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CAS No. : | 101-39-3 | MDL No. : | MFCD00006976 |
Formula : | C10H10O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | - |
M.W : | 146.19 | Pubchem ID : | - |
Synonyms : |
|
Num. heavy atoms : | 11 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.1 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 46.35 |
TPSA : | 17.07 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.64 cm/s |
Log Po/w (iLOGP) : | 1.92 |
Log Po/w (XLOGP3) : | 2.18 |
Log Po/w (WLOGP) : | 2.18 |
Log Po/w (MLOGP) : | 2.31 |
Log Po/w (SILICOS-IT) : | 2.67 |
Consensus Log Po/w : | 2.25 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.39 |
Solubility : | 0.594 mg/ml ; 0.00406 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.17 |
Solubility : | 0.984 mg/ml ; 0.00673 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -2.8 |
Solubility : | 0.231 mg/ml ; 0.00158 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 2.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.67 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
98% | With tetrabutylammomium bromide; toluene-4-sulfonic acid hydrazide; sodium hydroxide In water at 80℃; for 10 h; Air atmosphere | General procedure: A Schlenk tube with a magnetic stir bar charged with α,β-unsaturated carbonyl compounds (0.5 mmol, 1 equiv), tosyl hydrazide (0.6 mmol, 1.2 equiv), NaOH (1.5 equiv), (n-Bu)4NBr (1.5 equiv). The reaction vessel was placed in an 80 °C oil bath, and then stirring at this temperature for 10 h. The reaction mixture was then allowed to cool to ambient temperature, and diluted with 20 mL of ethyl acetate, and washed with brine (15 mL), water (15 mL), and then the organic layer was dried over Na2SO4. After concentrated in vacuo, the crude product was purified by column chromatography. The identity and purity of the known product was confirmed by 1H NMR, 13C NMR, and GC-MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | potassium fluoride on basic alumina; In PEG400; at 30℃; for 4h; | EXAMPLE 29 Preparation of 2-methylene-5-[(E)-2-methyl-3-phenylallylidene]cyclopentanone Step A :Preparation of 2-methyl-3-phenylacrylaldehyde 13.78 g (0.13 mol) of benzaldehyde, 5 g of KF-Al2O3 and 5 mL of PEG-400 were added to a 250 mL three-necked flask. At 30C, 5.80 g (0.10 mol) of n-propionaldehyde was added dropwise to the mixture while stirring, and reacted under the controlled dropping speed. After 4 h, the solution was transferred into a separating funnel, and the organic phase was collected, washed with saturated brine to neutral, and dried over anhydrous magnesium sulfate. After removal of most of the solvent, the solution was concentrated and distilled under reduced pressure. The fractions of bp:130-132C/2660 Pa was collected to yield 12.30 g of light yellow liquid product with a yield of 89.0%. |
89% | With KF-Al2O3; In PEG-400; at 30℃; for 4h; | Example 29; Preparation of 2-methylene-5-[(E)-2-methyl-3-phenylallylidene]cyclopentanone; Step A: Preparation of 2-methyl-3-phenylacrylaldehyde 13.78 g (0.13 mol) of benzaldehyde, 5 g of KF-Al2O3 and 5 mL of PEG-400 were added to a 250 mL three-necked flask. At 30 C., 5.80 g (0.10 mol) of n-propionaldehyde was added dropwise to the mixture while stirring, and reacted under the controlled dropping speed. After 4 h, the solution was transferred into a separating funnel, and the organic phase was collected, washed with saturated brine to neutral, and dried over anhydrous magnesium sulfate. After removal of most of the solvent, the solution was concentrated and distilled under reduced pressure. The fractions of bp: 130-132 C./2660 Pa was collected to yield 12.30 g of light yellow liquid product with a yield of 89.0%. Following the same steps B and C as mentioned in EXAMPLE 28, a light yellow flaky crystal as the desired final product was obtained with a yield of 66%. MS: M+ 224. 1H-NMR (CDCl3, delta ppm): 2.18 (s, 3H, -CH3), 2.70 (m, 2H), 2.99 (m, 2H), 5.47 (s, 1H), 5.93 (s, 1H), 7.06 (d, 2H, J=13.2 Hz), 7.30 (d, 1H, J=3.9 Hz), 7.40 (m, 4H). |
85% | With benzoic acid; L-proline; In neat (no solvent); at 125℃; for 1h;Inert atmosphere; | The aldol condensation was carried out by taking freshly distilled benzaldehyde (15.8 mmol) along with 40 mol% of the amino acid as a catalyst, 40 mol% of benzoic acid as co-catalyst and n-decane as an internal standard in a three-necked round bottom flask. The reaction was carried out under inert atmosphere at a desired temperature to minimize the oxidation of aldehydes used in the reaction. In order to improve the selectivity for the cross-aldol product and maximize atom efficiency of the reaction, 1-alkanaldehydes (7.9 mmol) were added to the reaction mixture under a controlled condition (1130 mul/h) using a syringe pump. The reaction mixture was colled down to room temperature after completion of the reaction (checked by GC). All the reactions were done in triplicate to ensure the reproducibility of the reaction. |
In acetonitrile; at 20℃; for 12h;Inert atmosphere; | General procedure for the retro-aldol/aldol one-pot condensation of cinnamaldehydes: To a solution of cinnamaldehyde (8, 1 mmol, 1.0 equiv) in acetonitrile (1 mL) were added water (2 mmol, 2.0 equiv) and pyrrolidine (0.5 mmol, 0.5 equiv). The reaction mixture was stirred at room temperature for 12 h under argon and aldehyde 10 (2.5 mmol, 2.5 equiv) was subsequently added. After another 12 h at rt, the reaction mixture was filtered through a short pad of MgSO4 and washed with dry dichloromethane. The solvent of the filtrate was removed in vacuo and the residue was chromatographed on silica gel (dichloromethane/hexane; 7:3) to give the alpha-substituted cinnamaldehyde 11. Compounds 11a-c are either commercially available or have been described previously, and their analytical data match the literature values. | |
