| 99.2% |
With TiO2-SO4(2-) In acetonitrile at 20℃; for 0.5h; |
|
| 99% |
With zinc oxide at 70℃; |
|
| 99% |
With sulfated tungstate at 70℃; for 0.166667h; Neat (no solvent); |
General procedure for N-formylation reaction: A stirred mixture of amine (1 mmol), formic acid (0.4 g, 1.2 mmol), and sulfated tungstate (10 wt %) was heated in an oil bath at 70 °C and the progress of the reaction was monitored by TLC. The reaction mixture was worked up as follows. It was cooled to rt, diluted by adding ethyl acetate (10 ml) with stirring and the insoluble catalyst was recovered by filtration and washed with ethyl acetate (3 × 5 ml). Combined organic layer (filtrate and washings) was washed with H2O (2 × 10 ml), dried over anhydrous Na2SO4 and the solvent was evaporated under reduced pressure to get product as residue in almost pure form. |
| 99% |
With [Ch-OSO3H]3W12PO40 In lithium hydroxide monohydrate at 27℃; for 0.0833333h; Green chemistry; chemoselective reaction; |
Experimental procedures for N-formylation of amines
A mixture of amine (1 mmol), aq. formic acid (98%, 3 mmol,0.11 mL) and 20 mg of HIL was thoroughly mixed in a mortar fol-lowed by grinding at room temperature (27 ± 1C) (Scheme 2).The syrupy mixture got solidified within 5-15 min. The mixture was pulverized till the completion of reaction as indicated by TLC(Table 4). The reaction mass was then dissolved in ethanol torecover the insoluble catalyst. The filtered catalyst was dried at80C under vacuum for 2 h after thorough washing with ethanol.Recovered HIL was recycled in the model reaction for six times to check its catalytic efficiency. The products were recrystallized fromhot ethanol. The structures of the products were confirmed by1HNMR, IR spectroscopy and elemental analysis. The spectral data forall compounds is in good agreement with the reported compounds. |
| 99% |
With 1-methyl-3-(3-triethoxysilylpropyl)imidazolium chloride immobilized on the surface of silica-coated ferrite nanoparticles In neat (no solvent) at 20℃; for 0.0833333h; |
|
| 99% |
With ZIF-8 In 2,2,2-trifluoroethanol at 40℃; for 1.5h; |
(30) N-Formylation: General Procedure
The appropriate amine (1 mmol), HCO2H (3 mmol), and ZIF-8 (5mg, 3 mol%) were added to TFE (3 mL), and the mixture wasstirred at 40 °C for the appropriate time (Table 2). When thereaction was complete (TLC), the catalyst was recovered by centrifugation,and the TFE was recovered by distillation (bp 78 °C).The resulting mixture was then purified by column chromatography(silica gel) to provide the desired product. The structuresof all products were confirmed by 1H and 13C NMR spectroscopy(see Supporting Information). N-Phenylformamide (3a)White solid; yield: 120 mg (>99%); mp 45 °C. 1H NMR (300MHz, CDCl3): δ = 7.28 (m, 3 H, CH of Ar), 7.57 (d, 3JHH = 8.4 Hz, 2H), 8.33 (s, 1 H, H of CHO), 9.15 (br s, 1 H, NH). |
| 99% |
With [((CH3)5Cp)2Zr(H2O)2OSO2C8F17]+[OSO2C8F17]-*THF In neat (no solvent) at 80℃; for 2h; |
|
| 99% |
With C44H39ClO2P2Pd; triethylamine In ethylene glycol dimethyl ether at 80℃; Inert atmosphere; Schlenk technique; chemoselective reaction; |
|
| 99% |
With CuO impregnated on mesoporous Fe3O4 nanocomposite at 25℃; |
|
| 99% |
With sulfonic acid and propylamine functionalized HY zeolite In neat (no solvent) at 20℃; for 0.15h; Green chemistry; |
General procedure for formylation of amines
General procedure: (1.2 mmol) Formic acid was added to a mixture of aniline(1 mmol) and catalyst (0.02 g). This mixture was stirredat room temperature for the appropriate time and the progressof reaction followed by TLC. After completion reaction,products extracted by 4 mL of ethanol and chloroformmixture and catalyst filtrated, washed and dried for reuse.The structures of the products were established from theirphysical properties and spectral (1H NMR, 13C NMR andFT-IR) analysis and compared with the data that reportedin the literature. |
| 98% |
With nano-MgO for 0.0166667h; Microwave irradiation; |
|
| 98% |
With aluminum(III) oxide at 40℃; for 0.0833333h; Neat (no solvent); Cooling with ice; |
|
| 98% |
With choline chloride*2SnCl2 at 70℃; for 0.333333h; |
2.2 General procedure for N-formylation of amine
