (no solvent); | |
78% | With aminopropyl functionalized nanoporous silica In neat (no solvent) at 100℃; for 0.166667h; Green chemistry; | General procedure for the preparation of compound(5a-5i) General procedure: The SBA-Pr-NH2 (0.02 g) was activated in vacuum at 100 °C and then after cooling to room temperature, acenaphthenequinone 3 (1 mmol) and indoles 4 (2 mmol) were added to it. The mixture was stirred under solvent free condition at 100 °C for an appropriate time to produce 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one derivatives 5a-5i. The completion of reaction was indicated by TLC, the resulting solid product was dissolved in hot ethyl acetate, filtered for removing the unsolvable catalyst and then the filtrate was cooled to give the pure yellow product. The spectroscopic and analytical data for compounds are offered in the following part. Finally,the recovered catalyst could then be reused after washing sequentially with diluted aqueous Et3N solution, water, and acetone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With toluene-4-sulfonic acid In ethanol at 80℃; for 0.25h; | 8 In a 50 ml round-bottom flask, add 91 mg Acenaphthoquinone (MW= 182,0.5mmol), 131mg1-methyl indole (MW= 131,1.0mmol), 8.6 mg benzosulfonate (MW= 172,0.05mmol), 5 ml anhydrous ethanol, deposited on 80 °C lower reflux stirring 15 minutes (reaction process TLC tracking, monitoring, developing agent: 60-90 petroleum ether: ethyl acetate = 2:1, volume ratio). After the reaction is complete, the reaction cooling to room temperature, add 5 ml distilled water, precipitated yellow solid powder, filtration, use 1 ml of cold anhydrous ethanol washing 2 times, dried under vacuum to get the product 209.0 mg, yield 98% |
92% | With ammonium cerium (IV) nitrate In ethanol for 2h; Reflux; | |
86% | With SO42-/TiO2 at 20℃; for 0.5h; Grinding; neat (no solvent); |
83% | With toluene-4-sulfonic acid In dichloromethane at 20℃; for 2h; | General procedure: A mixture of the isatin 1 or acenaphthenequinone 4 (1 mmol), indole 2 (2 mmol), p-TSA (10mol %), CH2Cl2 (10 mL) was added to 50 mL flask and stirred at room temperature until the thecompletion of the reaction (Scheme 1, 2). Then the solid was filtered and washed with CH2Cl2 (5mL) and ethanol (5 mL) in turns, affording the product in excellent yields, which wasrecrystallized from ethanol to produce pure crystalline products. The products were identified byelemental analysis, MS, 1H NMR, 13C NMR, and IR spectra. |
70% | With aminopropyl functionalized nanoporous silica In neat (no solvent) at 100℃; for 0.333333h; Green chemistry; | General procedure for the preparation of compound(5a-5i) General procedure: The SBA-Pr-NH2 (0.02 g) was activated in vacuum at 100 °C and then after cooling to room temperature, acenaphthenequinone 3 (1 mmol) and indoles 4 (2 mmol) were added to it. The mixture was stirred under solvent free condition at 100 °C for an appropriate time to produce 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one derivatives 5a-5i. The completion of reaction was indicated by TLC, the resulting solid product was dissolved in hot ethyl acetate, filtered for removing the unsolvable catalyst and then the filtrate was cooled to give the pure yellow product. The spectroscopic and analytical data for compounds are offered in the following part. Finally,the recovered catalyst could then be reused after washing sequentially with diluted aqueous Et3N solution, water, and acetone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With benzenesulfonic acid In ethanol at 80℃; for 0.25h; | 10 In a 50 ml round-bottom flask, add 91 mg Acenaphthoquinone (MW= 182,0.5mmol), 147mg5-methoxy-indole (MW= 147,1.0mmol), 7.9 mg benzene sulfonic acid (MW= 158,0.05mmol), 5 ml anhydrous ethanol, deposited on 80 °C lower reflux stirring 15 minutes (reaction process TLC tracking, monitoring, developing agent: 60-90 petroleum ether: ethyl acetate = 2:1, volume ratio). After the reaction is complete, the reaction cooling to room temperature, add 5 ml distilled water, precipitated yellow solid powder, filtration, use 1 ml of cold anhydrous ethanol washing 2 times, dried under vacuum to get the product 230.9 mg, yield 97%, |
93% | With ammonium cerium (IV) nitrate In ethanol for 2h; Reflux; | |
92% | With toluene-4-sulfonic acid In dichloromethane at 20℃; for 2.5h; | General procedure: A mixture of the isatin 1 or acenaphthenequinone 4 (1 mmol), indole 2 (2 mmol), p-TSA (10mol %), CH2Cl2 (10 mL) was added to 50 mL flask and stirred at room temperature until the thecompletion of the reaction (Scheme 1, 2). Then the solid was filtered and washed with CH2Cl2 (5mL) and ethanol (5 mL) in turns, affording the product in excellent yields, which wasrecrystallized from ethanol to produce pure crystalline products. The products were identified byelemental analysis, MS, 1H NMR, 13C NMR, and IR spectra. |
90% | With SO42-/TiO2 at 20℃; for 0.5h; Grinding; neat (no solvent); | |