With sodium hydroxide; In water; at 25℃; for 5h; | General procedure: In a typical experiment the flask was charged with the solvent and the catalyst, then 4-isobutylbenzadehyde (iBB) was added. The total amount of propanal was added dropwise to the mixture in three portions at the 0th, 30th and 60th min of the reaction. Except for monitoring the influence of temperature, all experiments were performed at room temperature (25 C). When a higher temperature was used, the flask was equipped with a condenser. Samples were neutralized by acetic acid, diluted with ethanol, centrifuged and analyzed. At the end of the reaction, the reaction mixture was neutralized using acetic acid, washed with water, extracted using diethyl ether and evaporated. | |
With N-benzyl-N,N,N-triethylammonium chloride; potassium carbonate; caesium carbonate; In dichloromethane; at 25℃;Inert atmosphere; Schlenk technique; | General procedure: 20 mmol Aromatic aldehyde, 20 mmol Cs2CO3, and 10 mmol benzyltriethylammonium chloride were added to a sealed 50 mL kolle flask. Then 15mL DCM was added under N2 (using Schlenk line technology). The reaction mixture was stirred at 25C and 30 mmol alkyl aldehyde was added dropwise into the reaction mixture over 3-5 h. The reaction progression was monitored using GC, and stirred at 25C until completion. After reaching completion the reaction mixture was diluted with 50 mL DCM, washed twice with 20 mL water and once with 10 mL brine. The organic phase was collected, dried over MgSO4, filtered, and then evaporated under vacuum. The resulting crude product was used without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
> 99% | With C48H43ClN2P2Ru; potassium tert-butylate; hydrogen; In methanol; at 50℃; under 3750.38 Torr; for 24h;Autoclave; Inert atmosphere;Catalytic behavior; | In an autoclave glass insert 10 mmol of substrate and the required KOfBu (2 mol%) were dissolved in the alcohol solvent (4 ml_) and with stir agitation switched on, purged with nitrogen (pressurise to 3 bar and vent to ambient pressure). The required amount of a complex stock solution in the reaction solvent was added. Directly after the addition, the mixture was purged three times with nitrogen (pressurise to 3 bar and vent to ambient pressure). Then it was purged twice with hydrogen (pressurise to 13 bar and vent to ambient pressure) and then kept pressurised at reaction pressure for the time defined as reaction duration. After this, the autoclave was vented and the product analysed by GC and HNMR. Table 13. Hydrogenation of 2 molar in methanol solutions of benzaldehyde 45 and trans- cinnamaldehyde 52 catalyzed by complexes RuCI2(dppb)(AMPY) (50) and RuCI2(dppf)(AMPY) (51 ) and pincer complexes 13-15. Base KOfBu (2 mol%). Hydrogenation in a Biotage Endeavour apparatus at 50 C. Complex Loading . . Alcohol By-products. Substrate131 P (H2) [atm] Time [h] Conv. [%][al [S/C] [%][al [%][al 45 50 1000 10 3 35 33 2 45 50 2000 10 8 22 7 15 45 51 2000 10 16 100 98 2 45 13 10000 10 8 100 96 4 45 13 20000 10 8 100 99 1 45 14 10000 10 16 98 98 2 45 14 40000 13 32 27 26 1 45 15 10000 13 16 63 60 3 52 50 1000 10 3 95 87 54: 8 52 51 2000 10 8 98 89 54: 9 52 13 10000 10 8 99 89 54: 10 52 13 20000 10 8 96 75 54: 21 52 14 10000 10 8 99 90 54: 1 1 la| Conversion and product content were determined by GC analysis or by -NMR spectroscopy. Table 14. Hydrogenation of 2 molar solutions of benzaldehyde 45 catalyzed pincer complexes 13-15. Base KOfBu (2 mol%). Hydrogenation at S/C =10000 in a Biotage Endeavour apparatus at 50 C and 13 bar H2 for 16 hours. Complex By-products. Solvent Conv. [%][al Alcohol [%][al [%][al 13 MeOH 100 96 4 13 MeOH/EtOH = 3/1 100 93 7 13 MeOH/EtOH = 1 /1 100 88 12 13 MeOH/EtOH = 1 /3 100 86 1 1 14 MeOH 100 98 2 14 MeOH/EtOH = 3/1 100 97 3 14 MeOH/EtOH = 1 /1 100 97 3 14 MeOH/EtOH = 1 /3 90 80 10 14 EtOH 100 82 18 15 MeOH 63 60 3 15 MeOH/EtOH = 3/1 23 19 4 15 MeOH/EtOH = 1 /1 23 18 5 15 MeOH/EtOH = 1 /3 19 16 3 [al Conversion and product content were determined by GC analysis or by -NMR spectroscopy. Table 15. Hydrogenation of methanol solutions of aldehydes catalyzed by complex 14. Base KOfBu (2 mol%). Hydrogenation in Parr autoclave at 50 C and 5 bar H2. Loading Alcohol By-products. Substrate'31 [S] Time [h] Conv. [%][al [S/C] [%][al [%][al 47 1 M 10000 1 100 >99 0 47 1 M 20000 7 98 >97 0 47 1 M 40000 22 98 >97 0 60 1 M 10000 1 100 99 1 60 2M 5000 0.66 100 95 5 61 2M 15000 24 100 >99 <1 62 1 M 5000 1 .5 99 >90 <9 Conversion and product content were determined by GC analysis or by -NMR spectroscopy. The advantage of using the pincer complexes 13-15 compared to using RuCI2(dppb)(AMPY) (50) and RuCI2(dppf)(AMPY) (51) is again shown by the hydrogenation data. In the hydrogenation of trans - cinnamaldehyde 52 the formation of fully saturated product cannot be suppressed to a similar degree as with the NH4-formate hydrogenation. Methanol as reaction solvent is clearly preferable over ethanol and methanol/ethanol mixtures. |
94% | With hydrogen; triphenylphosphine; sodium hydroxide;bis(triphenylphosphino)copper(I) nitrate; In ethanol; at 50℃; under 37503.8 Torr; for 16h;Inert atmosphere;Product distribution / selectivity; | Into a stainless steel autoclave equipped with a glass inner tube, Cu(NO3)(PPh3)2 (11.7 mg, 0.018 mmol) and triphenylphosphine (28.3 mg, 0.108 mmol) were introduced. The inside of the autoclave was then replaced with nitrogen. To the autoclave, an ethanolic solution of sodium hydroxide (0.03 M) (6.0 mL, 0.18 mmol) and alpha-methyl cinnamic aldehyde (1.26 mL, 9 mmol) were added, and stirring was performed at a hydrogen pressure of 5 MPa at 50 C. for 16 hours. The hydrogen was released with great care, and the conversion was analyzed by GC (>99%). The contents were concentrated, and then purified by silica gel chromatography. Thus, 1.25 g of the alpha-methyl cinnamic alcohol was obtained (yield: 94%). |
