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CAS No. : | 64064-56-8 | MDL No. : | MFCD09702465 |
Formula : | C8H8ClNO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | MXEIFGRJRCYUDJ-UHFFFAOYSA-N |
M.W : | 185.61 | Pubchem ID : | 13015359 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-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 |
---|---|---|
89% | Stage #1: at 100℃; for 6 h; Stage #2: at 20℃; for 20 h; |
Step-1 : Ethyl-4-chloroypicolinate: A mixture of 4-chloropicolinic acid (20 g, 127 mmol) and thionyl chloride (200 mL) was heated to 100 °C and maintained for 6 h. The reaction was cooled to RT, and the excess of thionyl chloride was removed under vacuum. To the above obtained residue was then added ethanol (200 mL) at 0 °C drop-wise and the resulting mixture was stirred at RT for 20 h.The solvent was evaporated under vacuum and the residue was taken in ethyl acetate (1000 mL), washed with water (2x500 mL), saturated sodium bicarbonate solution (2x500 mL), brine (500 mL), dried (Na2S04) and filtered. The filtrate was evaporated to yield 21.0 g (89percent) the desired product as a semi solid. XHNMR (400 MHz, DMSO) δ 8.66 (d, = 5.0 Hz, 1Η), 8.13 (d, = 2.0Hz, 1Η), 7.49 (dd, = 5.0 &2.0HZ 1Η), 4.47 (q, = 7.0 Hz, 2Η), 1.46 (t, = 7.0 Hz, 3H); GC-MS (m/z) 185, 187 [(M)+, CI35' 37]. |
83.6% | Stage #1: at 100℃; for 6 h; Inert atmosphere Stage #2: at 20℃; for 25.5 h; Cooling with ice Stage #3: With sodium hydrogencarbonate In water |
(Reference Example A-1) Ethyl 4-chloropyridine-2-carboxylate A mixture of 4-chloropyridine-2-carboxylic acid (39.4g) and thionyl chloride (64 ml) was heated and stirred at 100 °C under a nitrogen atmosphere for 6 hr. The reaction mixture was allowed to cool down to room temperature. This was concentrated under reduced pressure and distilled azeotropically with toluene. The resultant residue was gradually added to ethanol while stirring in an ice bath. The reaction mixture was stirred at room temperature for 25.5 hr. The reaction mixture was concentrated under reduced pressure. To the residue was added a saturated aqueous solution of sodium hydrogencarbonate and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to provide the titled compound as a brown oil (38.8 g, 83.6 percent). 1H-NMR Spectrum (CDCl3) δ (ppm): 1.46 (3H, t, J = 7.2 Hz), 4.50 (2H, q, J = 7.2 Hz), 7.49 (1H, dd, J = 2.0, 5.2 Hz), 8.15 (1H, d, J = 2.0 Hz), 8.67 (1H, d, J = 5.2 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83.6% | Stage #1: at 100℃; for 6 h; Stage #2: at 0 - 20℃; for 25.5 h; Stage #3: With sodium hydrogencarbonate In water; ethyl acetate |
(Production Example 15) Ethyl 4-chloropyridine-2-carboxylate A mixture of 4-chloropyridine-2-carboxylic acid (39.4g) and thionyl chloride (64 ml) was heated and stirred at 100 °C under a nitrogen atmosphere for 6 hr. The reaction mixture was allowed to cool down to room temperature. This was concentrated under reduced pressure and distilled azeotropically with toluene. The resultant residue was gradually added to ethanol while stirring in an ice bath. The reaction mixture was stirred at room temperature for 25.5 hr. The reaction mixture was concentrated under reduced pressure. To the residue was added a saturated aqueous solution of sodium hydrogencarbonate and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to provide the titled compound as a brown oil (38.8 g, 83.6 percent). 1H-NMR Spectrum (CDCl3) δ (ppm): 1.46 (3H, t, J = 7.2 Hz), 4.50 (2H, q, J = 7.2 Hz), 7.49 (1H, dd, J = 2.0, 5.2 Hz), 8.15 (1H, d, J = 2.0 Hz), 8.67 (1H, d, J = 5.2 Hz). |
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