General procedure: To a mixture of aniline (2 mmol) and formic acid (3 mmol) or trimethyl orthoformate (3 mmol) in water (0.5 mL), tin (II) chloride-choline chloride (2:1) (30 mol %) was added into a test tube with magnetic stirring. The test tube was heated in an oil bath at 70 °C for 20 min and then was cooled to room temperature slowly and, ethyl acetate (20 mL) was added and filtered off to extract the product from the deep eutectic solvent. In some cases, purification was not necessary and the products were analyzed by 1H NMR spectroscopy; however, where appropriate, short flash column chromatography and recrystallization in an appropriate solvent was used for further purification. All compounds are known and characterized on the basis of their spectroscopic data (IR, NMR) and melting point by comparison with those reported in the literature. |
| 98% |
With zinc oxide nanoparticles In lithium hydroxide monohydrate at 70℃; for 0.116667h; Green chemistry; chemoselective reaction; |
|
| 98% |
With melamine trisulfonic acid In neat (no solvent) at 60℃; for 1h; Green chemistry; |
|
| 98% |
With cerium(IV) oxide In lithium hydroxide monohydrate at 20℃; for 0.0666667h; Sonication; Green chemistry; chemoselective reaction; |
General Procedure for the N-formylation of Amines
General procedure: A mixture of the appropriate amine (1.0 mmol), aq. formic acid (1.2 mmol) and nano cerium oxide (5.0 mol %) was irradiated by ultrasound for the appropriate time at room temperature. After completion of the reaction, ethyl acetate was added and the catalyst was removed by filtration. After removal of the solvent, the pure products were obtained and no recrystallization or column chromatography is needed. |
| 98% |
With NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 at 20℃; |
General procedure for formylation of amines
General procedure: To a mixture of amine (1mmol) and NaY/SA/Cu(II) (0.01g), formic acid (5mmol, 0.19mL) was added and stirred for appropriate time at room temperature. After completion of the reaction as monitored by TLC (n-hexane/EtOAc=8/2), NaY/SA/Cu(II) catalyst was filtered and organic layer evaporated under reduced pressure to give pure product. The structure of the products was established from their physical properties and spectral (1H NMR, 13C NMR and IR) analysis and were compared with the data reported in the literature and are available as the Supporting information |
| 98% |
With sulfated polyborate In neat (no solvent) at 70℃; for 0.166667h; |
General procedure for N-formylation
General procedure: To a mixture of amine (2.0 mmol) and formic acid(2.4 mmol), sulfated polyborate (7.5 wt%) was added andthe reaction mixture was stirred at 70 °C. During the reaction,the mixture turns into homogenous liquid. The progressof the reaction was observed by TLC. After completion ofthe reaction, the mixture was cooled to room temperatureand poured into water (5 mL). The solid was filtered off orin few cases extracted with ethyl acetate (10 mL). The productswere isolated by evaporation of solvent in pure form orrecrystallized from ethyl acetate and petroleum ether. Theproducts obtained were known compounds and identifiedby their melting point and 1H NMR spectroscopy, and theanalytical data were compared with the literature values. |
| 97% |
With indium powder at 70℃; for 1h; neat (no solvent); |
|
| 97% |
With γ-Fe2O3@HAp-SO3H In lithium hydroxide monohydrate at 20℃; for 0.333333h; |
|
| 97% |
With hydrogenchloride; zinc In lithium hydroxide monohydrate at 70℃; for 0.5h; Neat (no solvent); |
|
| 97% |
With 2-methyl-1-butylimidazolium trifluoroacetate In neat (no solvent) at 70℃; for 1h; |
General experimental procedure
General procedure: To a magnetically stirred mixture of HCO2H (0.76 g, 14 mmol, 85%) and IL-III (126 mg, 0.5 mmol) was added N-allyl-N-benzyl amine (1.470 g, 10 mmol, Table 2, entry 6) and then the reaction mixture was heated in an oil bath at 70 °C. The progress of the reaction was monitored by TLC. After completion of reaction, the mixture was diluted with water (10 ml) and extracted with ether (10 ml ×3). The combined organic layer was washed with brine, dried over anhydrous Na2SO4 and evaporated to give residue under reduced pressure. The crude product was passed through a short pad silica-gel column (in order to remove any trace amount of ionic liquid left in the product) by elution with diethyl ether. The evaporation of the solvent under reduced pressure, dried under high vacuum afforded light yellowish sticky solid. The identity of the products was confirmed by IR, 1H, 13C NMR and mass spectroscopy. |
