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CAS No. : | 154926-98-4 | MDL No. : | MFCD03789032 |
Formula : | C6H8N2O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | BRWYDRSSDKRKBX-UHFFFAOYSA-N |
M.W : | 124.14 | Pubchem ID : | 2758901 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P264-P271-P280-P302+P352-P304+P340-P305+P351+P338-P312-P313-P337+P313-P362-P403+P233-P405-P501 | UN#: | |
Hazard Statements: | H315-H319-H335 | 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 |
---|---|---|
Stage #1: 3-ethyl-1H-pyrazole-4-carbaldehyde; tert-butyl 2-[(4-piperidin-4-ylbenzoyl)amino]phenylcarbamate In dichloromethane at 20℃; for 1h; Stage #2: With sodium tris(acetoxy)borohydride In dichloromethane at 20℃; for 24h; Stage #3: With ammonia In methanol | 5 tert-Butyl 2-[(4-piperidin-4-ylbenzoyl)amino]phenylcarbamate (prepared as described in Method 1 below; 395 mg, 1.0 mmol) and 3-ethyl-lH-pyrazole-4-carbaldehyde (149 mg, o 1.2 mmol) were stirred at ambient temperature in dichloromethane (10 ml) for 1 hour. Sodium triacetoxyborohydride (297 mg, 1.4 mmol) was added and the mixture stirred at ambient temperature for 24 hours. The resulting solution was absorbed onto an SCX-2 column which was washed with methanol (2 column volumes) and then the product eluted EPO with a 2M solution of ammonia in methanol (2 column volumes) to give the product as a white foam. This was purified by chromatography on silica eluting with 10% methanol in dichloromethane. The residue was dissolved in dichloromethane (4 ml) and trifluoroacetic acid (1 ml) was added and the mixture stirred for 3 hours at ambient temperature. The resulting solution was absorbed onto an SCX-2 column which was washed with methanol (2 column volumes) and then the product eluted with a 2M solution of ammonia in methanol (2 column volumes) to give the title compound (232 mg, 75 %). NMR Spectrum: (DMSO dβ) δ 1.18 (t, 3H), 1.65 (m, 2H), 1.77 (m, 2H), 2.00 (m, 2H), 2.57 (m, 3H), 2.95 (m, 2H), 3.34 (s, 2H), 4.86 (br s, 2H), 6.60 (m, IH), 6.78 (d, IH), 6.97 (m, IH), 7.17 (d, IH), 7.29 (br s, IH), 7.37 (d, 2H), 7.91 (d, 2H), 9.55 (s, IH), 12.39 (s, IH); Mass Spectrum: M+H+ 404. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
16% | Stage #1: N,N-dimethyl-formamide With trichlorophosphate at 0℃; for 1.5h; Stage #2: butan-2-one semicarbazone at 0 - 70℃; Stage #3: With sodium hydroxide In water Cooling with ice; | 2 To cool DMF (50 mL) at 0 9C, POCI3 (30 mL) was added dropwise over 30 minutes, and maintained at 0 9C for 1 hour. To the mixture was added butan-2-one semicarbazone (10 g, 78 mmol) in portions at 02C and maintained at 70 9C for 4 hours. The mixture was poured into crushed ice (700 g), neutralized using 10% NaOH solution and extracted using ethyl acetate (3x100 ml_). The combined organic layers were washed with water (2x80 ml_), saturated aqueous NaCI (100 mL), dried over anhydrous Na2SO4 and concentrated to obtain a crude product, which was purified by column chromatography (60-120 mesh silica gel) using 3-5% methanol in chloroform as eluents to afford 3-ethyl-1 H-pyrazole-4-carbaldehyde (1.5 g, 16%) as solid. 1H NMR (CDCI3) δ 9.95 (s, 1 H), 8.0 (s, 1 H), 3.0 (q, 2H), 1.35 (t, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: 3-ethyl-1H-pyrazole-4-carbaldehyde; succinic acid diethyl ester With potassium <i>tert</i>-butylate; <i>tert</i>-butyl alcohol at 80℃; for 3h; Stage #2: With hydrogenchloride In water | 2 To a solution of 3-ethyl-1 H-pyrazole-4-carbaldehyde (2.2 g, 18 mmol) and diethyl succinate (12.3 g, 71.0 mmol) in t-butanol (15 mL) was added a solution of t-BuOK (8.08 g, 53.2 mmol) in t-butanol (10 mL). The mixture was heated to 80 eC for 3 hours before the mixture was concentrated. The obtained residue was dissolved in water (30 mL), acidified (pH~2) using 6 N HCI and extracted with ethyl acetate (2x30 mL). The combined organic layers were washed with aqueous NaHCO3 (2x50 mL). The combined aqueous layers were acidified (pH~2) and extracted with ethyl acetate (2x75 mL). The combined ethyl acetate layers were washed with saturated aqueous NaCI (25 mL), dried over anhydrous Na2SO4 and concentrated to afford ethyl 2-[(3-ethyl-1 H-pyrazol-4-yl)methylene]-4-oxopentanoate (4 g, 100%) as gum, which was taken as such into next step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With sulfuric acid In ethanol for 10h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | With sulfuric acid In ethanol for 10h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With sulfuric acid In ethanol for 10h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With sulfuric acid In ethanol for 10h; Reflux; |
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