93% | With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H2O); isopropyl alcohol; at 82℃; for 6h;Inert atmosphere; Green chemistry; | alpha-methylcinnamaldehyde (146 mg, 1.0 mmol), cat. [Ir] (1.1 mg, 0.002 mmol, 0.2 mol%) and isopropanol (5 mL) were sequentially added to a 25 mL Kelvin tube, N2 protected, 82 C reaction for 6h. Cool to room temperature and remove the solvent by rotary evaporation.The pure target compound was obtained by column chromatography (developing solvent: petroleum ether / ethyl acetate), yield: 93% |
91% | General procedure: To a 25 mL Schlenk tube containing a solution of 1 in 2 mL of THF was added an aldehyde (1.0 mmol) and (EtO)3 SiH (0.20 g, 1.2 mmol). The reaction mixture was stirred at 50-55 C until there was no aldehyde left (monitored by TLC and GC-MS). The reaction was then quenched byMeOH (2mL) and a 10% aqueous solution of NaOH (5 mL) with vigorous stirring at 60 C for about 24 h.The organic product was extracted with diethyl ether (10 mL × 3), dried over anhydrous MgSO4, and concentrated under vacuum. The alcohol product was further purified using flash column chromatography (elute with 5-10% ethyl acetate in petroleum ether). The 1H NMR and 13C NMR spectra of the alcohol products are providedin Supporting information. | |
90% | With formic acid; C14H16ClIrN3O(1+)*Cl(1-); In water; at 90℃; for 0.5h;pH 1.5; | In a 25 ml test tube reaction flask, 1.0 mmol of alpha-methylcinnamaldehyde, 0.001 mmol of bisazide chelate 1 (R1 is methoxy, R2 is hydrogen), 5.0 mmol of formic acid, 2 ml of water are added. The pH of the solution was adjusted to about 1.5, and the reaction system was stirred at 90 C for 0.5 hour, the heating and stirring were stopped, and the mixture was cooled to room temperature. The reaction solution was extracted with ethyl acetate. The solvent was evaporated under reduced pressure, and then purified and purified by column chromatography to give the desired product. The column chromatography eluent was used as a petroleum ether: ethyl acetate mixed solvent in a volume ratio of 5:1. The yield is 90% and the semi-complete reduction is >99%. |
52% | With piperidine; hydrogen; at 60℃; under 11251.1 Torr; for 24h;Autoclave; | AuNPore (10.0 mg, 10 mol%), alpha-methylcinnamaldehyde (73.03 mg, 0.5 mmol) and piperidine (4 mL) were added all at once into a stainless steel autoclave with a built-in magnet and the autoclave was charged with 15 bar H2. Place the autoclave in a 60 C oil bath Under a reaction of 24 h, column chromatography (silica gel, 200-300 mesh; developing solvent, petroleum ether: ethyl acetate = 20: 1) gave alpha-methylcinnamyl alcohol38.48 mg, yield 52%. |
99%Chromat. | With formic acid; iron(II) tetrafluoroborate hexahydrate; tris(2-diphenylphosphinoethyl)phosphine; In tetrahydrofuran; at 60℃; for 2h;Schlenk technique; Inert atmosphere; | General procedure: Fe(BF4)2·6H2O (0.7 mg; 0.002 mmol) and tris[2-(diphenyl-phosphino)-ethyl]phosphine [P(CH2CH2PPh2)3; tetraphos] (1.4 mg; 0.002 mmol) are placed in a Schlenk-tube under argon atmosphere. 1 mL dry tetrahydrofurane is added and the purple solution is stirred for 2 min. Cinnamaldehyde (63 muL; 0.5 mmol) and 100 muL n-hexadecane as an internal GC-standard are injected and a sample is taken for GC-analysis. The solution is heated to 60 C and the reaction starts by addition of 1.1 equiv formic acid (22 muL; 0.55 mmol). After 2 h, a second sample is taken for GC-analysis and conversion and yield are determined by comparison with authentic samples. For the isolation, the reaction is scaled up by a factor of 20. When the reaction is completed, the reaction solution is diluted with a mixture of n-hexane and ethyl acetate (3:1), filtered through a plug of silica and the solvent removed in vacuum. |
85%Spectr. | With C20H39BrFeN3OP2; water; sodium formate; at 80℃; for 1h; | General procedure: In a typical experiment, a vial containing a magnetic stirringbar was charged with catalyst 1 and the substrate(2.0 mmol) inside a glovebox. The vial was sealed with aseptum screw cap, taken out from the glovebox and asolution of sodium formate in degassed water (1.0 cm3,2.5 M) was added through the septum. The reaction mixturewas stirred at 80 C for the specified time after whichit was quickly cooled to room temperature and the reactionwas quenched by exposure to air. A sample was taken fromthe organic phase, diluted in CDCl3, and analyzed by NMRspectroscopy. For the isolation of the reaction products,1 cm3 diethyl ether was added and the phases were separated.The aqueous phase was washed with diethyl etherand the combined extracts were filtered over a short plug ofsilica to remove the catalyst. The solution was dried overMgSO4 and the solvent removed under reduced pressure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With hydrogen; In ethanol; at 20℃; under 760.051 Torr; for 2h; | General procedure: In a typical reaction, 0.015 g of catalyst and 2 mmol of the reactant were taken in 10 mL of ethanol under hydrogen atmosphere. The reaction was monitored by thin-layer chromatography (TLC). After complete disappearance of the starting material, the catalyst was separated by simple filtration and the solvent was removed under reduced pressure to obtain the pure product. |
With hydrogen; In methanol; at 120℃; under 60006.0 Torr; for 5h;Autoclave; | General procedure: Hydrogenations were performed in an autoclave (volume 160 ml; Parr). Fractions containing 80-97% of 3-(4-alkylphenyl)-2-methylprop-2-enal were used for hydrogenation. The autoclave was filled with an appropriate amount of catalyst (1 wt.% in case of Pd catalysts, 10 wt.% in case of other catalysts, Table 1), 10 g of 3-(4-alkylphenyl)-2-methylprop-2-enal and 90 ml of solvent, isopropyl alcohol. Samples taken during the reaction were centrifuged and analyzed. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