| 97% |
With cerium(IV) oxide In neat (no solvent) at 20℃; for 0.166667h; Green chemistry; chemoselective reaction; |
|
| 97% |
In neat (no solvent) at 20℃; for 0.0666667h; UV-irradiation; Green chemistry; |
3 General experimental procedure for the synthesis of N-phenyl formamide (the mole ratio of amine to HCOOH, 1:1)
General procedure: A mixture of formic acid (1 mM) and aniline (1 mM) was irradiated by ultrasound for 5 h at room temperature (Table 1). During stirring, a white crystalline solid was separated out. After completion (as monitored by TLC), the solid was separated and characterized by NMR, FT-IR, elemental analysis (CHN), and melting point measurement (Table 2, entry 1). |
| 97% |
With NH2-MIL-53 at 50℃; for 0.333333h; |
2.2. General procedure for N-formylation of an amine
General procedure: To a mixture of amine (1 mmol) and formic acid (3 mmol),42 mg of NH2-MIL-53(Al) (2 mol%) was added and the mixture was stirred at 50 C under solvent free condition. The progressof the reaction was monitored by TLC. After completion of thereaction, ethyl acetate was added to the solidified mixture andthe solid catalyst was separated by filtration. The filtrate wasdried over anhydrous Na2SO4. The solvent was evaporated andthe product, obtained, was subjected to column chromatography.The isolated catalyst could be reused by addition of new portionsof substrate. The structure of products obtained had been confirmedby physical properties such as 1H NMR. Selected spectroscopydata: N-(4-nitrophenyl)formamide (Table 2, Entry 5): 1HNMR (300.13 MHz, CHCl3): d 7.40(1H, s, CH of CHO), 7.74(2H, d,3JHH 8.7 Hz, CH of Ar), 8.24(2H, d, 3JHH 8.7 Hz, CH of Ar),8.49(1H, broad, NH). |
| 97% |
With mesoporous silica SBA-15 functionalized with acidic [HNMP]ZnCl3 based deep eutectic solvent In neat (no solvent) at 20℃; for 0.666667h; |
|
| 97% |
With palladium (II) nanoparticles supported on Schiff-base modified clinoptilolite nanocatalyst In neat (no solvent) at 20℃; for 0.333333h; Green chemistry; chemoselective reaction; |
2.3 General procedure for N-formylation of amines
General procedure: Amine (1mmol) and HCO2H (1.2mmol) were added to a round-bottomed flask in the presence of Pd(at)MCP (0.012g), and the mixture was vigorously stirred at the room temperature for appropriate times (Table 2). The progress of the reactions was monitored by TLC visualized with UV short wavelengths followed by iodine. After completion, the mixture was diluted with ethyl acetate (10mL) and the nano catalyst was separated by filtration. The filtrate was washed with 1M HCl (3×5mL) and then the organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated in vacuum to obtain pure N-formylated without column purification. For recycling the nanocatalyst, after washing PdMCP with water and ethyl acetate totally, the nanocatalyst was recycled and re-utilized for the next run. The products were characterized by 1H NMR, and all data were compared to their physical data with those of known formamides [50-56] and acetamides products [57-64]. |
| 97% |
With ammonium heptamolybdate on silica coated magnetite nanoparticles In neat (no solvent) at 70℃; for 0.166667h; Green chemistry; |
General method for N-Formylation of amine derivativesby using Fe3O4SiO2(NH4)6Mo7O24 nanocatalyst
General procedure: A solution of 1 mmol of amine, 2mol% of Fe3O4SiO2(NH4)6Mo7O24, and 1 ml of formic acid was heated at70°C, and the progress of the reaction was monitored bythin-layer chromatography (TLC). The reaction mass wascooled to room temperature after the completion of the reaction.Ethyl acetate was added to the reaction mass, and thecatalyst was separated by the external magnetic field, washedwith ethanol, and dried at 60°C to be reused for further reaction.On the other hand, the ethyl acetate layer was evaporatedunder reduced pressure to afford the crude product. |
| 96% |
With anhydrous zinc chloride at 70℃; for 0.166667h; neat (no solvent); |
|
| 96% |
With thiamine chloride hydrochloride at 80℃; for 0.166667h; |
|
| 96% |
With silica supported perchloric acid at 20℃; for 0.25h; Neat (no solvent); chemoselective reaction; |
25.
