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CAS No. : | 372118-01-9 | MDL No. : | MFCD09953612 |
Formula : | C6H4Cl2N2O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | MZEVRGMQXLNKEZ-UHFFFAOYSA-N |
M.W : | 207.01 | Pubchem ID : | 17848322 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | 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 |
---|---|---|
72% | With trichlorophosphate; at 95.0℃; for 5h; | Step 3 4,6-Dichloro-pyridazine-3-carboxylic acid methyl ester A mixture of <strong>[372118-00-8]4,6-dihydroxy-pyridazine-3-carboxylic acid methyl ester</strong> (10.5 g, 61.7 mmol) and POCl3 (70 mL) was heated to 95 C. for 5 h. The excess POCl3 was removed under reduced pressure, then the crude residue was added to ice-water (250 mL) and extracted with ethyl acetate (3*100 mL). The combined extracts were dried then concentrated to give a crude residue which was purified by chromatography (silica, 100-200 mesh, 30% ethyl acetate in hexane) to give 4,6-dichloro-pyridazine-3-carboxylic acid methyl ester (9.2 g, 72%) as an off white solid. LC-MS: 207.0 [M+H]+. |
64.3% | With trichlorophosphate; for 3h;Reflux; | A slurry of <strong>[372118-00-8]methyl 4,6-dihydroxypyridazine-3-carboxylate</strong> (11.7 g, 68.8 mmol) in POCl3 (110 mL, 1180 mmol) was heated to reflux for 3h during which time the mixture became a nearly homogeneous dark brown solution. The reaction mixture was cooled to rt, allowed to stand overnight and concentrated in vacuo. The resulting dark brown residue was dissolved in DCM (?300 mL) and was slowly poured onto ?500 mL of crushed ice with swirling of the flask. After the addition was complete, water was slowly added (?200 mL) until the mixture became stirrable and the mixture was stirred while warming to rt over ?3 h. The resulting phases were separated and the aqueous portion was extracted with additional DCM (3*100 mL). The combined extracts were washed with brine, dried over anhydrous sodium sulfate, decanted and concentrated under vacuum to afford a white solid as the pure product, methyl 4,6-dichloropyridazine-3-carboxylate (9.16 g, 44.2 mmol, 64.3% yield). Material was used as is without any further purification. MS (M+1) m/z: 206.9 (MH+). LC retention time 0.80 min [A]. |
With trichlorophosphate; at 95.0℃; for 4h; | Step 3.Preparation of 4,6-dichloro-pyridazine-3-carboxylic acid methyl or ethyl ester 5 A mixture of 4,6-dihydroxy-pyridazine-3-carboxylic acid methyl or ethyl ester (50 mmol) and POCl3 (90 ML) is heated at 95 C. for 4 hours.The excess POCl3 is evaporated in vacuo and to the residue cooled to 0 C. was added ice (150 g) followed by EtOAc (200 ML).The layers are separated and the aqueous layer is extracted with EtOAc (2*100 ML).The combined extracts are washed with brine (200 ML), dried (Na2SO4) and evaporated in vacuo.This residue is purified by flash column chromatography (225 g silica gel, eluted with 4:1 hexane, EtOAc).The desired 4,6 dichloro-pyridazine-3-carboxylic acid methyl ester is obtained as a white solid, while the 4,6 dichloro-pyridazine-3-carboxylic acid ethyl ester is a colorless liquid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | In acetonitrile; at 130℃; for 36.0h; | Step 1 Methyl 6-chloro-4-(5-chloro-6-methylpyridin-2-ylamino)pyridazine-3-carboxylate A pressure tube was charged with methyl 4,6-dichloropyridazine-3-carboxylate (2 g, 9.66 mmol) and <strong>[36936-23-9]5-chloro-6-methylpyridin-2-amine</strong> (2.76 g, 19.3 mmol). To the mixture was added acetonitrile (12 mL) and the reaction mixture heated with stirring at 130 C. for 1.5 days. After cooling to room temperature, the acetonitrile was removed in vacuo. The residue obtained was purified by chromatography (silica, 80 g, 50 mum from Analogix, 0% to 5% acetone in dichloromethane over 20 min., holding at 5% for 5 min, then increasing the gradient from 5% to 10% over the next 20 min) to give methyl 6-chloro-4-(5-chloro-6-methylpyridin-2-ylamino)pyridazine-3-carboxylate (618 mg, 20%) as an orange solid. 1H NMR (400 MHz, CHLOROFORM-d) delta ppm 10.70 (br. s., 1H), 9.18 (s, 1H), 7.63 (d, J=8.34 Hz, 1H), 6.78 (d, J=8.34 Hz, 1H), 4.12 (s, 3H), 2.66 (s, 3H), 1.58 (br. s., 1H); LC-MS 313 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
