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CAS No. : | 5932-30-9 | MDL No. : | MFCD02130942 |
Formula : | C12H12N2O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | AZZHJDRWBMQEKD-UHFFFAOYSA-N |
M.W : | 216.24 | Pubchem ID : | 138628 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H332-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 |
---|---|---|
With 1,4-diaza-bicyclo[2.2.2]octane; at 20℃; for 6h; | To a mixture of phenyl acetylene 1 (0.1 g, 1 mmol) and ethyldiazoacetate 2 (0.114 g) was added DABCO (1,4-diazabicyclo[2.2.2]octane) (0.011 g, 0.1 mmol) and stirred for 6 h at ambienttemperature. Upon completion of the reaction which was monitoredby TLC, the crude reaction product was purified by passingthrough Silica gel using 20% ethyl acetate in pet. ether to affordcompound 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With hydrazine hydrate; acetic acid; In ethanol; at 20℃; for 5h; | To a solution of compound 22 (l. lg, 5 mmol) and AcOH (0.360 g, 5.00 mmol) in 20 ml EtOH was added 80% hydrazine hydrate (0.316 g, 5.05 mmol). After stirred at rt for 5h, the mixture was diluted with water,' then EtOH was removed under reduced pressure, and aqueous solution was made alkaline by saturated aqueous solution of NaHC03 then extracted with ethyl acetate, dried by anhydrous Na2S04, concentrated to afford compound 23 (1.08 g, 99% yield).LCMS m/z=217 [M+H] + LC/MS informationColumn: Xbridge C 18 (3.5μιη 4.6x50mm)Flow rate: 1.8 mL/minUV detection wavelength: 254nmMobile phase: [A] is 0.05% TFA-containing aqueoous solution, and [B] is 0.05% TFA- containing acetonitrile solutionFrom 0 to 1.5 minutes, . the percentage of [B] in the mobile phase was gradually increased from 5% to 100%. Thereafter a solution of 100% of [B] was used as the mobile phase.retention time= 1.21 minutes. |
95.6% | With hydrazine hydrate; In ethanol; at 20℃; for 3h;Reflux; | The above obtained intermediate 2-1 (9.3 g, 0.042 mol) was added into a round-bottom flask charged with 50 mL of ethanol, followed by addition of hydrazine hydrate (2.1 g, 0.042 mol) dropwise under stirring at room temperature. After the completion of the addition, the mixture was refluxed for 3 hours and then cooled to room temperature. The ethanol was evaporated, and 10 mL of water was added. The mixture was extracted with ethyl acetate (3×20 mL), and the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was recrystallized with ethyl acetate/petroleum ether (1:5) to give 8.68 g of intermediate 3-1 with a yield of 95.6%. |
67% | With hydrazine; In ethanol; for 3h;Heating / reflux; | Reference Example 23 Ethyl 5-phenyl-1H-pyrazole-3-carboxylate To a solution of ethyl 2,4-dioxo-4-phenylbutanoate (16.0 g) in ethanol (150 mL) was added hydrazine monohydrate (4.0 mL), and the mixture was heated under reflux for 3 hr. The reaction mixture was concentrated under reduced pressure, and the residue was crystallized from diisopropyl ether to give the title compound as a pale-brown solid (yield 12.0 g, 67%). 1H-NMR (CDCl3) δ: 1.41 (3H, t, J=7.4 Hz), 4.41 (2H, q, J=7.4 Hz), 4.80-6.50 (1H, brs), 7.12 (1H, s), 7.30-7.50 (3H, m), 7.79 (2H, d, J=7.9 Hz). |
40.7% | With hydrazine hydrate; In ethanol; at 20℃; for 5h; | To a solution of REX-P-INT-2 (8.6 g, 39.1 mmol) in EtOH (50 mL) was added hydrazine hydrate (2.3 g, 46.9 mmol). The reaction mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into aqueous solution of sodium bicarbonate (100 mL), extracted with EtOAc, washed with brine, dried with anhydrous Na2SO4, filtered and concentrated to give the crude product. The crude product was purified by silica gel chromatography eluted to give product 1-3 (3.4 g, 40.7%). MS m/z [ESI]: 217.1 [M+1]. |
