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CAS No. : | 36404-88-3 | MDL No. : | MFCD01315308 |
Formula : | C6H4ClNO | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | KHPAGGHFIDLUMB-UHFFFAOYSA-N |
M.W : | 141.56 | Pubchem ID : | 737607 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H317-H319 | 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 |
---|---|---|
87% | With toluene-4-sulfonic acid; hydrazine hydrate; at 130℃; for 3h;Inert atmosphere; | Hydrazine hydrate (10 mL) was added to a mixture of 2-chloro-3-formylpyridine 1 (5.00 g, 35 mmol) and p-TsOH (3.50 g, 18 mmol). The reaction mixture was stirred for 3 h at 130 °C. Upon cooling with cold water, the mixture was extracted with EtOAc. The combined organic extracts were dried over anhydrous MgSO4. After filtration, the solvent was removed in vacuum and gave compound 2 (3.65 g, 87percent) as a yellow solid; mp 88?90 °C(97-98 °C);34 FTIR (KBr) numax/cm-1 3450 (N-H), 3089, 3026 (C-H Ar), 2958, 2915 (C-H), 1606, 1588, 1509, 1470, 1429 (C=N, C=C); 1H NMR (300 MHz, CDCl3) delta/ppm 1.69 (s, 1H, N-H), 7.19 (dd, 1H, J 4.7 and 7.5, ArH, 5-H), 8.12 (s, 1H, ArH, 3-H), 8.15 (d, 1H, J 8.1, ArH, 4-H), 8.63 (d, 1H, J 4.5, ArH, 6-H). |
62% | Preparation of 1H-pyrazolo[3,4-b]pyridine 2-Chloro-3-pyridinecarboxyaldehyde (1.0 g, 7.0 mmol) and p-toluenesulfonic acid monohydrate (700 mg) were dissolved in hydrazine monohydrate (1.4 mL, 28.0 mmol). The resulting mixture was heated at 120°C for 10 minutes in a sealed tube under irradiation with a macrowave of 100 watts. After cooled to room temperature, the mixture was neutralized with a saturated sodium bicarbonate aqueous solution and extracted with DCM (50 mL) three times. The organic layer was dried over anhydrous sodium sulfate. The concentrated residue was purified by silica gel (Fuji Silysia, BW300, 30 g, n-hexane: ethyl acetate = 1:1) to give 1H-pyrazolo[3,4-b]pyridine (513 mg, yield: 62percent). 1H-NMR (270MHz, CDCl3) delta (ppm): 7.16 (1H, dd, J=4.6, 8.1Hz), 8.08 (1H, d, J=2.0Hz), 8.10 (1H, d, J=1.5Hz), 8.60 (1H, d, J=4.6Hz) ESI (LC-MS positive mode) m/z 120 (M+H). | |
With hydrazine; In ethanol; water; for 24h;Heating / reflux; | EXAMPLE 49; 3-Chloro-5-{2-chloro-5-[2-(1H-pyrazolo[3,4-b]pyridin-3-yl)ethyl]phenoxy}benzonitrile (49-9); Step 1: 1H-pyrazolo[3,4-b]pyridine (49-2) A mixture of 10.00 g (70.65 mmol) of 2-chloro-3-formylpyridine(49-1) in 225 mL of absolute ethanol/100 mL of hydrazine hydrate was heated at reflux for 24 hours. The reaction mixture was then cooled to room temperature and concentrated in vacuo to a brown oil-solid. The crude product was chromatographed over silica gel with 2.5percent methanol/chloroform to give the desired product as a yellow oil that slowly crystallized to a yellow solid. 1H NMR (CDCl3): 7.20(m,1H), 8.15(m,2H), 8.66 (dd,1H), 12.49 (br s, 1H). |
With hydrazine hydrate; In water; at 100℃; for 72h;Inert atmosphere; | A solution of 2-chloropyridine-3-carbaldehyde (20g, 141mmol) and hydrazine monohydrate(60percent in water, 1 13g, 2.1 mol) in 140 mL water was heated at 100 °C for 72 hours. The reaction mixture was cooled to room temperature and diluted with 200 mL of EtOAc. The aqueous layer was separated and extracted with EtOAc (3x). The combined organics were dried over MgS04, filtered and concentrated in vacuo to give a light orange solid which was crystallized from hexanes to give the title compound as an off-white solid. NMR (400 MHz, CH3CN-d3): delta11.56 (s, 1 H); 8.51 (dd, J = 4.52, 1.56 Hz, 1 H); 8.17 (dd, J = 8.05, 1.58 Hz, 1 H); 8.05 (s, 1H); 7.17 (dd, J = 8.05, 4.51 Hz, 1 H). | |
Reference Example 1; (1); According to the method of Chemical Communications 293-294 (1966), to a mixture of Compound 1 (20.0 g) and p-toluenesulfonic acid monohydrate (15.6 g) was added slowly hydrazine monohydrate (26.6 ml) with stirring under ice-cooling. The mixture was heated to stir at 130° C. for 21 hours. The reaction mixture was let stand to cool, and then poured into 25percent aqueous potassium carbonate solution, and extracted with ethyl acetate. The extracted layer was combined, and dried over anhydrous magnesium sulfate. The solvent was distilled away under reduced pressure, and the resulting residue was purified by silica gel column chromatography (eluent: hexane-ethyl acetate 2:1 to 1:1). The resulting solid was triturated by hexane-ethyl acetate (1:1) to give Compound 2 (12.27 g) as colorless powdery crystals.MS (APCI) 120 [M+H]+ | ||
4 g | With hydrazine; In ethanol; for 24h;Reflux; | A stirred solution of 2-chloronicotinaldehyde (I-5) (5.1 g, 36 mmol) in EtOH (100 mL) and NH2NH2 (85 percent in H20, 50 mL) was heated to reflux for 24 hr. TLC (petroleum ether/ EtOAc = 1 :1) showed the reaction was complete. The mixture was concentrated and separated between H20 (100 mL) and EtOAc (200 mL). The aqueous layer was extracted with EtOAc (100 mL x 2). The combined organic layers were washed with brine (100 mL), dried over Na2S04 and concentrated in vacuo to give 1 H-pyrazolo[3,4-b]pyridine (I-6) (4 g, 93percent) as a yellow solid. |
With toluene-4-sulfonic acid; hydrazine hydrate; at 130℃; for 16h; | To a solution of 2-chloropyridine-3-carbaldehyde (3.00 g, 21.19 mmol, 1.00 eq) in hydrazine; hydrate (6.36 g, 127.14 mmol, 6.18 mL, 6.00 eq) was added PTSA (1.82 g, 10.60 mmol, 0.50 eq). The mixture was stirred at 130 C for 16 h. It was concentrated. The residue was purified by column chromatography to afford the title compound (1.50 g, 11.33 mmol, 53.48percent yield, 90percent purity) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With sodium sulfate; triethylamine; In tetrahydrofuran; at 80℃; for 1.75h;Microwave irradiation; | General procedure: In a 20 mL glass tube equipped with septa, the aldehyde, dry Na2SO4 (2.81 equiv) and triethylamine (2 equiv) were suspended in dry THF. Then, the hydroxylamine hydrochloride (2 equiv) was added. The mixture was stirred for 30 s, and then exposed to MWI (250 W) at 80 °C during the time indicated for each compound. When the reaction was over (TLC analysis), the reaction mixture was diluted with water, extracted with CH2Cl2, dried over anhydrous sodium sulphate, filtered and the solvent was evaporated. The resultant solid was purified by column chromatography to give pure compounds. |
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