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CAS No. : | 98121-41-6 | MDL No. : | MFCD03840434 |
Formula : | C5H4Cl2N2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | XTCHZNJJTQACES-UHFFFAOYSA-N |
M.W : | 163.01 | Pubchem ID : | 14595219 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | |
Hazard Statements: | 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 |
---|---|---|
With hydrogenchloride; tin(ll) chloride; In water; at 0 - 65℃; for 2h; | Anhydrous SnCl2 (300 g, 1.58 mol) and concentrated HCl (350 mL) were charged to a 5L flask with mechanical stirrer and thermocouple. The flask was cooled in ice and the product of Example 2B (100 g, 0.518 mol) was added in portions maintaining the temperature below 65 C. After the addition was complete, the cold bath was removed, and the mixture was stirred for 2 hours at ambient temperature. The mixture was cooled in ice as 25% aqueous NaOH (1000 mL) was added to bring the mixture to pH>10. The mixture was extracted with CH2Cl2 (1*600 mL, 2*400 mL) and the combined extracts were washed with brine (200 mL), dried (MgSO4), and concentrated under vacuum. The residual solid was crystallized from a mixture of water (500 mL) and ethanol (100 mL) to provide the title compound as a solid. 1H NMR (CDCl3, 300 MHz) delta 3.80 (br s, 2H), 7.10 (d, J=3 Hz, 1H), 7.77 (d, J=3 Hz, 1H); MS (DCI/NH3) m/z 180/182/184 (M+NH4)+163/165/167 (M+H)+. | |
With hydrogenchloride; stannous chloride; In sodium hydroxide; ethanol; | Example 2C 5-amino-2,3-dichloropyridine Anhydrous SnCl2 (300 g, 1.58 mol) and concentrated HCl (350 mL) were charged to a 5 L flask with mechanical stirrer and thermocouple. The flask was cooled in ice and the product of Example 2B (100 g, 0.518 mol) was added in portions maintaining the temperature below 65 C. After the addition was complete, the cold bath was removed, and the mixture was stirred for 2 hours at ambient temperature. The mixture was cooled in ice as 25% aqueous NaOH (1000 mL) was added to bring the mixture to pH>10. The mixture was extracted with CH2Cl2 (1*600 mL, 2*400 mL) and the combined extracts were washed with brine (200 mL), dried (MgSO4), and concentrated under vacuum. The residual solid was crystallized from a mixture of water (500 mL) and ethanol (100 mL) to provide the title compound as a solid. 1H NMR (CDCl3, 300 MHz) delta 3.80 (br s, 2H), 7.10 (d, J=3 Hz, 1H), 7.77 (d, J=3 Hz, 1H); MS (DCI/NH3) m/Z 180/182/184 (M+NH4)+163/165/167 (M+H)+. | |
With iron; acetic acid; at 25℃; | 2,3-Dichloro-5-nitropyridine (100 g, 0.518 mol, 1.0 equiv.) was dissolved in acetic acid (1000 mL) and iron (metallic, chips) (115.7 g, 2.07 mol, 4.0 equiv.) added in portions, keeping the temperature below 50 C. and the mixture was stirred at 25 C overnight. The solid was filtered and washed with MeOH. The organic phase was evaporated in vacuo, and the residue was dissolved in EtOAc and washed with water, dried (Na2SO4), evaporated in vacuo to afford a gray yellow solid. |
EXAMPLE 2C 5-amino-2,3-dichloropyridine Anhydrous SnCl2 (300 g, 1.58 mol) and concentrated HCl (350 mL) were charged to a 5 L flask with mechanical stirrer and thermocouple. The flask was cooled in ice and the product of Example 2B (100 g, 0.518 mol) was added in portions maintaining the temperature below 65 C. After the addition was complete, the cold bath was removed, and the mixture was stirred for 2 hours at ambient temperature. The mixture was cooled in ice as 25% aqueous NaOH (1000 mL) was added to bring the mixture to pH >10. The mixture was extracted with CH2Cl2 (1*600 mL, 2*400 mL) and the combined extracts were washed with brine (200 mL), dried (MgSO4), and concentrated under vacuum. The residual solid was crystallized from a mixture of water (500 mL) and ethanol (100 mL) to provide the title compound as a solid. 