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CAS No. : | 123-56-8 | MDL No. : | MFCD00005495 |
Formula : | C4H5NO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | KZNICNPSHKQLFF-UHFFFAOYSA-N |
M.W : | 99.09 | Pubchem ID : | 11439 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302 | 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 |
---|---|---|
95% | With potassium carbonate; In neat (no solvent); at 60 - 65℃; for 0.0666667h;Microwave irradiation; Green chemistry; | General procedure: A mixture of phthalimide (4.8 mmol, 0.70 g), alkyl halide(6.0 mmol), 4a or 4b (0.3 mmol, 3 mol%) and potassiumcarbonate (18.8 mmol, 2.6 g) was heated in a commercialmicrowave oven in an open Erlenmeyer flask at 60 8C-65 8Cfor the required time (as shown in Table 3) according to a50:10-s heating: cooling cycle, each at an 80% power level.The completion of the reaction was monitored using TLC.After cooling to r.t., the reaction mixture was extracted withmethylene chloride (2 25 mL). Then the extracts weredried over anhydrous Na2SO4, filtered, and the solvent wasevaporated to dryness to give the crude product. Solids werepurified through recrystallization in absolute EtOH, and liquids were purified over a silica gel column using hexane:EtOAc (96:4) as the eluent. The successful formation of theproducts was confirmed by 1H NMR, 13C NMR and FT-IRspectra. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | General procedure: A mixture of 50 mg of imide and the required amount of K2CO3 were placed in a 10 mL stainlesssteel grinding jar and milled for 1 hour at 30 Hz. Upon completion, the required amount of alkylhalide was added and milling was continued for 1 hour in the presence of 100 muL of dry DMF(LAG experiment, eta = 2 muL mg-1). The obtained mixture was suspended in dichloromethane andwashed with water. The organic layers were collected and the solvent was evaporated. Where itwas necessary, the products were separated by using column chromatography | |
57% | With potassium carbonate; In N,N-dimethyl-formamide; at 55℃; | Intermediate 53; 1-(Phenylmethyl)-2,5-pyrrolidinedione; To 2,5-pyrrolidinedione (2.5 g, 25.2 mmol) in DMF (50 ml.) was added K2CO3 (4.18 g, 30.3 mmol) followed by benzyl bromide (3.00 ml_, 25.2 mmol), and the reaction mixture was stirred overnight at 55 0C. Water was added to the reaction mixture (-200 ml.) and a precipitate was immediately observed. The precipitate was filtered, and the white solid was washed with water and dried to afford the title compound (2.7 g, 57%). 1H NMR (400 MHz, CDCI3): delta 2.73 (s, 4H), 4.68 (s, 2H), 7.28 - 7.37 (m, 3H), 7.39 - 7.44 (m, 2H). |
57% | With potassium carbonate; In N,N-dimethyl-formamide; at 55℃; | To 2,5-pyrrolidinedione (2.5 g, 25.2 mmol) in DMF (50 ml.) was added K2CO3 (4.18 g, 30.3 mmol) followed by benzyl bromide (3.00 ml_, 25.2 mmol), and the reaction mixture was stirred overnight at 55 0C. Water was added to the reaction mixture (-200 ml.) and a precipitate was immediately observed. The precipitate was filtered, and the white solid was washed with water and dried to afford the title compound (2.7 g, 57%). 1H NMR (400 MHz, CDCI3): delta 2.73 (s, 4H), 4.68 (s, 2H), 7.28 - 7.37 (m, 3H), 7.39 - 7.44 (m, 2H). |
With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 3h; | In 200 mL of carbon tetrachloride, 18.4 g of toluene, 42.6 g of bromosuccinimide and 0.65 g of azobisisobutyronitrile were added and the reaction was heated at reflux for 5 h.Carbon tetrachloride was removed by distillation under reduced pressure, 100 mL of dimethylformamide and 45 g of potassium carbonate were added, and the mixture was heated to 80 C for 3 h.Then, 50 mL of concentrated hydrochloric acid was added and the mixture was heated to 100 C for 3 h.Cool to room temperature, filter out part of the succinic acid, extracted with 50mL of ethyl acetate to further remove the succinic acid.The pH of the reaction system was adjusted