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CAS No. : | 6102-15-4 | MDL No. : | MFCD00019433 |
Formula : | C11H16O3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | FMQHLVMBLLFWPK-UHFFFAOYSA-N |
M.W : | 196.24 | Pubchem ID : | 223002 |
Synonyms : |
|
Signal Word: | Warning | Class: | |
Precautionary Statements: | P264-P270-P301+P312-P330 | UN#: | |
Hazard Statements: | H302 | Packing Group: | |
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 |
---|---|---|
Reaktion ueber 2 Stufen; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide anschliessend mit wss. H2SO4; | ||
3.7 g | Stage #1: 2,6-dimethyl-4-oxo-cyclohex-2-enecarboxylic acid ethyl ester With sodium hydroxide In methanol; water at 100℃; for 2h; Stage #2: With sulfuric acid In methanol; water at 85℃; for 2h; | 3-4 Example 4: Preparation of compound V (3,5-dimethyl-2-cyclohexen-1-one) Add 4-ethoxycarbonyl-3,5-dimethyl-2-cyclohexen-1-one (11.6g, 59.1mmol) into the flask,Add methanol (1.1mL),Stir evenly, add sodium hydroxide aqueous solution (7.1g dissolved in 30mL water) at room temperature, increase the temperature to 100°C and react for 120min, then cool downAdjust pH>2 with sulfuric acid (15.1g, 154mmol), continue to heat up to 85°C and react for 120min, then cool down,After extraction with methyl tert-butyl ether, the extract was desolvated and distilled under reduced pressure to obtain 3.7 g of compound V. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ammonia; sodium amide Erwaermen des nach Zusatz von Aether vom Ammoniak befreiten Reaktionsgemisches mit Aethyljodid in Aether und Toluol; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With palladium on activated charcoal Hydrogenation.anschliessend mit heisser wss.-aethanol. Natronlauge behandeln; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium <i>tert</i>-butylate In <i>tert</i>-butyl alcohol Inert atmosphere; | |
80% | With potassium <i>tert</i>-butylate In <i>tert</i>-butyl alcohol Heating; | |
71% | With potassium <i>tert</i>-butylate In <i>tert</i>-butyl alcohol for 20h; Heating; |
With piperidine Erhitzen des Reaktionsprodukts mit Eisessig und konz. Schwefelsaeure; | ||
With piperidine In ethanol at 80℃; | ||
23 g | With piperidine In water; toluene for 3h; Reflux; | 1-2 Example 1: Preparation of compound VI (4-ethoxycarbonyl-3,5-dimethyl-2-cyclohexen-1-one) Add 40% acetaldehyde aqueous solution (14.5g, 131.7mmol) and ethyl acetoacetate (37.7g, 289.7mmol) to the flask, add toluene (58mL), stir well, add piperidine (0.11g, 1.3mmol) at room temperature After heating and refluxing reaction for 3 hours, the temperature was lowered, and distillation under reduced pressure was carried out to obtain 23 g of compound VI. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid; mercury(II) sulfate at 70 - 80℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With anion-exchanger; cationen-exchanger |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 1.3% 2: 1% 3: 8.6% | With dmap In chloroform at 60℃; for 48h; | |
1: 8.6% 2: 1.3% 3: 1% | With dmap In chloroform at 60℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With N-Bromosuccinimide; trimethylsilyl trifluoromethanesulfonate In acetonitrile at 25℃; for 12h; Inert atmosphere; | Representative experimental procedure for 1a: To a stirred solution of cyclohexenone 2a (11.30 g, 57.60 mmol) in MeCN (50 mL) were added N-bromosuccinimide (10.25 g, 57.60 mmol) and TMS OTf (1.28 g, 5.76 mmol, 10 mol%). The mixture was stirred at room temperature for 12 h under argon atmosphere, diluted with EtOAc, washed with 1 M HCl, dried over anhydrous Na2SO4, filtered and concentrated to give the crude product (16.02 g) as reddish yellow oil. The crude product was purified by SiO2 flash column chromatography (eluent 25-45% EtOAc/hexane gradient) to give pure phenol 1a (10.18 g, 52.42 mmol) in 91% yield as yellow oil. Data for 1a: Rf = 0.23 (1:4 EtOAc/hexane); 1H-NMR (CDCl3) δ 1.36 (t, J = 7.2 Hz, 3H), 2.25 (s, 6H), 4.35 (q, J = 7.2 Hz, 2H), 6.45 (s, 2H) ppm; 13C-NMR (CDCl3) δ 13.9, 19.8, 61.0, 114.5, 125.2, 137.4, 156.8, 171.0 ppm; IR (KBr) 3381, 2978, 2933, 1715, 1655, 1610, 1592, 1461, 1446, 1368, 1256, 1159, 1088, 1029, 854, 783, 716, 637, 604 cm-1; HRMS (EI) calcd for C11H14O3 194.0943, found 194.0947.. |
45% | With carbon disulfide; bromine 1) -10 deg C; 2) RT,; | |