69% | With aminopropyl functionalized nanoporous silica In neat (no solvent) at 100℃; for 0.166667h; Green chemistry; | General procedure for the preparation of compound(5a-5i) General procedure: The SBA-Pr-NH2 (0.02 g) was activated in vacuum at 100 °C and then after cooling to room temperature, acenaphthenequinone 3 (1 mmol) and indoles 4 (2 mmol) were added to it. The mixture was stirred under solvent free condition at 100 °C for an appropriate time to produce 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one derivatives 5a-5i. The completion of reaction was indicated by TLC, the resulting solid product was dissolved in hot ethyl acetate, filtered for removing the unsolvable catalyst and then the filtrate was cooled to give the pure yellow product. The spectroscopic and analytical data for compounds are offered in the following part. Finally,the recovered catalyst could then be reused after washing sequentially with diluted aqueous Et3N solution, water, and acetone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With Mn(II) complex with 2,2'-bipyridine 1,1'-dioxide ligand within nanoreactors of MCM-41 In water for 0.416667h; Reflux; Green chemistry; | |
91% | With sodium hydrogencarbonate In ethanol for 0.333333h; Reflux; | |
91% | With glutathione functionalized Fe3O4 nanoparticles In water at 80℃; for 0.25h; Green chemistry; |
91% | With Eosin Y In water at 20℃; for 4.5h; Irradiation; Green chemistry; | 2.1.1. Overall process of preparing (4a-j) General procedure: To a mixture of malononitrile (2, 1.0 mmol), acenaphthequinone (1,1.0 mmol) and various reagents including a-methylencarbonyl compounds/enols (3a-j, 1.0 mmol) in a EL1/H2O (2:1) (3 mL), was addedNa2 eosin Y (1.5 mol%), under white light emitting diode (LED) (18 W)irradiation (Scheme 3). The mixture was stirred for 4 h at ambient temperature. The reaction progress was monitored by TLC utilizing nhexane/EtOAc (3:1) as an eluent. After completing the reaction, theachieved solid was filtered, rinsed with water and the crude solid was recrystallized from ethanol to provide the pure material without requiring more purification |
90% | With 1-deoxy-1-(methylamino)-D-glucitol In ethanol; water at 20℃; for 0.583333h; Green chemistry; | |
90% | With nickel ferrite(at)SiO2(at)melamine magnetic nanoparticles In ethanol for 0.333333h; Reflux; Green chemistry; | 2.4. General procedure for the synthesis of spiropyran derivatives General procedure: The mixture of the ninhydrin or acenaphthenequinone(1 mmol), malononitrile/ethyl cyanoacetate (1 mmol), 1,3-dicarbonyl compounds (1 mmol) and 0.025 g NiFe2O4(at)SiO2(at)Melaminein 5mL of ethanol were added to it. The mixture was run in reflux condition for an appropriate time. Upon completion of the reaction, monitored by TLC (hexane/AcOEt 1:3), the magnetic catalyst was removed by an external magnet and the generated solid product was filtered and recrystallized by EtOH to give pure products. Spectral data of all compounds are available on the supporting information. |
88% | With Pyridine-2,3-dicarboxylic acid In ethanol; water at 70℃; for 0.116667h; | |
87% | In water at 20℃; for 5h; Irradiation; Green chemistry; | 2.2. The overall process of preparing (4a-i) General procedure: Multifarious reagents including acenaphthequinone (1, 1.0 mmol),malononitrile (2, 1.0 mmol) and various reagents including a-methylencarbonylcompounds/enols (3a-i, 1.0 mmol) were reacted opposed toCFL (23 W) irradiation at room temperature in aqueous ethyl lactate(2:1, 3 mL) (Scheme 1). This was observed by TLC that employed (ethyl acetate/n-hexane (1:3)). Afterwards, the filtering of the acquired solidwas conducted, then the solid was rinsed water (2 × 3 mL) and ethanol(2 × 3 mL) and solid composition became recrystallized by EtOH. Theproducts were classified after the comparison of spectroscopic information(1H NMR). Support for this manuscript can be found in the onlineversion. |
86% | With 1-butyl-3-methylimidazolium hydroxide In neat (no solvent) at 20℃; for 0.333333h; | |
86% | With (2-hydroxy-ethyl)ammonium acetate In water at 90℃; for 0.5h; | |
84% | With edetate disodium In neat (no solvent) at 70℃; for 0.25h; Green chemistry; | General procedure for the synthesis of spirooxindoles, spiroacenaphthylenes, and spiro-2-amino-4H-pyrans (4-6) General procedure: A mixture of isatin/acenaphthoquinone/ninhydrin)1 mmol) 1a-c, malononitrile 2 (1 mmol), CH-acid 3a-g (1 mmol),and 15 mol % of Na2EDTAwas heated under solventfreeconditions at 70 °C for the mentioned time shown intables. The progress of the reaction was monitored by TLCusing EtOAc/n-hexane (1:3) as an eluent. Upon completion,the reaction mixture was allowed to cool to roomtemperature. Then, 5 mL of water was then added to thereaction mixture, the resulting solid was collected by filtrationand washed twice with water (2 × 5 mL), and then thepure solid products 4/5/6 were recrystallized from ethanol. |