813 g | With platinum on activated charcoal; hydrogen; at 0 - 20℃; under 37503.8 Torr; for 72h; | To a 2 L stainless steel autoclave, 800 g of alpha-methylcinnamaldehyde was added without a solvent.After nitrogen replacement, 0.8 g of platinum carbon was added under nitrogen protection. Replace with nitrogen three times,Replace the hydrogen three times, keep warm at 0 C - 20 C and continue to pass 5MPa hydrogen.The reaction was stirred for 72 hours. The reaction was stopped, and after replacing the nitrogen three times, the reaction solution was taken out and filtered.The filtrate was concentrated to give 813 g of (±)-2-methyl-3-phenyl-1-propanol. |
813 g | With palladium on activated charcoal; hydrogen; at 0 - 20℃; under 37503.8 Torr; for 72h;Autoclave; | Add to 2L stainless steel autoclave800g of alpha-methylcinnamaldehyde,No solvent added.After nitrogen replacement,0.8g of platinum on carbon was added under nitrogen.Replace with nitrogen three times,Replace the hydrogen three times,Insulation 0 C - 20 C continuous access to 5MPa hydrogen,The reaction was stirred for 72 hours.Stop the reaction,After replacing the nitrogen three times,Remove the reaction solution and filter.The filtrate was concentrated to give 813 g(±)-2-methyl-3-phenyl-1-propanol,Gas chromatographic purity ? 99%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride at 200℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With trifluorormethanesulfonic acid; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione; In 1,4-dioxane; at 20℃; for 0.433333h; | General procedure: To the suspension of IBX (1.1 equiv., or 1.1 mmol) and TfOH (2-5 mol %, or 0.02-0.05 mmol) in 3 mL 1,4-dioxane, alcohol (1.0 equiv., 1.0 mmol in 2 mL 1,4-dioxane) was added at room temperature, and the reaction mixture was vigorously stirred till the complete consumption of alcohol, as indicated by TLC. The solvent was evaporated under reduced pressure, and the resulting residue was diluted with 10 mL of dichloromethane. The heterogeneous mixture was stirred for 5 minutes and filtered. The residue was washed with dichloromethane (3×3 mL) and the filtrate was evaporated to dryness to obtain the desired product in sufficiently pure form. |
75% | With RuCl2(AsPh3)2(Ph-DPMP); 4-methylmorpholine N-oxide; In dichloromethane; at 20℃; for 1h; | General procedure: The reaction mixture of Primary or secondary alcohol (1 mmol),RuIIICl2 (AsPh3)2 (Ph-DPMP) Schiff base complex (0.1 mmol), NMO(1.1 mmol) and dichloromethane (2 mL) was stirred at room temperature.The filtrate obtained was evaporated under reduced pressureand the residual mass was dissolved in a mixture of ethylacetate/hexane (1:4) and then passed through a short column ofsilica gel using hexane/ethyl acetate (4:1) as eluent. Removal ofsolvent and usual workup gave the corresponding aldehydes andketones, which were identified by comparing their physical andspectral data with those of authentic compounds reported in literature[27]. |
71% | With copper(l) iodide; TEMPOL; N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)ethane-1,2-diamine; In acetonitrile; at 20℃; for 3h;Inert atmosphere; | General procedure: The copper salt and the ligand (each 0.025 mmol) were added to CH3CN (1 mL) in an Ar atmosphere and stirred for 30min. Then 4-OH-TEMPO (0.025 mmol) and substrate (0.5mmol) were added successively, and the mixture was stirred at room temperature. The reaction progress was checked using thin-layer chromatography. The reaction conversion and yield were obtained from GC measurements using nitrobenzene or nonane as an internal standard, or by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With tert.-butylhydroperoxide; ammonium acetate; iodine; sodium carbonate; In ethanol; at 50℃; for 17h; | In a 25 mL two-necked round bottom flask equipped with a thermometer and a magnetic stirrer4mmolAlpha-methyl cinnamaldehyde(formula (1-22)), 6 mmol of NH4OAc, 4 mmol of Na2CO3, 4.4 mmol of TBHP, 0.1 mmol of I2, 5 mL of anhydrous ethanol And the reaction flask was then placed in an oil bath preheated to 50 C and the magnetic stirrer was opened for 17 h. Reaction solution Adding sodium thiosulfate solution and stirring, then extracting with ether, separating the organic layer, distilling off the solvent under reduced pressure, and then performing column chromatography The eluent was taken as a mixture of ethyl acetate / petroleum ether in a volume ratio of 1: 100 as the eluent, and the eluate containing the title compound was collected. In addition to solvent that alpha-methyl cinnamonitrile, the separation yield of 72%. |
65% | With potassium hexafluorophosphate; tert.-butylnitrite; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen; 1,1,1,3,3,3-hexamethyl-disilazane; In acetonitrile; at 50℃; for 8h;Sealed tube; | In a 100ml flask, 30mL acetonitrile, 10mmolHMDS, 0.4mmol the TEMPO, 0.4mmol of KPF6And 0.6mmol of a TBN, replacement of oxygen to the air bottle, sealed with a rubber stopper after the bottle, oxygen ball insert, the reaction flask was placed in a pre-heated water bath was heated to 30 , 4mmol slowly added methyl cinnamate of alpha- aldehyde (formula (1-6)), the reaction 8h.The reaction mixture was added sodium thiosulfate solution stirred, then extracted with diethyl ether, the organic layer was separated, the solvent was distilled off under reduced pressure, and then separated by column chromatography with ethyl acetate / petroleum ether volume ratio of 1: 100 mixture of eluent, the eluate containing the object compound were collected, the solvent was distilled off to give methyl alpha- cinnamonitrile, isolated in 61% yield.; The reaction steps described in Example 18, except that the reaction temperature was changed to acetonitrile is 50 50mL, alpha- methyl cinnamate isolated yield of 65% nitrile. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