General procedure: Preparation of HClO4-SiO2 Catalyst5: Perchloric acid (1.25 g, 12.5 mmol, 70% aq. solution) was added to a suspension of silica-gel (230-400 mesh, 23.75 g) in Et2O (70.0 mL) and the mixture was stirred for 30 min. The residue obtained on the removal of excess solvent was heated at 100 °C for 72 h under vacuum to furnish silica supported perchloric acid as a free flowing powder (1 g silica gel contains 0.5 mmol of HClO4). General procedure of N-formylation-To a mixture of 2-bromoaniline (0.11 ml, 1 mmol) and formic acid (0.12 ml, 3 mmol) in a 10 ml round bottomed flask was added HClO4-SiO2 (50 mg, 0.025 mmol). The reaction mixture was stirred at room temperature for 25 min. On completion, the mixture was diluted with diethyl ether and filtered to remove the solid catalyst. The filtrate was washed with sat. solution of NaHCO3 (5 ml × 3), water, and dried over anhy. Na2SO4. The solvent was evaporated and the crude residue was purified by column chromatography to give a colourless solid, yield 94% |
| 96% |
With cobalt ferrite nanoparticles at 20℃; for 0.05h; Irradiation; Green chemistry; chemoselective reaction; |
General Procedure for the Synthesis of Formamides
General procedure: CoFe2O4 magnetic nanocatalyst (20 mol%) was added toa mixture of amine (1.0 mmol) and formic acid (1.2 mmol)and irradiated in a PARSONIC 2600s ultrasound cleanerwith a frequency of 28 kHz and an output power of 50 W,for the appropriate time at room temperature as specified inTable 2. After completion of the reaction (monitored byTLC) ethyl acetate was added to the reaction mixture and thecatalyst was separated from the reaction mixture with anexternal magnet. The solvent was concentrated under reducedpressure on a rotary evaporator to afford the pureproduct as solid in excellent yields. All compounds wereknown and were characterized by melting points, elementalanalysis (CHN), IR, 1H NMR and 13C NMR. The physicaldata (mp, IR, NMR) of known compounds were found to beidentical with those reported in the literature [13-17,21-29]. |
| 96% |
at 20℃; for 0.0333333h; Irradiation; |
|
| 95% |
In toluene |
|
| 95% |
With anhydrous sodium formate at 20℃; for 1h; Neat (no solvent); |
|
| 95% |
With aminopropylated mesoporous SBA-15 silica at 40℃; for 0.25h; Neat (no solvent); chemoselective reaction; |
|
| 95% |
With (1-methyl-3-(3-sulfopropyl)-1H-imidazol-3-ium)3[PW12O403-] In neat (no solvent) at 70℃; for 0.333333h; Green chemistry; |
4.3 General procedure for the synthesis of formamides (Table 2)
General procedure: To a mixture of amine (2 mmol) and formic acid (3 mmol) in a 10 mL round bottomed flask was added [MIMPS]3PW12O40 (140 mg, 0.04 mmol). The reaction mixture was stirred at 70 °C. The progress of the reaction was monitored by TLC. On completion, the mixture was diluted with ethyl acetate (20 mL) with stirring for 30 min. The insoluble catalyst was recovered by filtration. The filtrate was washed with satd solution of NaHCO3 (5 mL×3), brine, and dried over anhyd Na2SO4. The solvent was evaporated and the residue in almost pure form. Recrystallization or column chromatography could be used for further purification. |
| 95% |
With sulfonated rice husk ash In neat (no solvent) at 60℃; for 0.0833333h; |
|
| 95% |
With phosphotungstic acid supported on silica-coated CoFe2O4 nanoparticles In neat (no solvent) at 20℃; for 0.5h; |
4.1 General procedure for N-formylation reactions catalyzed byCoFe2O4SiO2-PTA under solvent-free conditions