78% | With copper(II) acetate monohydrate In neat (no solvent) at 80℃; for 6h; | General procedure for preparation of spiro-4H-pyran derivatives (4a-f) and (8a-f) General procedure: A mixture of isatin/acenaphthoquinone (1.0 mmol), malononitrile (1.0 mmol) and 1,3-dicarbonyl compounds/4-hydroxycumarin/naphthlol 3 (1.0 mmol) in the presence of copper(II) acetate monohydrate as a mild, environmentally benign and natural catalyst under thermal and solvent-free conditions was heated for the appropriate time. After completion of the reaction [as determined by thin layer chromatography (TLC)], the mixture was cooled to room temperature (rt), the solid products were filtered and then were recrystallized from ethanol to give pure compounds (4a-f) and (7a-f). All products were characterized by comparison of spectroscopic data (1HNMR). Spectra data of selected and known products are represented below: |
68% | With SBA-Pr-NH2 In ethanol at 20℃; for 0.416667h; | |
60% | With triethylamine In ethanol for 8h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With monodispersed polyethylene glycol-stabilized nickel nanoparticles In ethylene glycol at 20℃; for 0.133333h; | |
93% | With D-glucose In water at 45℃; for 0.133333h; Green chemistry; | |
86% | With Eosin Y In water at 20℃; for 5h; Irradiation; Green chemistry; | 2.1.1. Overall process of preparing (4a-j) General procedure: To a mixture of malononitrile (2, 1.0 mmol), acenaphthequinone (1,1.0 mmol) and various reagents including a-methylencarbonyl compounds/enols (3a-j, 1.0 mmol) in a EL1/H2O (2:1) (3 mL), was addedNa2 eosin Y (1.5 mol%), under white light emitting diode (LED) (18 W)irradiation (Scheme 3). The mixture was stirred for 4 h at ambient temperature. The reaction progress was monitored by TLC utilizing nhexane/EtOAc (3:1) as an eluent. After completing the reaction, theachieved solid was filtered, rinsed with water and the crude solid was recrystallized from ethanol to provide the pure material without requiring more purification |
65% | With triethylamine In ethanol for 5h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | In lithium hydroxide monohydrate at 20℃; for 5h; Irradiation; Green chemistry; | 2.2. The overall process of preparing (4a-i) General procedure: Multifarious reagents including acenaphthequinone (1, 1.0 mmol),malononitrile (2, 1.0 mmol) and various reagents including a-methylencarbonylcompounds/enols (3a-i, 1.0 mmol) were reacted opposed toCFL (23 W) irradiation at room temperature in aqueous ethyl lactate(2:1, 3 mL) (Scheme 1). This was observed by TLC that employed (ethyl acetate/n-hexane (1:3)). Afterwards, the filtering of the acquired solidwas conducted, then the solid was rinsed water (2 × 3 mL) and ethanol(2 × 3 mL) and solid composition became recrystallized by EtOH. Theproducts were classified after the comparison of spectroscopic information(1H NMR). Support for this manuscript can be found in the onlineversion. |
91% | With Bromoeosine In lithium hydroxide monohydrate at 20℃; for 4h; Irradiation; Green chemistry; | 2.1.1. Overall process of preparing (4a-j) General procedure: To a mixture of malononitrile (2, 1.0 mmol), acenaphthequinone (1,1.0 mmol) and various reagents including a-methylencarbonyl compounds/enols (3a-j, 1.0 mmol) in a EL1/H2O (2:1) (3 mL), was addedNa2 eosin Y (1.5 mol%), under white light emitting diode (LED) (18 W)irradiation (Scheme 3). The mixture was stirred for 4 h at ambient temperature. The reaction progress was monitored by TLC utilizing nhexane/EtOAc (3:1) as an eluent. After completing the reaction, theachieved solid was filtered, rinsed with water and the crude solid was recrystallized from ethanol to provide the pure material without requiring more purification |
87% | With Cu(OAc)2*H2O In neat (no solvent) at 80℃; for 6h; | General procedure for preparation of spiro-4H-pyran derivatives (4a-f) and (8a-f) General procedure: A mixture of isatin/acenaphthoquinone (1.0 mmol), malononitrile (1.0 mmol) and 1,3-dicarbonyl compounds/4-hydroxycumarin/naphthlol 3 (1.0 mmol) in the presence of copper(II) acetate monohydrate as a mild, environmentally benign and natural catalyst under thermal and solvent-free conditions was heated for the appropriate time. After completion of the reaction [as determined by thin layer chromatography (TLC)], the mixture was cooled to room temperature (rt), the solid products were filtered and then were recrystallized from ethanol to give pure compounds (4a-f) and (7a-f). All products were characterized by comparison of spectroscopic data (1HNMR). Spectra data of selected and known products are represented below: |
84% | With [Cu(2,2′-bipyridine-1,1′-dioxide)2*2H2O]2+/montmorillonite KSF In ethanol; lithium hydroxide monohydrate for 1.08333h; Reflux; Green chemistry; | Synthesis ofspirochromene (19a) andspiroacenaphthylene (19b-h): general procedure General procedure: A mixture of isatins (18) or acenaphthenequinone (20) (1.0 mmol), malononitrile (8a) or ethyl cyanoacetate (8b) (1.0 mmol) and 1,3-dicarbonyl compounds (dimedone (9), ethyl acetoacetate (11), meldrum′s acid (17)) or activated phenols (α-naphthol (13), 4-hydroxycoumarin (15)) (1.0 mmol), and also [Cu(bpdo)2·2H2O]2+/Mont (0.2mol%) in EtOH/H2O (4mL, 1:1) were placed in a 10mL round-bottomed fask and heated under refux conditions. The progress of the reaction was monitored by TLC (n-hexane/ethyl acetate, (1:1)). Upon completion of the reaction, the mixture was cooled to room temperature, fltered, and washed with EtOH at room temperature. The fltration was evaporated under reduced pressure, and the obtained residue was recrystallized from EtOH to aford the expected products (Table4). |