a: Acetic anhydride, RT, then 50C, 4 h b: Ethyl iodide, DMF, 65oC, 3 h c: Sodium borohydride, THF, 0C to RT, 14 H d: 10% Pd/C, methanol, H2 3Kg pressure, 14 h e: HCI, 100C, 14 H, f : 1/a-methyl cinnamaldehyde, dichloromethane 2/Sodium borohydride, methanol Scheme 21: Preparation of (1-ETHYL-PIPERIDIN-3-YL)- (2-METHYL-3-PHENYL-ALLYL)-AMINE [00337] Experimental condition analogous to Example 18 were used with (1-ethyl-piperidin-3-yl)- (2-methyl-3-phenyl-allyl)-amine 0.35 g (1.3 MMOL), 3,4, 5-trimethoxybenzoic acid 0.18 g (0.86 MMOL), thionyl chloride 0.39 g, and triethylamine 0.19 ml, in 10 ml of dichlorometane. The reaction yielded 35 mg of free amine, which was converted to the HCI salt as an off-white solid. Yield: 9%. [00338] LC-MSD, m/z for C27H36N204 [M+H] +: 453.3, [00339] 1H NMR (300 MHz, MeOD) : 5 1. 2-1.5 (m, 3 H), 1.7-2. 4 (m, 7 H), 3.0 (t, 1 H), 3.3-3. 4 (m, 2 H), 3.6 (d, 2 H), 3.6-3. 9 (m, 10 H), 4.1-4. 3 (m, 2 H), 4.3-4. 4 (m, 1 H), 6.4 (s, 1 H), 6.8 (s, 2 H), 7.2-7. 5 (m, 5 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | [0097] 0.5 g of 2- (1-methyl-prrolidin-2-yl)-ethylamine (3.89 MMOL) and 0.56 g of 2-methyl-3-phenyl-propenal were combined in 20 ml of anhydrous dichloromethane. The mixture was stirred under nitrogen on 5 g of magnesium sulfate. After two days, thin layer chromatography (TLC) using a 9: 1: 0.1 DICHLOROMETHANE/METHANOL/AMMONIUM hydroxide eluent showed an absence of the starting material. The reaction mixture was filtered, and the collected solid was washed with dichloromethane. The resultant organic layer was then concentrated under vacuum. Ten ml of dry methanol was added to the residual mixture under nitrogen and the solution was cooled to 0C. To this mixture was added 0.14 g of sodium borohydride. TLC showed an absence of starting material after about 15 minutes. The reaction was then quenched with acetone (1 ML), and the solvent was removed by distillation. The mixture was partitioned between 5 mi of water in chloroform and the layers were separated. The aqueous layer was then extracted 3 times with 30 mi chloroform. The combined organic layer was washed with brine, dried over sodium sulfate, and filtered. Concentration under vacuum gave 0.78 g of a pale yellow solid. Yield: 77%. [0098] LC-MSD, m/z for C17H26N2 [M+H] +: 259, [M+2H] +: 260 [0099] H NMR (400 MHz, CDCI3) : 8 1.4-1. 6 (m, 2H), 1.67-1. 82 (m, 3H), 1.9-2. 0 (m, 3 H), 2. 02- 2. 20 (m, 2H), 2.38 (s, 3H), 2. 58- 2. 79 (m, 2, H), 3.02-3. 08 (m, 1 H), 3.39 (s, 2H), 7.16-7. 39 (m, 5H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
a: Borane dimethylsulfide, THF, 14 h, RT b: METHANESULFONYLCHLORIDE, triethylamine, dichloromethane, 4 h, RT c: Sodium cyanide, DIMETHYLFORMAMIDE, 5 h, RT d: Raney nickel, ammonia gas in methanol, H2 2. 5 kg pressure, 14 h e: 1/ 1-methyl cinnamaldehyde, dichloromethane, 16 H, RT, N2 2/Sodium borohydride, methanol, 30 minutes at 0C Scheme 2: Preparation OF2- [2- (2-METHYL-3-PHENYL-ALLYLAMINO)-ETHYL- (S)-PYRROLIDINE-L-CARBOXYLIC acid tert-butyl ester [00138] Compound 2- [2- (2-Methyl-3-phenyl-allylamino)-ethyl- (S)- PYRROLIDINE-1-CARBOXYLIC acid tert-butyl ester (prepared from (S)-Pyrrolidine- 1, 2-DICARBOXYLIC ACID-1-TERT-BUTYL ester according to the scheme 2) 0.47 g (1.3 MMOL) and 3,4, 5-trimethoxy benzoic acid 0.3 g (1.6 MMOL) in dry dichloromethane 10ml, triethyl amine 0.1 ml was added and stirred at room temperature for 20 min. Then 1-DIMETHYLAMINOPROPYL-3-ETHYL CARBODIIMIDE 0.3 g (2 MMOL) and 1-hydroxybenzotriazole 0.018 g (0.13 MMOL) was added at 0C. The reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with dichloromethane and was washed with 10% sodium bicarbonate solution, water and brine, dried, concentrated and subjected to column chromatography (silica gel, n-hexane: ethylacetate as eluent) to yield 0.57 g 2-{2-[(2-METHYL-3-PHENYL-ALLYL)-3, 4,5-trimethoxy- BENZOYL)-AMINO]-ETHYL}-(S)-PYRROLIDINE-1-CARBOXYLIC acid tert-butyl ester (Yield : 76%). The compound 0.22 g (0.4 MMOL) was dissolved in 5ML of dry ether and 5ML of dry ether saturated with HCI was added at 0C. The reaction mixture was stirred at room temperature for 10 hrs. The ether was concentrated and the residue was washed with dry ether three to four times to yield 0.12 g as a white solid. Yield : 30%. [00139] LC-MSD, m/z for C26H34N204 [M+H] +: 439.3 [00140] 1H NMR (300 MHz, MeOD) : 8 1. 6-1.8 (m, 4 H), 2.0-2. 25 (m, 6H), 3.3-3. 5 (m, 3H), 3.2 (m, 3H), 3.5-4. 0 (m, 12H), 4.1 (s, 1H), 6.5 (s, 1H), 6.8-7. 0 (m, 2H), 7.2-7. 5 (m, 5H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
a: Acrylonitrile, 70 C, 14 h b: Raney nickel, ammonia gas, methanol, H2 3kg pressure c: 1/A-METHYL CINNAMALDEHYDE, DICHLOROMETHANE, N2, 18 h, RT 2/Sodium borohydride, methanol, 0C, 15 minutes Scheme 6: Preparation of (2-METHYL-3-PHENYL-ALLYL)- [3- (3-METHYL-PIPERIDIN-1-YL-PROPYL-AMINE [00150] Experimental condition analogous to Example 13 were used with (2-METHYL-3-PHENYL-ALLYL)- [3- (3-METHYL-PIPERIDIN-1-YL)-PROPYL]-AMINE (prepared from 3-methyl-piperidine described on the scheme 6) 1 g (3.5 MMOL), 3,4, 5-trimethoxy benzoic acid 0.89 g (4.2 MMOL), triethylamine 0.5 ML and 0- (BENZOTRIAZOL-1-YL)-N, N, N', N'-TETRAMETHYLURONIUM TETRAFLUOROBORATE 1.68 g (5.7 MMOL). The reaction yielded the free amine, which was converted to its hydrochloride salt (using dry HCI in ether) 0.9 g as white solid. Yield: 49%. [00151] LC-MSD, m/z for C29H40N204 [M+H] +: 481.2, [M+2H] +: 482.2. [00152] 1H NMR (300 MHZ, MEOD) : 6 0. 8- 1. 1 (m, 4 H), 1.1-1. 3 (m, 1H), 1.3-1. 4 (s, 1 H), 1.6-2. 0 (m, 3H), 2.1-2. 3 (m, 2 H), 2.4-2. 5 (m, 1 H), 2.5-2. 7 (m, 1H), 3.0-. 3.1 (m, 2H), 3.3-3. 5 (m, 2 H), 3.5-3. 7 (m, 2 H), 3.7-3. 9 (m, 10H), 4.0- 4.4 (m, 2H), 6.5 (s, 1 H), 6.7-7. 0 (m, 2H), 7.2-7. 5 (m, 5H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