to 7 with sodium hydroxide and extracted twice with 100 mL of ethyl acetate. The ethyl acetate phase was combined and the ethyl acetate was distilled off under reduced pressure to obtain 13.8 g of benzylamine in a yield of 64.4%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sodium hydroxide; N-chloro-succinimide; In dichloromethane; | (c) 4-Methoxy-6-(methylthiomethyl)-2-(alpha,alpha,alpha-trifluoromethyl)aniline was prepared by substituting 4-methoxy-2-(alpha,alpha,alpha-trifluoromethyl)aniline as follows: In a 250 ml three-necked flask equipped with an overhead stirrer was placed 20.12 g (0.105 mol) of 4-methoxy-2-(alpha,alpha,alpha-trifluoromethyl)aniline in 100 ml of methylene chloride. To the solution was then added 15.63 g (0.117 mol) of N-chlorosuccinimide was added with vigorous stirring. After cooling to 0 C. under a nitrogen atmosphere, a solution of 9.2 ml (8.02 g, 0.129 mol) dimethylsulfide in 40 ml of methylene chloride was then added over a one hour period while maintaining the temperature below 5 C. The reaction mixture became very thick. The ice bath was removed and after stirring at room temperature for one hour, 200 ml of ice cold 5% aqueous sodium hydroxide solution was added. The methylene chloride layer was separated, dried over anhydrous potassium carbonate, filtered and the solvent removed under reduced pressure. To the residue was then added 60 ml of 1,2-dichloroethane and 1.00 g (10 mmol) of succinimide. After refluxing for twelve hours under a nitrogen atmosphere, the reaction mixture was cooled, washed twice with 100 ml of 5% sodium hydroxide solution, dried with magnesium sulfate, filtered and concentrated under reduced pressure to afford 24.9 g of a black oil. This was distilled under reduced pressure to afford 16.5 g (63% yield) of the desired product as a clear, colorless liquid (Bp 106-110 at 0.35 mm Hg) of 95% purity as assayed by gas chromatography; 1 H NMR analysis indicated: (delta, CDCl3) 6.94 (d, J=1.8 Hz, 1H), 6.78 (d, J=1.8 Hz, 1H), 4.32 (br s, 2H, NHz), 3.54 (s, 3H), 3.51 (s, 2H) and 1.82 (s, 3H). Mass spectrum analysis indicated: (m/e) 251 (M+), 204 (100%) and 181. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With dicyclohexyl-carbodiimide; In N,N-dimethyl-formamide; at 25℃; for 17h;Inert atmosphere; | To a solution of 6-Boc-hydrazinopyridine-3-carboxylicacid 4b (0.57 g, 2.26 mmol) and N-hydrosuccinimide (0.27g, 2.26 mmol) in DMF DCC (0.47 g, 2.26 mmol) was added.The reaction mixture became cloudy after 1h. After 16h, thereaction mixture was concentrated to dryness and the residuewas purified by chromatography on silica gel with ethyl acetateas eluant to give a white solid (0.66 g, 84%). Mp =174C. IR (ATR, cm-1) 3321; 2979; 1729; 1594; 1365; 1240;1198; 1068; 974; 641. 1H NMR (DMSO) 9.46 (s, 1H), 9.20(s, 1H), 8.76 (d, 1H, J= 2.1 Hz), 8.11 (d, 1H, J= 8.1 Hz),6.67 (d, 1H, J= 9 Hz), 2.88 (s, 4H), 1.44 (s, 9H). 13C NMR(DMSO) 172.8; 170.5; 160.9; 155.4; 151.8; 110.0; 79.6;28.0; 25.5. MS (ESI+) [M+H]: 351.00. HRMS (ESI+)[M+H]+: 351.1299 observed, 351.1305 calculated forC15H19N4O6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With copper; at 50℃; for 3h; | General procedure: b. A mixture of 0.13 g (0.002 mol) of copper nanoparticles, 5 g (0.11 mol) of formamide, and 11.9 g(0.12 mol) of amine Va was stirred for 30 min at 20-40C. An excess of the amine was distilled off, and the residue was distilled. Yield 11.3 g (0.1 mol, 91%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | The bis(cyclopentadiene) zirconium dihydride (denoted as Cp2ZrH2, 0.01mmol, 2.23mg), pyrrolidine-2,5-dione (denoted as 3t, 0.2mmol, 19.8mg) and pinacol borane ( Recorded as HBpin, 0.6mmol, 87μL), stirred at room temperature under nitrogen (1atm) atmosphere for 12h, treated with hydrogen chloride in ether solution to obtain the hydrochloride compound of formula 4t structure (white solid, pyrrolidine hydrochloride). The isolated yield was 76%. |