78% | With 3-butyl-1-methyl-1H-imidazol-3-ium hydroxide In neat (no solvent) at 20℃; for 0.333333h; | |
71% | With SBA-Pr-NH2 In ethanol at 20℃; for 0.0833333h; | |
65% | With triethylamine In ethanol for 4h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With Mn(II) complex with 2,2'-bipyridine 1,1'-dioxide ligand within nanoreactors of MCM-41 In water for 0.466667h; Reflux; Green chemistry; | |
87% | With supported palladium oxide nanoparticles in aluminum-substituted mesoporous SBA-15 In ethanol; water for 1.25h; Reflux; Green chemistry; | General procedure for the synthesis of 6-amino-3,4-dimethyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (17a-d), spiro[indoline-3,4’-pyrano[2,3-c]pyrazole (19a) and spiro[acenaphthylene-1,4’-pyrano[2,3-c]pyrazole(19b-c) General procedure: A mixture of ketones or isatin or acenaphthenequinone (1.0 mmol), malononitrileor ethylcyanoacetate (1.0 mmol), 3-methyl-1H-pyrazol-5(4H)-one (1.0 mmol) andPdO/Al-SBA-15 (0.016 g, 0.09 mol%) were added into EtOH/ H2O(4 mL, 1:1) in a10-mL round-bottomed flask and stirred under reflux conditions. The progress of thereaction was monitored by TLC (EtOAc/n-hexane, (1:1)). After completion of thereaction, mixture was cooled to room temperature, filtered and washed with EtOH.The filtrated was evaporated under reduced pressure, and the obtained residue wasrecrystallized from EtOH |
80% | With triethylamine In ethanol for 4.5h; Reflux; |
78% | With 1,8-diazabicyclo[5.4.0]undec-7-ene In water for 0.416667h; Reflux; | Typical Procedure for the Synthesis of Ethyl 2’-Amino-7’-methyl-2,5’-dioxo-5’,6’,7’,8’-tetrahydro-2H-spiro[acenaphthylene-1,4’-chromene]-3’-carboxylate (4j) General procedure: In a typical procedure, acenaphthenequinone (1 equiv.), ethyl cyanoacetate (1.2 equiv.), and 10 mL of water were placed in a 50-mL round-bottomed flask mounted over a magnetic stirrer. DBU (10 mol%) was added to the mixture, and the contents were stirred. 5-Methyl-cyclohexane-1,3-dione (1 equiv.) was added to this stirred mixture, and the reaction mixture was refluxed for15 min. The progress of the reaction was monitored by TLC for disappearance of 5-methyl-cyclohexane-1,3-dione. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and water was decanted.Ethanol (3mL) was added to the mixture, and the mixture was stirred. The solid product was collected by Buchner filtration and subsequently washed with ethanol to give the analytically pure spiropyran (4j) without recrystallization. The aqueous filtrate containing DBU was used as such for investigating the recyclability of the catalyst. The product was identified as ethyl 2'-amino-7'-methyl-2,5'-dioxo-5',6',7',8'-tetrahydro-2H-spiro[acenaphthylene-1,4'-chromene]-3'-carboxylate (4j) by spectral data |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With monodispersed polyethylene glycol-stabilized nickel nanoparticles In ethylene glycol at 20℃; for 0.1h; | |
92% | With Mn(II) complex with 2,2'-bipyridine 1,1'-dioxide ligand within nanoreactors of MCM-41 In water for 0.366667h; Reflux; Green chemistry; | |
92% | With nickel ferrite(at)SiO2(at)melamine magnetic nanoparticles In ethanol for 0.25h; Reflux; Green chemistry; | 2.4. General procedure for the synthesis of spiropyran derivatives General procedure: The mixture of the ninhydrin or acenaphthenequinone(1 mmol), malononitrile/ethyl cyanoacetate (1 mmol), 1,3-dicarbonyl compounds (1 mmol) and 0.025 g NiFe2O4(at)SiO2(at)Melaminein 5mL of ethanol were added to it. The mixture was run in reflux condition for an appropriate time. Upon completion of the reaction, monitored by TLC (hexane/AcOEt 1:3), the magnetic catalyst was removed by an external magnet and the generated solid product was filtered and recrystallized by EtOH to give pure products. Spectral data of all compounds are available on the supporting information. |
91% | In water at 80℃; for 0.25h; | 4.3. General non-catalytic multicomponent procedure General procedure: A mixture of acenaphthenequinone 1 (5 mmol), cyclic CH-acid 2 (5 mmol), malononitrile (5 mmol), and water (3 mL) was stirred at 80 °C for 15 min. Then the reaction mixture was cooled and filtered to isolate the solid product 3, which was washed with ethanol (2×5 mL), and dried under reduced pressure. For 3h, the mixture of acenaphthenequinone 1 (5 mmol), 2h (5 mmol), and malononitrile (5 mmol) was boiled in n-propanol (3 mL); the product was isolated as above. |