General procedure: A mixture of aniline (1.0 mmol), formic acid (1.0 mmol), andCoFe2O4SiO2-PTA (0.05 g) was stirred at room temperature. Theprogress of the reaction was continuously monitored by TLC. After 30 m period of time and upon completion of the reaction, as indi-cated by TLC tests, ethyl acetate was added to the reaction mixture.The catalyst was magnetically fixed at the side wall of the reactorand the liquid phase was decanted. The catalyst was then washedwith ethyl acetate and dried to be reused in a new N-formylationreaction. The isolated organic phase was washed with a saturatedsolution of NaHCO3and dried over anhydrous Na2SO4. The sol-vent, ethyl acetate, was removed by a rotary evaporator and theresulted residue was then subjected to recrystallization to obtainpure formamide product with 95% yield. Characterization of theN-formylated products, as well as determination of the yields, inthis and other similar reactions were achieved by GC analysis. Tofurther confirm the identity of the products, their physical andFT-IR spectral data were compared with those reported in theliterature. 1H NMR (CDCl3, 250 MHz): 7.1, 7.5 (m; cis and trans, para, metaand ortho Ar-H), 7.8 (s, broad, cis, NH), 8.3 (s, cis, CHO), 8.7 (d, trans,CHO), 8.8 (s, broad, trans, NH).EI-MS: m/z = 121.2(M+). |
| 95% |
With Co3O4 nanoparticles at 40℃; for 0.0666667h; Green chemistry; |
General procedure for N-formylation of amines
General procedure: To a mixture of HCO2H (4 mmol, 0.15 mL) and Co3O4 nanoparticles (0.015 g) was added aniline (1 mmol), and then the reaction mixture was heated at 40 C and stirred with a magnetic stirrer. The progress of the reaction was monitored by TLC. After the reaction was completed, EtOAc was added to the reaction mixture, and the catalyst was removed by filtration. The organic solvent was then washed with H2O (2 x 10 mL) and dried over anhydrous Na2SO4. After removal of the solvent, the pure product was obtained. This was further purified by recrystallization with a suitable solvent (ether or CHCl3). |
| 95% |
With α-CoNi binary hydroxide In neat (no solvent) at 20℃; for 0.0833333h; |
2.6. N-formylation of aniline
Aniline (1.5 mmol), formic acid (4.5 mmol) and catalyst (10 and30 mg) were added into a 10-ml vial and the mixture was stirred at room temperature for an appropriate amount of time. The reaction was performed in solvent-free and acetonitrile conditions and monitored byTLC |
| 95% |
With sulfonic acid functionalized on biguanidine fabricated silica coated heterogeneous magnetic nanoparticles In ethanol at 20℃; for 0.166667h; |
|
| 95% |
With titanium(IV) dioxide at 120℃; for 6h; Sealed tube; |
9 The method for preparing N-phenylformamide as catalyzed by titanium dioxide:
Add 0.0016 g (0.02 mmol) of titanium dioxide, 3.725 g (40 mmol) of aniline, and 1.841 g (40 mmol) of formic acid to the pressure-resistant bottle in sequence, seal it, place it in an oil bath, react at 120 °C for 6 h, cool to room temperature, and centrifuge, The catalyst was separated from the reaction solution, the titanium dioxide catalyst was recovered, and the internal standard mesitylene 0.1202 g (1 mmol) was added to the reaction solution obtained by centrifugation, diluted with 10 mL of DCM, and the NMR yield was measured by the internal standard method to obtain N-phenylformamide. The yield is 95%. |
| 94% |
With iodine at 70℃; for 2h; |
|
| 94% |
With 1-methyl-3-(trimethoxysilylpropyl)-imidazolium hydrogen sulfate supported on rice husk ash In neat (no solvent) at 60℃; for 5h; Green chemistry; chemoselective reaction; |
|
| 93% |
With hexachlorocyclotriphosphazene In neat (no solvent) at 50℃; for 0.0166667h; |
Generalprocedure for the synthesis of formamides 11a-l
General procedure: To the mixture of formic acid (2 mmol, 0.075mL) and amine (1 mmol), TAPC (0.5 mmol, 0.18 g), was added at 50 oC withcontinuous stirring for the appropriate reaction time as indicated in Table 3.The progress of the reaction was monitored by TLC. After completion of thereaction, H2O (10 mL) was added to the reaction mixture. Theresi-due was then extracted with EtOAc (4×5 mL), and the combined extracts weredried (MgSO4). The organic layer was concentrated under reducedpressure to afford the pure title products. |
| 92% |
With ZnO nanofluid at 110℃; for 3h; neat (no solvent); |
|
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