With hydrazine hydrate; triethylamine; In ethanol; at 20℃; for 1h; | Preparation 149Ethyl 5-phenyl-1 H-pyrazole- -carboxylateTo a solution of Preparation 28 in ethanol (350 mL) hydrazine hydrate (2.51 g, 16.72 mmol) in ethanol (70 mL) and triethylamine (2.33 mL, 16.72 mmol) were added and mixture stirred at room temperature for 1 h. Solvent was removed and crude used for next reaction withouth further purification.LRMS: m/z 217 (M+1 )+ Retention time: 5.77 min (Method B) | |
With hydrazine hydrate; triethylamine; In ethanol; at 20℃; for 1h; | To a solution of Preparation 28 in ethanol (350 mL) hydrazine hydrate (2.51 g, 16.72 mmol) in ethanol (70 mL) and triethylamine (2.33 mL, 16.72 mmol) were added and mixture stirred at room temperature for 1 h. Solvent was removed and crude used for next reaction withouth further purification.LRMS: m/z 217 (M+1)+Retention time: 5.77 min (Method B) | |
750 mg | With hydrazine hydro-chloride; In ethanol; for 2h;Reflux; | 383 mg (16.7 mmol) of sodium metal was added in portions to 15 mL of absolute ethanol.After stirring at room temperature until dissolved, diethyl oxalate (1.28 g, 8.75 mmol) was added.After 1 g (8.33 mmol) of acetophenone was dissolved in 15 mL of absolute ethanol,Add to the fresh sodium ethoxide solution under ice bath, and return to room temperature after the addition.After stirring for 6 h, 15 mL of 15% dilute hydrochloric acid was added for acidification, followed by rotary evaporation to remove most of the ethanol.Dilute with 10 mL of water and extract three times with 100 mL of ethyl acetate.The organic phases were combined and dried over anhydrous sodium sulfate.The ethyl acetate in which the product is dissolved is directly dried to obtain a crude intermediate.Re-dissolved by adding 15 mL of absolute ethanol, followed by the addition of hydrazine hydrochloride (1.31 g, 12.50 mmol) and warming to reflux.After reacting for 2 hours, it was cooled to room temperature, and 40 mL of water was added to the reaction mixture, and the mixture was extracted three times with 100 mL of ethyl acetate.The organic phases were combined and dried over anhydrous sodium sulfate.Purification by column chromatography (petroleum ether: ethyl acetate = 4: 1) to give a yellow solid 750mg,The yield is 41.7%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With α,α,α-trifluorotoluene; for 0.166667h;Reflux; | General procedure: A solution of vinyldiazo compound (1.0 eq) in benzotrifluoride (1.2 M) was heated to reflux until complete consumption of the vinyldiazo compound (<10 min). Silica gel was then added and the solvent evaporated. The product was purified by column chromatography (50 - 70% v/v% ethyl acetate/petrol ether) and isolated as off-white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.4% | With sodium hydroxide; In methanol; at 20℃; for 2h; | To a solution of 1-3 (3.4 g, 15.9 mmol) in MeOH (40 mL) was added NaOH (140 mL, 4M). The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure to remove MeOH. The aqueous phase was acidified with aqueous HCl (1 M) till pH=3 and the mixture was extracted with EtOAc, dried with anhydrous Na2SO4, filtered and concentrated to give the crude product. The crude product was purified by silica gel chromatography eluted to give product 1-4 (2.4 g, 80.4%). MS m/z [ESI]: 189.1 [M+1]. |
With sodium hydroxide; In methanol; at 20℃; for 0.5h; | A solution of the ester 3 (0.1 g, 0.46 mmol) in MeOH (4 mL) was treated with 4 N NaOH (4 mL) and stirred at rt for 30 min. Later methanol was removed in vacuo and adjusted to pH 2-3 with aq1 N HCl and extracted with EtOAc. The organic layer was dried over anhydrous sodium sulfate and evaporated to get acid 4. |
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