90% | With supported palladium oxide nanoparticles in aluminum-substituted mesoporous SBA-15 In ethanol; water for 0.916667h; Reflux; Green chemistry; | General procedure for the synthesis of 6-amino-3,4-dimethyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (17a-d), spiro[indoline-3,4’-pyrano[2,3-c]pyrazole (19a) and spiro[acenaphthylene-1,4’-pyrano[2,3-c]pyrazole(19b-c) General procedure: A mixture of ketones or isatin or acenaphthenequinone (1.0 mmol), malononitrileor ethylcyanoacetate (1.0 mmol), 3-methyl-1H-pyrazol-5(4H)-one (1.0 mmol) andPdO/Al-SBA-15 (0.016 g, 0.09 mol%) were added into EtOH/ H2O(4 mL, 1:1) in a10-mL round-bottomed flask and stirred under reflux conditions. The progress of thereaction was monitored by TLC (EtOAc/n-hexane, (1:1)). After completion of thereaction, mixture was cooled to room temperature, filtered and washed with EtOH.The filtrated was evaporated under reduced pressure, and the obtained residue wasrecrystallized from EtOH |
89% | With (benzyl)(2-(N,N-dimethylamino)ethyl)dimethylammonium chloride In water at 80℃; for 1h; | |
85% | With triethylamine In ethanol for 4h; Reflux; | |
84% | With 1,8-diazabicyclo[5.4.0]undec-7-ene In water for 0.25h; Reflux; | Typical Procedure for the Synthesis of Ethyl 2’-Amino-7’-methyl-2,5’-dioxo-5’,6’,7’,8’-tetrahydro-2H-spiro[acenaphthylene-1,4’-chromene]-3’-carboxylate (4j) General procedure: In a typical procedure, acenaphthenequinone (1 equiv.), ethyl cyanoacetate (1.2 equiv.), and 10 mL of water were placed in a 50-mL round-bottomed flask mounted over a magnetic stirrer. DBU (10 mol%) was added to the mixture, and the contents were stirred. 5-Methyl-cyclohexane-1,3-dione (1 equiv.) was added to this stirred mixture, and the reaction mixture was refluxed for15 min. The progress of the reaction was monitored by TLC for disappearance of 5-methyl-cyclohexane-1,3-dione. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and water was decanted.Ethanol (3mL) was added to the mixture, and the mixture was stirred. The solid product was collected by Buchner filtration and subsequently washed with ethanol to give the analytically pure spiropyran (4j) without recrystallization. The aqueous filtrate containing DBU was used as such for investigating the recyclability of the catalyst. The product was identified as ethyl 2'-amino-7'-methyl-2,5'-dioxo-5',6',7',8'-tetrahydro-2H-spiro[acenaphthylene-1,4'-chromene]-3'-carboxylate (4j) by spectral data |
With aspirin In neat (no solvent) at 80℃; for 2.5h; Green chemistry; | General procedure for the synthesis of dihydropyrano[2,3-c]pyrazole and spiroindoline-pyranopyrazole derivatives General procedure: A mixture of hydrazine hydrate (1.0 mmol) and ethylacetoacetate (1.0 mmol) was stirred for 5 min until 3-methyl-2-pyrazolin-5-one was precipitated. Aromatic aldehydes (1.0 mmol) or isains (1.0 mmol), malononitrile derivatives (1.0 mmol), and aspirin (20 mol%) were then added, and the mixture was heated to 80 °C under solvent-free conditions. The progress of the reaction was monitored by TLC. Then, the reaction mixture was cooled to room temperature. The mixture was washed with EtOH for separating the product. Finally, the crude product was recrystallized from ethanol to afford the pure pyranopyrazole derivatives. | |
With α-casein-(90-95) In ethanol; water at 60℃; for 0.833333h; | General procedure for the synthesis of dihydropyrano[2,3-c]pyrazole (6) and spiropyranopyrazolesderivatives (8, 10 and 12) General procedure: A mixture of hydrazine hydrate (1.0 mmol) and ethyl acetoacetate(1.0 mmol) was stirred for 5 min in EtOH/H2O (1:1)until 3-methyl-2-pyrazolin-5-one was precipitated. Then, the-Casein, malononitrile 5 (1.0 mmol) and aromatic aldehyde3 (1.0 mmol), isatins 7 (1.0 mmol), acenaphthenequinone 9(1.0 mmol) or ninhydrin 11 (1.0 mmol) were added, and themixture was heated at 60 °C. The progress of the reactionwas monitored by TLC. After completion of the reaction,the reaction mixture was cooled down to room temperature, followed by addition of 5 mL water, and subsequent filtrationof the mixture for separation of the product. Afterwards,the solid product was washed twice (each time 5 mL) with amixture of water and ethanol. Then, the resultant product wasrecrystallized from ethanol to obtain the pure pyranopyrazolederivative. To recover the catalyst, the filtrate was extractedby diethyl ether. The aqueous layer containing α-Casein was separated, followed by evaporation of the solvent componentunder reduced pressure, resulting in the recovery of α-Caseinand reusing it (Fig. 3). As Fig. 3 shows, the catalytic systemworked well, up to four catalytic runs and slightly reduced the product yield, which might have been due to the little weight loss of the catalyst during the recovery processes. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With Eosin Y In water at 20℃; for 3h; Irradiation; Green chemistry; | 2.1.1. Overall process of preparing (4a-j) General procedure: To a mixture of malononitrile (2, 1.0 mmol), acenaphthequinone (1,1.0 mmol) and various reagents including a-methylencarbonyl compounds/enols (3a-j, 1.0 mmol) in a EL1/H2O (2:1) (3 mL), was addedNa2 eosin Y (1.5 mol%), under white light emitting diode (LED) (18 W)irradiation (Scheme 3). The mixture was stirred for 4 h at ambient temperature. The reaction progress was monitored by TLC utilizing nhexane/EtOAc (3:1) as an eluent. After completing the reaction, theachieved solid was filtered, rinsed with water and the crude solid was recrystallized from ethanol to provide the pure material without requiring more purification |