83.5 %Chromat. | With palladium 10% on activated carbon In N,N-dimethyl acetamide at 150℃; for 24h; | 8 Implementation Example 4-7 Is a starting compound, 2-methyl-4-oxo-2-cyclohexene carboxylate wherein (2), R1 = H, R2 = CH3] N of (730 mg), N-dimethylacetamide (DMA; bp.165 ) solution (4mL) taken up in the reactor, a further 10% palladium charcoal (50% moisture; plus 100mg). The amount after the reaction system was reacted for 2 hours while heating and stirring at 0.99 ° C., the amount of the raw material 4-hydroxy-2-methylbenzoic acid methyl in the reaction mixture (target compound (1)) (2) It was analyzed by HPLC. As a result, the yield of the objective compound (1) is 94.8% residual ratio of the starting compound (2) was 0.1%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 62% 2: 1% | With potassium fluoride; oxygen In dimethyl sulfoxide at 60℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66 g | With toluene-4-sulfonic acid In benzene for 40h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium tetrahydroborate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With water at 140℃; im geschlossenen Rohr; | ||
With sodium ethanolate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 0℃; Erwaermen des Produkts; unter Abspaltung von HBr; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With potassium carbonate In acetone for 48h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With (S)-2-(1-pyrrolidinylmethyl)pyrrolidine In N,N-dimethyl-formamide at 25℃; | |
65% | With (S)-2-(1-pyrrolidinylmethyl)pyrrolidine In dimethyl sulfoxide at 25℃; for 12h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With (S)-2-(1-pyrrolidinylmethyl)pyrrolidine In N,N-dimethyl-formamide at 25℃; | |
50% | With (S)-2-(1-pyrrolidinylmethyl)pyrrolidine In dimethyl sulfoxide at 25℃; for 12h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With 4 A molecular sieve In ethanol at 25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With pyrrolidine In dimethyl sulfoxide at 25℃; | |
Stage #1: 2,6-dimethyl-4-oxo-cyclohex-2-enecarboxylic acid ethyl ester With piperidine In N,N-dimethyl-formamide at 25℃; for 0.5h; Stage #2: Nitrosobenzene In N,N-dimethyl-formamide at 25℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 66 g / p-toluenesulfonic acid / benzene / 40 h / Heating 2: 48 g / lithium aluminium hydride / diethyl ether; tetrahydrofuran / 10 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: aq.-ethanolic NaOH / anschliessend mit wss. H2SO4 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: sodium amide; liquid ammonia / Erwaermen des nach Zusatz von Aether vom Ammoniak befreiten Reaktionsgemisches mit Aethyljodid in Aether und Toluol 2: aq.-ethanolic NaOH / Ansaeuern mit wss. H2SO4 und erneuten Kochen |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: Reaktion ueber 2 Stufen 2: aq.-ethanolic NaOH / anschliessend Behandeln mit wss. H2SO4 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: palladium/charcoal / Hydrogenation.anschliessend mit heisser wss.-aethanol. Natronlauge behandeln 2: acetic acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | Stage #1: 2,6-dimethyl-4-oxo-cyclohex-2-enecarboxylic acid ethyl ester; Nitrosobenzene With piperidine In N,N-dimethyl-formamide at 25℃; for 1.5h; Stage #2: allyl bromide With potassium carbonate In N,N-dimethyl-formamide at 25℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | Stage #1: 2,6-dimethyl-4-oxo-cyclohex-2-enecarboxylic acid ethyl ester With benzylamine In dimethyl sulfoxide Stage #2: With 4-toluenesulfonyl azide In dimethyl sulfoxide at 25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Stage #1: 2,6-dimethyl-4-oxo-cyclohex-2-enecarboxylic acid ethyl ester With <i>L</i>-proline In dimethyl sulfoxide at 25℃; for 0.25h; Stage #2: With 4-toluenesulfonyl azide In dimethyl sulfoxide at 25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With pyrrolidine In dimethyl sulfoxide at 25℃; for 4h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With Lawessons reagent In tetrahydrofuran at 20℃; for 72h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: sodium hydroxide / water; methanol / 2 h / 100 °C 1.2: 2 h / 85 °C / pH > 2 2.1: palladium 10% on activated carbon; hydrogen / methanol / 0.5 h / 25 °C / 18751.9 Torr / Autoclave |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: sodium hydroxide / water; methanol / 2 h / 100 °C 1.2: 2 h / 85 °C / pH > 2 2.1: palladium 10% on activated carbon; hydrogen / methanol / 0.5 h / 25 °C / 18751.9 Torr / Autoclave 3.1: borane tert-butylamine / dichloromethane / 0.5 h / 35 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1.1: sodium hydroxide / water; methanol / 2 h / 100 °C 1.2: 2 h / 85 °C / pH > 2 2.1: palladium 10% on activated carbon; hydrogen / methanol / 0.5 h / 25 °C / 18751.9 Torr / Autoclave 3.1: borane tert-butylamine / dichloromethane / 0.5 h / 35 °C 4.1: dmap; dicyclohexyl-carbodiimide / dichloromethane / 5 h / 40 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 5 steps 1.1: sodium hydroxide / water; methanol / 2 h / 100 °C 1.2: 2 h / 85 °C / pH > 2 2.1: palladium 10% on activated carbon; hydrogen / methanol / 0.5 h / 25 °C / 18751.9 Torr / Autoclave 3.1: borane tert-butylamine / dichloromethane / 0.5 h / 35 °C 4.1: dmap; dicyclohexyl-carbodiimide / dichloromethane / 5 h / 40 °C 5.1: water; methanol; sodium hydroxide / tetrahydrofuran / 1 h / 60 °C |
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