a: Acrylonitrile, 70 C, 14 h b: Raney nickel, ammonia gas, methanol, H2 3 kg pressure c: 1/SX-METHYL CINNAMALDEHYDE, DICHLOROMETLLANE, N2, 18 h, RT 2/Sodium borohydride, methanol, 0C, 15 minutes Scheme 8: Preparation OF 1- (R)- (3- (2-METHYL-3-PHENYL-ALLYLAMINO)- propyl]-pyrrolidin-3-ol [00157] Experimental condition analogous to Example 3 were used with 1- (R)- [3- (2-METHYL-3-PHENYL-ALLYLAMINO)-PROPYL]-PYRROLIDIN-3-OL (prepared from (R)-pyrrolidin-3-ol described in the scheme 8) 0.5 g (1. 845MMOL), 3,4, 5- trimethoxybenzoic acid 0.46 g (2.1 MMOL), triethylamine 0.3 ml, and 1- propanephosphonic acid cyclic anhydride solution (50% in ethyl acetate) 0.34 g in 20 ml ethyl acetate. The reaction yielded 28mg of free amine. The compound was dissolved in dry ether and transformed to the HCI salt, giving 30 mg of white solid. Yield : 3%. [00158] LC-MSD, m/z for C27H36N205 [M+H] +: 469.4 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: tert-butyl (2R)-2-(2-aminoethyl)-1-pyrrolidinecarboxylate; 2-methyl-3-phenyl-2-propenal In dichloromethane at 20℃; for 16h; Stage #2: With sodium tetrahydroborate In methanol at 0℃; for 0.5h; | 17.e Example 17: 3,4, 5-TRIMETHOXY-N-(2-METHYL-3-PHENYL-ALLYL)-N-(2-(R)- pyrrolidin-2-yl-ethyl)-benzamide a: Borane dimethylsulfid, THF, 14 h, RT b: Methansulfonylchloride, triethylamine, dichloromethane, 4 h, RT c: Sodium cyanide, DIMETHYLFORMAMIDE, 5 h, RT d: Raney nickel, ammonia gas in methanol, H2 2.5 kg pressure, 14 h e: 1/1-METLIYL CINNAMALDEHYDE, DICHLOROMETHANE, 16 h, RT, N2 2/Sodium borohydride, methanol, 30 minutes at 0°C Scheme 3: Preparation OF 2-[2-(2-METHYL-3-PHENYL-ALLYLAMINO)-ETHYL-(R)-PYRROLIDINE-1-CARBOXYLIC acid tert-butyl ester [00141] Experimental condition analogous to Example 13 were used with 2- [2- (2-METHYL-3-PHENYL-ALLYLAMINO)]-ETHYL- (R) PYRROLIDINE-1-CARBOXYLIC acid tert-butyl ester (prepared from (R)-Pyrrolidine-1, 2-dicarboxylic ACID-1-TERT- butyl ester according to the scheme 3) 0.6 g (2 MMOL), 3,4, 5-trimethoxy benzoic acid 0.51 g (2.4 mmol), O-(BENZOTRIAZOLE-1-YL)-N, N, N', N'- TETRAMETHYLURONIUM tetrafluoroborate 1. 3-G (4-MMOL) and triethylamine 0-. 2 ml. The intermediate 2-{2-[(2-methyl-3-phenyl-allyl)-(3, 4, 5-TRIMETHOXY-BENZOYL)- amino-]-ethyl}-pyrrolidine-1-carboxylic acid tert-butyl ester was dissolved in 10 ML of dioxane and 5 ml of 6 N HCI, yielding 0.35 g of the compound after basic work-up and purification. Yield: 39%. [00142] LC-MSD, m/z for C26H34N204 [M+H] + : 439.3 [00143] 1H NMR (300 MHz, MeOD/D20): 61. 8 (s, 4 H), 1.9-2. 25 (m, 6H), 3.2 (m, 3H), 3.5-4. 0 (m, 12H), 4.1 (s, 1H), 6.5 (s, 1H), 6.8-7. 0 (m, 2H), 7.2-7. 5 (m, 5H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With lithium diisopropyl amide In tetrahydrofuran at -78℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70 %Chromat. | With montmorillonite K-10 at 90℃; for 0.1h; Microwave irradiation; neat (no solvent); | |
Stage #1: 2-methyl-3-phenyl-2-propenal; aniline With hydrogenchloride In water for 5h; Reflux; Stage #2: With sodium hydroxide In water; ethyl acetate at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.3%Spectr.; 17.7%Spectr. | With formic acid; [Ir(2,2':6',2'?-terpyridine)(1,10-phenanthroline)Cl](PF6)2; sodium formate; In ethanol; water; at 100℃; for 1.66667h;pH Ca.5.2;Microwave irradiation; | General procedure: An aldehyde (1 mmol),sodium formate (4.5 eq), and catalyst (0.2 mol%) were taken in70% ethanol in water (4 mL) in a microwave vial and vortexed togenerate a homogenous solution. The mixture was heated in MWat 100 C using 150W of irradiation. Reaction progress was monitored by TLC. If complete conversion took place, the reaction colorturns to emerald green (color disappears after sometime) from paleyellow, and byproduct Na2CO3 precipitates. The Na2CO3 solid wasremoved by decanting the supernatant. The solid was washed withethyl acetate (20 mL). The combined decanted solution waswashed with water (5.0 mL), followed by brine solution (5.0 mL),dried over Na2SO4, filtered, and evaporated to dryness to affordthe desired alcohol as a pale-yellow liquid or off-white solid. |
24.5%Spectr.; 75.5%Spectr. | With [Ir(2,2':6',2'?-terpyridine)(1,10-phenanthroline)Cl](PF6)2; sodium formate; In ethanol; water; at 100℃; for 1.5h;pH 9;Microwave irradiation; | General procedure: An aldehyde (1 mmol),sodium formate (4.5 eq), and catalyst (0.2 mol%) were taken in70% ethanol in water (4 mL) in a microwave vial and vortexed togenerate a homogenous solution. The mixture was heated in MWat 100 C using 150W of irradiation. Reaction progress was monitored by TLC. If complete conversion took place, the reaction colorturns to emerald green (color disappears after sometime) from paleyellow, and byproduct Na2CO3 precipitates. The Na2CO3 solid wasremoved by decanting the supernatant. The solid was washed withethyl acetate (20 mL). The combined decanted solution waswashed with water (5.0 mL), followed by brine solution (5.0 mL),dried over Na2SO4, filtered, and evaporated to dryness to affordthe desired alcohol as a pale-yellow liquid or off-white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tetrabutylammomium bromide; toluene-4-sulfonic acid hydrazide; sodium hydroxide; In water; at 80℃; for 10h;Air atmosphere; | General procedure: A Schlenk tube with a magnetic stir bar charged with alpha,beta-unsaturated carbonyl compounds (0.5 mmol, 1 equiv), tosyl hydrazide (0.6 mmol, 1.2 equiv), NaOH (1.5 equiv), (n-Bu)4NBr (1.5 equiv). The reaction vessel was placed in an 80 C oil bath, and then stirring at this temperature for 10 h. The reaction mixture was then allowed to cool to ambient temperature, and diluted with 20 mL of ethyl acetate, and washed with brine (15 mL), water (15 mL), and then the organic layer was dried over Na2SO4. After concentrated in vacuo, the crude product was purified by column chromatography. The identity and purity of the known product was confirmed by 1H NMR, 13C NMR, and GC-MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 35% 2: 44% | In chloroform at 20℃; for 144h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With ammonium acetate; In neat (no solvent); at 20℃; for 0.25h;Green chemistry; | General procedure: The nickel(II) Schiff base complex immobilized on MWCNTs as a heterogeneous catalyst (0.005 g) was added to a mixture of aromatic aldehyde (1 mmol), 1,3-dione (1 mmol), ethyl acetoacetate (1 mmol), and ammonium acetate (1.5 mmol) in a round bottom flask and the resulting mixture was stirred magnetically under solvent-free conditions at room temperature. After reaction, as observed by TLC (n-hexane/ethyl acetate: 5/2), ethyl acetate (5 mL) was added to the reaction mixture, stirred and refluxed for 10 min, washed with ethanol (5 mL) and decanted to separate catalyst from other materials (the reaction mixture was soluble in hot ethyl acetate and nanocatalyst was insoluble). The solvent of organic layer was evaporated and the crude product was purified by recrystallization from ethanol. In this study, nanoheterogeneous catalyst was recycled and reused for seven times without significant loss of its catalytic activity. |