81% | With copper(II) acetate monohydrate In neat (no solvent) at 80℃; for 6h; | General procedure for preparation of spiro-4H-pyran derivatives (4a-f) and (8a-f) General procedure: A mixture of isatin/acenaphthoquinone (1.0 mmol), malononitrile (1.0 mmol) and 1,3-dicarbonyl compounds/4-hydroxycumarin/naphthlol 3 (1.0 mmol) in the presence of copper(II) acetate monohydrate as a mild, environmentally benign and natural catalyst under thermal and solvent-free conditions was heated for the appropriate time. After completion of the reaction [as determined by thin layer chromatography (TLC)], the mixture was cooled to room temperature (rt), the solid products were filtered and then were recrystallized from ethanol to give pure compounds (4a-f) and (7a-f). All products were characterized by comparison of spectroscopic data (1HNMR). Spectra data of selected and known products are represented below: |
65% | With triethylamine In ethanol for 4h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With niobium pentachloride In ethanol at 20℃; for 0.0666667h; | |
95% | With lithium chloride In ethanol at 20℃; for 0.75h; | |
95% | With lead(II) chloride In ethanol at 20℃; for 0.333333h; | General procedure: A mixture of 1,2- dicarbonyl compound or aryl glyoxal (1 mmol),o-phenylenediamine (1.1 mmol) and lead dichloride( 20 mol%) in ethanol(5 mL) was stirred at room temperature. The progress of the reaction wasmonitored by TLC (hexane/AcOEt, 3:7). After the completion of the reaction,the solid which separated was filtered and then recrystallized from ethanol toafford pure product. |
93% | With titanium(IV) oxide In 1,2-dichloro-ethane at 25℃; for 0.666667h; | |
92% | With tungstate sulfuric acid at 20℃; for 0.416667h; Neat (no solvent); | |
89% | With iron(II,III) oxide In water at 20℃; for 4h; | |
85% | With polyvinylimidazole-based Bronsted acidic ionic liquid grafted silica In ethanol at 20℃; for 1h; | 3.3. General procedure for preparation of quinoxaline derivatives General procedure: To a mixture of 1,2-diketone (1 mmol) and 1,2-diamine (1 mmol) in 4 mL of ethanol was added catalyst III (0.006 g, 0.5 mol%) or catalyst IV (0.017 g, 1 mol%). The reaction mixture was stirred at room temperature for the appropriate time. The progress of the reaction was followed by TLC. Upon completion, the product and the catalyst were separated easily from each other by simple ltration. The ltrate was concentrated under reduced pressure and the crude product was puried by silica gel column chromatography with petroleum ether (bp 60 °C) and ethyl acetate (in some cases recrystallization was used). The obtained quinoxalines were identied by their 1H NMR and 13C NMR spectra and comparison of their melting points with those of the authentic samples. |
82% | With camphor sulfonic acid In ethanol; water at 28 - 32℃; for 0.75h; Green chemistry; | Synthesis of dibenzo[a,c]phenazine (3a) General procedure: In an oven dried clean reaction tube o-phenylenediamine (1; 0.5 mmol), phenanthrene-9,10-dione (2; 0.5 mmol) and a catalytic amount of camphor sulfonic acid (20 mol%) were taken sequentially. The reaction mixture was then stirred vigorously in aqueous ethanol as solvent at room temperature. Progress of the reaction was monitored byTLC. After completion of the reaction, synthesized dibenzo[a,c]phenazine (3a) was isolated pure with 92% yield just by simple filtration and subsequent washing with aqueous ethanol (EtOH:H2O 1:1). The structure of the synthesized compound was determinedby the detail spectral analysis including 1H NMR, 13C NMR and HRMS spectroscopy. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With zirconium oxide salicylaldehyde-(3-aminopropyl)trimethoxysilane imine complex modified SBA-15 In water for 2h; Reflux; | |
98% | With Cu(II)-Schiff base/SBA-15 In water for 2h; Reflux; | General procedure for the synthesis of pyrido[2,3-b]pyrazines, pyrido[3,4-b]pyrazines and 2,3-disubstituted quinoxalines in water General procedure: A round-bottomed flask equipped with a magnet and condenser was charged with desired 1,2-diamine (1.0 mmol), 1,2-diketone (1.0 mmol), water (2 mL) and catalyst Cu/SBA-15 (0.01 g (0.0014 mmol)). The resulting mixture was stirred at reflux temperature for the appropriate times, and the course of the reaction was monitored using TLC on silica gel. For separation of the catalyst, the reaction mixture (at the end of reaction) was filtered and the precipitates on the filter were dissolved in ethanol or ethyl acetate. These solvents can dissolve the products (and also organic starting materials), but the catalyst was remained insoluble. After filtration of the later solution, the catalyst was recovered |
98% | With SBA-15 mesoporous silica supported Fe(III)-Schiff base In water for 2h; Reflux; |