19% | With tris-(dibenzylideneacetone)dipalladium(0); 4a,9a-dihydro-9,9-dimethyl-4,5-bis(diphenylphosphino)-xanthene; caesium carbonate; In 1,4-dioxane; at 100℃; for 1h;Inert atmosphere; | Step 1 Methyl 6-chloro-4-(5-(methylsulfonyl)pyridin-2-ylamino)pyridazine-3-carboxylate A flask was charged with methyl 4,6-dichloropyridazine-3-carboxylate (200 mg, 0.966 mmol), <strong>[35196-11-3]5-(methylsulfonyl)pyridin-2-amine</strong> (183 mg, 1.06 mmol), Pd2(dba)3 (88.5 mg, 0.097 mmol), xantphos (112 mg, 0.193 mmol) and cesium carbonate (944 mg, 2.9 mmol). 1,4-Dioxane (6.0 mL) was added and argon was bubbled through it while sonicating the flask for 5 min. The flask was sealed and heated at 100 C. for 1 h. After cooling the mixture was filtered through celite and the filter cake washed with CH2Cl2. The filtrates were concentrated in vacuo then purified by chromatography (spherical silica 20-45 μM, 23 g, Versaflash Supelco, 0 to 100% ethyl acetate in hexanes, 30 min) to give methyl 6-chloro-4-(5-(methylsulfonyl)pyridin-2-ylamino)pyridazine-3-carboxylate (62 mg, 19%) as a light yellow solid. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 11.18 (s, 1H) 9.31 (s, 1H) 8.98 (d, J=2.27 Hz, 1H) 8.19 (dd, J=8.59, 2.53 Hz, 1H) 7.09 (dd, J=8.84, 0.76 Hz, 1H) 4.15 (s, 3H) 3.15 (s, 3H). LCMS (EI/CI) m/z: 342.9 [M+H]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
28% | In ethanol; at 90℃; for 5h; | Compound 4,6-dichloropyridazine-3-carboxylic acid methyl ester 1a (1 g, 5 mmol) and tert-butyl 2- (4-aminophenyl) acetate 55c (1 g, 5 mmol) were dissolved in ethanol (10 mL), Heat to 90 C and stir for 5 hours.After cooling to room temperature, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 100/0 to 7/3),The target product 4-((4- (2-tert-butoxy-2-oxoethyl) phenyl) amino) -6-chloropyridazine-3-carboxylic acid methyl ester 55d (540 mg, colorless oil was obtained ). Yield: 28%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With N-ethyl-N,N-diisopropylamine; In ethanol; at 80℃; for 18h; | Compound 4,6-dichloropyridazine-3-carboxylic acid methyl ester 1a (1 g, 4.83 mmol),6-morpholinopyridine-3-amine (870 mg, 4.83 mmol),Diisopropylethylamine (1.24 g, 9.66 mmol) and ethanol (20 mL) were mixed, heated to 80 C and stirred for 18 hours.After cooling to room temperature, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (dichloromethane / methanol = 19/1).The target product 6-chloro-4-((6-morpholinopyridin-3-yl) amino) pyridazine-3-carboxylic acid methyl ester 36a (1.5 g, yellow solid) was obtained,Yield: 89%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With N-ethyl-N,N-diisopropylamine; In ethanol; at 80℃; for 2h; | Compound 4,6-dichloropyridazine-3-carboxylic acid methyl ester 1a (206 mg, 1 mmol),<strong>[28466-26-4]1H-pyrazole-4-amine</strong> (83mg, 1mmol),Diisopropylethylamine (258mg, 2mmol)Mix with ethanol (20 mL), heat to 80 C and stir for 2 hours.After cooling to room temperature, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (dichloromethane / methanol = 19/1).The target product 4-((1H-pyrazol-4-yl) amino) -6-chloropyridazine-3-carboxylic acid methyl ester 41a (150 mg, yellow solid) was obtained,Yield: 59%. |
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