83% | With ammonium acetate; chitosan; at 60℃; for 0.183333h;Green chemistry; | General procedure: Substituted aldehyde (0.5 mmol), ammonium acetate (1 mmol, 0.077 g), dimedone(0.5 mmol, 0.071 g), ethyl or methyl acetoacetate (0.6 mmol, 0.065 or 0.059 g) or acetoacetanilide (0.6 mmol, 0.106 g) in the presence of a catalytic amount of chitosan (0.015 g, more than 0.011 g deacetylated) were magnetically stirred without solvent at 60 C for appropriate times as specified in Tables 3 and 4. The progress of the reaction was monitored by TLC 30 % EA: Hex. After completion of the reaction, the resulting solid products was dissolved in hot ethanol, filtered for removing the unsolvable catalyst and then the filtrate was concentrated and the crude was purified by recrystallization from ethanol to afford the pure 1,4-dihidropyridine drivatives (5a-5x). The catalyst was subsequently washed with5 ml ethanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With pyrazine-1,4-diium trinitromethanide; In neat (no solvent); at 25℃; for 0.416667h;Green chemistry; | General procedure: To a mixture of aromatic aldehydes (1 mmol), beta-naphthol (1 mmol; 0.144 g) and 2 or 4-aminopyridine (1 mmol; 0.094 g) in a round bottom flask, 1 mol% of [1,4-DHPyrazine][C(NO2)3]2} nano-structured molten salt or 2 mol% of Ag-TiO2 nano composite was added as catalyst and stirred at room temperature under solvent-free conditions for appropriate time (Table 4). After completion of the reaction as monitored by thin layer chromathography (TLC) (n-hexane/ethyl acetate: 5/2), ethyl acetate (10 mL) was added to reaction mixture and stirred under reflux condition for 10 min. Then, the resulting mixture was washed with water (10 mL) and decanted to separate catalyst from the other materials (the reaction mixture was soluble in hot ethyl acetate and nano molten salt catalyst was soluble in water). The aqueous layer was decanted, separated and removed the water to give the catalyst for another reaction. The solvent of organic layer was removed and the crude product was purified by recrystallization from ethanol (95%). Note: In another procedure, for the recycle of Ag-TiO2 nano composite, at the end of reaction, warm ethyl acetate was added to the reaction mixture and centrifuged to separate product and starting materials from the catalyst (Ag-TiO2 nano composite as catalyst is insoluble in ethyl acetate). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With 1-methylimidazolium tricyanomethanide; ammonium acetate; In neat (no solvent); at 20℃; for 0.166667h;Green chemistry; | General procedure: [HMIM]C(CN)3} as a nanostructuredmolten salt catalyst (0.5mol%;0.0009 g) was added to a mixture of various aromatic aldehydes(1 mmol), 1,3-diketone (2 mmol) and ammonium acetate or severalanilines (1 mmol) in a round bottom flask, and the produced mixturewas stirredmagnetically under solvent-free conditions at roomtemperature.After completion of the reaction, as monitored by TLC n-hexane/ethyl acetate (5:3), ethyl acetate (10 mL) was added to reaction mixture,stirred and refluxed for 3 min, and then was washed with water(10 mL) and decanted to separate catalyst from the other materials(the reaction mixture was soluble in hot ethyl acetate and describedmolten salt catalyst was soluble in water). The aqueous layer wasdecanted and the catalyst was separated after removing of water. Theremained catalyst was used for alternative reaction. The solvent oforganic layerwas evaporated and the crude productwas purified by recrystallizationfrom ethanol/water (10:1). In this study, the describedcatalyst was recycled and reused for five times without important lossof its catalytic activity (spectral data for analysis compounds: refer tosupplementary data). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With 1-methylimidazolium tricyanomethanide; In neat (no solvent); at 20℃; for 0.416667h;Green chemistry; | General procedure: [HMIM]C(CN)3} as a nanostructuredmolten salt catalyst (0.5mol%;0.0009 g) was added to a mixture of various aromatic aldehydes(1 mmol), 1,3-diketone (2 mmol) and ammonium acetate or severalanilines (1 mmol) in a round bottom flask, and the produced mixturewas stirredmagnetically under solvent-free conditions at roomtemperature.After completion of the reaction, as monitored by TLC n-hexane/ethyl acetate (5:3), ethyl acetate (10 mL) was added to reaction mixture,stirred and refluxed for 3 min, and then was washed with water(10 mL) and decanted to separate catalyst from the other materials(the reaction mixture was soluble in hot ethyl acetate and describedmolten salt catalyst was soluble in water). The aqueous layer wasdecanted and the catalyst was separated after removing of water. Theremained catalyst was used for alternative reaction. The solvent oforganic layerwas evaporated and the crude productwas purified by recrystallizationfrom ethanol/water (10:1). In this study, the describedcatalyst was recycled and reused for five times without important lossof its catalytic activity (spectral data for analysis compounds: refer tosupplementary data). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With 1-methylimidazolium tricyanomethanide; In neat (no solvent); at 20℃; for 0.333333h;Green chemistry; | General procedure: [HMIM]C(CN)3} as a nanostructuredmolten salt catalyst (0.5mol%;0.0009 g) was added to a mixture of various aromatic aldehydes(1 mmol), 1,3-diketone (2 mmol) and ammonium acetate or severalanilines (1 mmol) in a round bottom flask, and the produced mixturewas stirredmagnetically under solvent-free conditions at roomtemperature.After completion of the reaction, as monitored by TLC n-hexane/ethyl acetate (5:3), ethyl acetate (10 mL) was added to reaction mixture,stirred and refluxed for 3 min, and then was washed with water(10 mL) and decanted to separate catalyst from the other materials(the reaction mixture was soluble in hot ethyl acetate and describedmolten salt catalyst was soluble in water). The aqueous layer wasdecanted and the catalyst was separated after removing of water. Theremained catalyst was used for alternative reaction. The solvent oforganic layerwas evaporated and the crude productwas purified by recrystallizationfrom ethanol/water (10:1). In this study, the describedcatalyst was recycled and reused for five times without important lossof its catalytic activity (spectral data for analysis compounds: refer tosupplementary data). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With 1-methylimidazolium tricyanomethanide; ammonium acetate; In neat (no solvent); at 20℃; for 0.2h;Green chemistry; | General procedure: [HMIM]C(CN)3} as a nanostructuredmolten salt catalyst (0.5mol%;0.0009 g) was added to a mixture of various aromatic aldehydes(1 mmol), 1,3-diketone (2 mmol) and ammonium acetate or severalanilines (1 mmol) in a round bottom flask, and the produced mixturewas stirredmagnetically under solvent-free conditions at roomtemperature.After completion of the reaction, as monitored by TLC n-hexane/ethyl acetate (5:3), ethyl acetate (10 mL) was added to reaction mixture,stirred and refluxed for 3 min, and then was washed with water(10 mL) and decanted to separate catalyst from the other materials(the reaction mixture was soluble in hot ethyl acetate and describedmolten salt catalyst was soluble in water). The aqueous layer wasdecanted and the catalyst was separated after removing of water. Theremained catalyst was used for alternative reaction. The solvent oforganic layerwas evaporated and the crude productwas purified by recrystallizationfrom ethanol/water (10:1). In this study, the describedcatalyst was recycled and reused for five times without important lossof its catalytic activity (spectral data for analysis compounds: refer tosupplementary data). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With 1-methylimidazolium tricyanomethanide; In neat (no solvent); at 20℃; for 0.5h;Green chemistry; | General procedure: [HMIM]C(CN)3} as a nanostructuredmolten salt catalyst (0.5mol%;0.0009 g) was added to a mixture of various aromatic aldehydes(1 mmol), 1,3-diketone (2 mmol) and ammonium acetate or severalanilines (1 mmol) in a round bottom flask, and the produced mixturewas stirredmagnetically under solvent-free conditions at roomtemperature.After completion of the reaction, as monitored by TLC n-hexane/ethyl acetate (5:3), ethyl acetate (10 mL) was added to reaction mixture,stirred and refluxed for 3 min, and then was washed with water(10 mL) and decanted to separate catalyst from the other materials(the reaction mixture was soluble in hot ethyl acetate and describedmolten salt catalyst was soluble in water). The aqueous layer wasdecanted and the catalyst was separated after removing of water. Theremained catalyst was used for alternative reaction. The solvent oforganic layerwas evaporated and the crude productwas purified by recrystallizationfrom ethanol/water (10:1). In this study, the describedcatalyst was recycled and reused for five times without important lossof its catalytic activity (spectral data for analysis compounds: refer tosupplementary data). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With 1-methylimidazolium tricyanomethanide; In neat (no solvent); at 20℃; for 0.416667h;Green chemistry; | General procedure: [HMIM]C(CN)3} as a nanostructuredmolten salt catalyst (0.5mol%;0.0009 g) was added to a mixture of various aromatic aldehydes(1 mmol), 1,3-diketone (2 mmol) and ammonium acetate or severalanilines (1 mmol) in a round bottom flask, and the produced mixturewas stirredmagnetically under solvent-free conditions at roomtemperature.After completion of the reaction, as monitored by TLC n-hexane/ethyl acetate (5:3), ethyl acetate (10 mL) was added to reaction mixture,stirred and refluxed for 3 min, and then was washed with water(10 mL) and decanted to separate catalyst from the other materials(the reaction mixture was soluble in hot ethyl acetate and describedmolten salt catalyst was soluble in water). The aqueous layer wasdecanted and the catalyst was separated after removing of water. Theremained catalyst was used for alternative reaction. The solvent oforganic layerwas evaporated and the crude productwas purified by recrystallizationfrom ethanol/water (10:1). In this study, the describedcatalyst was recycled and reused for five times without important lossof its catalytic activity (spectral data for analysis compounds: refer tosupplementary data). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | Stage #1: 7-methoxy-1H-indole; 2-methyl-3-phenyl-2-propenal With trimethylsilyl trifluoromethanesulfonate; N-ethyl-N,N-diisopropylamine In diethyl ether at -50℃; for 1h; Inert atmosphere; Stage #2: With lithium aluminium tetrahydride In tetrahydrofuran; diethyl ether at -50 - 25℃; for 1h; Inert atmosphere; |
Tags: 101-39-3 synthesis path| 101-39-3 SDS| 101-39-3 COA| 101-39-3 purity| 101-39-3 application| 101-39-3 NMR| 101-39-3 COA| 101-39-3 structure
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P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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