88% | With mesoporous silica SBA-15 functionalized with Cu(II)-DiAmSar complex In neat (no solvent) at 100℃; for 1h; | 2.3. General procedure for the synthesis of pyrazine-basedheterocycles under solvent-free conditions General procedure: A round-bottomed flask equipped with a magnet and condenserwas charged with the desired 1,2-diamine (1.0 mmol),1,2-diketone (1.0 mmol), and catalyst (Cu(II)DiAmSar/SBA-15,0.005 g). The resulting mixture was heated at 100 °C for theappropriate time. The course of the reaction was monitoredusing TLC on silica gel. Finally, the reaction mixture was cooled,and the crude mixture was purified by column chromatographyor crystallization to get the desired product. Spectral and physicaldata for all heterocycles were compared with referencesamples and were in accord with previously reported data. |
86% | With niobium pentachloride In acetonitrile at 80 - 85℃; for 5h; | |
86% | With cerium(III) chloride heptahydrate In glycerol at 75℃; for 5h; | |
85% | With zinc trifluoromethanesulfonate In acetonitrile at 80 - 85℃; for 5h; | |
85% | With samarium(III) trifluoromethanesulfonate In acetonitrile for 5h; Reflux; | |
85% | With 1,1,1,3',3',3'-hexafluoro-propanol at 20℃; for 1h; | |
85% | With ziconium(IV) oxychloride octahydrate In water at 100℃; for 2.5h; Green chemistry; | 4 4.2. General procedure for the synthesis of compounds 3a-3p For the synthesis of entitled heterocycles, a roundbottom flask equipped with a stir bar was chargedwith 1,2-phenylenediamine (1.0 mmol), 1,2-diketones(1.0 mmol), water (2 mL) and zirconium(IV) oxide chloride(25 mol%). The resulting mixture was heated in an oil bathat 100 8C for the appropriate time, and the course of the reaction was monitored using TLC on silica gel. Finally, thereaction mixture was cooled and the crude mixture waspurified by column chromatography or crystallization togive the desired product. The authenticity of the productswas established by comparing their melting points withdata of the literature and by analyzing the spectroscopicdata of 1H and 13C NMR and IR [9-16,26,27]. |
82% | With PVPP*OTf In water at 20℃; for 1h; | 2.2 Typical experimental procedure General procedure: A mixture of 1,2-dicarbonyl compounds (1 mmol), aryl 1,2-diamines (1 mmol) dissolved in 4 mL water, and PVPP·OTf (30 mg) was stirred for 1 h. The reaction was monitored by TLC. After completion of the reaction, the mixture was washed with chloroform and filtered to recover the catalyst. The filtrate was evaporated and purified by recrystallization from hot ethanol to afford pure products. Products were characterized by comparison of their physical and spectral data with those of authentic samples. Spectroscopic data for selected examples as follows: |
80% | With (2,3,4,5,6-pentafluorophenyl)ammonium triflate In water at 20℃; for 1h; Green chemistry; | Typical experimental procedure A mixture of 1,2-dicarbonyl compounds (1 mmol), aryl1,2-diamines (1 mmol) dissolved in 4 mL water, and PFPAT(10 mol%) was stirred for the appropriate reaction time. Thereaction was monitored by TLC. After completion of thereaction (monitored by TLC), the resultant was cooled withice-salt bath, filtered and washed with ethanol and purifiedby recrystallization from hot ethanol to afford pure products3a-p, and the filtrate containing PFPAT could be directlyused by adding the reactants. After three recycles, thecatalytic activity of PFPAT remained unchanged. Theproducts were characterized by comparison of their physicaland spectral data with those of authentic samples. |
80% | With 3,5-bis(trifluoromethyl)phenylammonium hexafluorophosphate In water at 20℃; for 2h; Combinatorial reaction / High throughput screening (HTS); | 2.2. General Procedure for the Preparation ofQuinoxaline Derivatives General procedure: A mixture of 1,2-dicarbonyl compounds (1 mmol), aryl1,2-diamines (1 mmol), and BFPHP (10 mol%) in water (3mL) was stirred at room temperature for an appropriate time.Upon completion of the reaction, (monitored by TLC), theresultant was cooled with ice bath, filtered and washed withethanol and purified by recrystallization from hot ethanol toafford pure products. |
80% | With 3,5-bis(trifluoromethyl)phenylammonium triflate In water at 20℃; for 1h; | 3.2. General Procedure for the Preparation of QuinoxalineDerivatives 3a-m General procedure: A water solution (3 mL) of 1,2-dicarbonyl compounds 2(1 mmol) and arene-1,2-diamines 1 (1 mmol) was mixedwith BFPAT (4) (10 mol%), and the resulting mixture wasstirred at rt for an appropriate time. Upon completion of thereaction, (monitored by TLC), the resultant was cooled in anice bath, filtered, washed with ethanol, and purified by recrystallizationfrom hot ethanol to afford pure products 3.The products were characterized by comparison of theirphysical and spectral data with those of authentic samples |
78% | With acetic acid In ethanol Reflux; | |
67% | With 5-sulfosalicylic acid anchored to silica-modified Fe3O4 nanocomposite In ethanol at 60℃; | General procedure for the synthesis of quinoxaline derivatives General procedure: To a mixture of a 1,2-diketone (1.0 mmol) and 1,2-diaminobenzene (1.0 mmol) in ethanol (2.0 mL), Fe3O4(at)SiO2(at)5-SA (20 mg) was added and the mixture was stirred at 60 °C. The progress of the reaction was monitored by TLC. After completion of the reaction, the magnetic catalyst was separated by an external magnet. The products were purified by recrystallization from ethanol or methanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: acenaphthene quinone With acetic acid In acetonitrile at 80℃; Inert atmosphere; Stage #2: 2,4,6-trimethylaniline for 3.33333h; Reflux; Inert atmosphere; | |
85% | Stage #1: acenaphthene quinone In acetic acid; acetonitrile at 80℃; for 1h; Reflux; Stage #2: 2,4,6-trimethylaniline In acetic acid; acetonitrile for 3h; Reflux; | |
72% | With zinc(II) chloride In acetic acid for 1h; Reflux; Inert atmosphere; |
72% | With formic acid In ethanol at 65℃; for 144h; | 2 4.2.2 Preparation of bis[N,N'-(2,4,6-trimethylphenyl)imino]acenaphthene (MesBIAN, 3b) To a slurry of acenapthenequinone (1) (5.80 g, 31.8 mmol) and formic acid (1.0 mL) in ethanol (400 mL) was added 2,4,6-trimethylaniline (2b) (9.00 mL, 64.1 mmol) in ethanol (200 mL) dropwise over 6 days at 65 °C. The resulting mixture was cooled to ambient temperature and the solid was collected by vacuum filtration. The remaining solution was concentrated in vacuo, cooledto 12 °C for crystallization, and then vacuum filtered to collect 3b (9.51 g, 72%) as an red-orange solid; 1H NMR (400 MHz, CDCl3): δ 7.87 (d, J = 8.3 Hz, 2H), 7.4-7.3 (m, 2H), 6.98 (s, 4H, m-Ar), 6.79 (d,J = 7.2 Hz, 2H), 2.38 (s, 6H, p-Me-Ar), 2.11 (s, 12H, o-Me-Ar); 13C{1H} NMR (100 MHz, CDCl3): δ 161.12, 146.83, 140.58, 132.84,131.04, 129.74, 128.97, 128.82, 128.26, 124.63, 122.51, 20.98,17.76; IR, v/cm-1: 2966, 2941, 2908, 2851, 1673, 1647, 1601,1593, 1472, 1420, 1437. |
In acetonitrile Reflux; | ||
Multi-step reaction with 2 steps 1: acetic acid / 1 h / 60 °C 2: potassium carbonate / water / Reflux | ||
With toluene-4-sulfonic acid In toluene at 110℃; | ||
With formic acid at 50℃; Glovebox; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With acetic acid In methanol at 20℃; | 1 Synthesis of ligand L1a General procedure: In 100 mL egg-shaped flask, acenaphthoquinone (3.644 g, 20 mmol), methanol(40ml), 2,6-diisopropyl aniline(4.0 mL, 20 mmol), two drops of acetic acid were added and the mixture was stirred at room temperature. The reaction was monitored by TLC until ended. The reaction mixture was concentrated under reduced pressure ,and purified by column chromatography on alumina N-neutral using EA:PE from 1:20 to 1:10 to give the single imine as orange yellow product (yield 60%). 1H NMR (300 MHz, CDCl3): δ = 8.21 (2 H, m), 8.01 (1 H, d), 7.82 (1 H, t), 7.41 (1 H, t), 7.27 (3 H, s), 6.64 (1 H, d), 2.84 (2 H, m), 1.18 (6 H, d), 0.90 (6 H, d) |
60% | With formic acid In ethanol at 80℃; for 20h; | 3 2.3. Synthesis of 2-[(2,6-diisopropylphenyl)imino]acenaphthylen-1-one 2,6-Diisopropyl aniline (1.45 g, 8.22 mmol) dissolved in ethanol (50 mL) was added slowly to a mixture of acenaphthequinone (2.0 g, 11.0 mmol) with ethanol (65 mL) at 60 °C. The catalytic amount of formic acid (1 mL, 26.5 mmol) was added. The solution was heated to under reflux for 20 h. Unreacted acenaphthequinone was removed by filtration at room temperature. The filtrate was further purified by column chromatography (silica gel, ethyl acetate:hexane = 1:16) to give an orange red solid (1.68 g, yield 60%). H NMR (500 MHz, CDCl3, δ in ppm): 8.20 (d, 1H, An-Ho), 8.17 (d, 1H, An-Hp), 7.98 (d, 1H, An-Ho), 7.41 (t, 1H, An-Hm), 7.26 (m, 3H, Ar-H), 6.64 (d, 1H, An-Hp), 2.84 (sept, 2H, CH(CH3)2), 1.18 (d, 6H, CH(CH3)2), 0.91 (d, 6H, CH(CH3)2). |
45% | With formic acid In ethanol at 60℃; for 16h; | Synthesis of ((2,6-diisopropylphenyl)imino)-acenaphthenone (A1) In modification of the literature procedures [7, 19], an ethanol (80 mL) solution of acenaphthenequinone (4 g, 0.02 mol) was treated with 1 mL of formic acid, followed by slow, dropwise addition (over approx. 8 h) of a solution of 2,6-diisopropylaniline (3.76 mL, 0.02 mol) in 50 mL of ethanol. The resulting mixture was stirred at 60 °C (over 8 h), cooled to room temperature, and filtered to remove unreacted acenaphthenequinone. The filtrate was cooled to -10 °C overnight. The red-orange solid that deposited was filtered, washed with ether, and dried to yield 3.6 g (45%) of product. 1H NMR (250 MHz, CDCl3, δ) 8.18-8.22 (dd, 2H, acenaphthene protons), 8.0 (d, 1H, acenaphthene protons), 7.84 (t, 1H, acenaphthene protons), 7.42 (t, 1H, acenaphthene protons),7.27 (m, 3H, aromatic protons), 6.61 (d, 1H, acenaphthene protons), 2.38 (hep, 2H,CH(CH3)2), 1.15, 0.82 (2d, 12H, CH(CH3)2). 13C NMR (100 MHz, CDCl3, δ selected resonances) 189.87 (C=O), 160.52 (C=N), 28.31 (CH(CH3)2), 23.39, 23.12 (CH(CH3)2). IR(KBr): 1425.41, 1652.33 cm-1 (C=N), 1724.47 cm-1 (C=O). Its spectroscopic data matched that given in the literature [7]. |
In ethanol Acidic conditions; | ||
With formic acid In dichloromethane for 24h; Cooling with ice; | ||
Inert atmosphere; Schlenk technique; |
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