1H NMR (CDCl3, 300 MHz) delta 3.80 (br s, 2H), 7.10 (d, J=3 Hz, 1H), 7.77 (d, J=3 Hz, 1H); MS (DCI/NH3) m/z 180/182/184 (M+NH4)+163/165/167 (M+H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84 g | To a solution of 5,6-dichloro-pyridin-3-ylamine (40.0 g, 0.245 mol, 1.0 equiv.) in dichloromethane (300 mL) at 0 C was added boron trifluoride diethyl etherate (42.0 g, 0.296 mol, 1.2 equiv.) followed by 2-methyl-2-nitrosooxy-propane (38.0 g, 0.369 mol, 1.5 equiv.). The resulting reaction was allowed to warm to 25 C. The slurry of the product was stirred at this temperature for 30-60 min and filtered to afford 5,6-dichloro-pyridine-3-diazonium tetrafluoroborate (51.0 g, 0.195 mol).5,6-Dichloro-pyridine-3-diazonium tetrafluoroborate (180 g, 0.688 mol, 1.0 equiv.) was dissolved in Ac2O (540 mL) and stirred at RT for a few minutes. Then, the mixture was heated to 60 C. Acetic acid 5,6-dichloro-pyridin-3-yl ester was detected by LCMS. The acetic acid was evaporated, the precipitate was diluted with DCM and evaporated in vacuo. The mixture was purified on silica gel (1% EtOAc in petroleum ether as eluent) to afford acetic acid 5,6-dichloro-pyridin-3-yl ester (84.0 g, 0.408 mol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium nitrite; In sulfuric acid; water; toluene; | EXAMPLE 11 5,6-dichloro-3-pyridinol Process (a) 8.15 g (50 mmol) of <strong>[98121-41-6]3-amino-5,6-dichloropyridine</strong> were dissolved in 100 ml of 8N H2 SO4 and diazotized at 0 C. using 3.55 g (53 mmol) of sodium nitrite in 9 ml of water. The cold diazonium salt solution was added dropwise to 100 C. warm 60% strength sulfuric acid. After completion of the nitrogen elimination, the mixture was neutralized and extractively distilled using toluene. The dried toluene phase was concentrated by evaporation and the residue was recrystallized repeatedly from toluene. Melting point 184-185 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
A 5L flask with mechanical stirrer, thermocouple, and addition funnel was charged with the product of Example 2C (70 g, 429 mmol) and 48% HBraq (240 mL). The suspension was maintained at 0-5 C. as a solution of NaNO2 (32.0g, 464 mmol) in water (100 mL) was added dropwise over 1 hour. Additional water (200 mL) was added and the mixture was stirred for 10 minutes at 0-5 C. The mixture was treated with CuBr (32.6 g, 227 mmol) in portions over 20 minutes followed by additional water to maintain a fluid reaction mixture. The mixture was allowed to warm to room temperature and diluted with water. The mixture was distilled at ambient pressure, until the distillate ran clear (1.5 L collected). The distillate was extracted with EtOAc (3*500 mL) and the combined extracts were washed with brine (100 mL), dried (MgSO4), and concentrated to provide 5-bromo-2,3-dichloropyridine as a solid. 1H NMR (CDCl3, 300 MHz) delta 7.94 (d, J=3 Hz, 1H), 8.38 (d, J=3 Hz, 1H). | ||
With sodium nitrite;copper(I) bromide; In water; | Example 2D 5-bromo-2,3-dichloropyridine A 5 L flask with mechanical stirrer, thermocouple, and addition funnel was charged with the product of Example 2C (70 g, 429 mmol) and 48% HBraq (240 mL). The suspension was maintained at 0-5 C. as a solution of NaNO2 (32.0 g, 464 mmol) in water (100 mL) was added dropwise over 1 hour. Additional water (200 mL) was added and the mixture was stirred for 10 minutes at 0-5 C. The mixture was treated with CuBr (32.6 g, 227 mmol) in portions over 20 minutes followed by additional water to maintain a fluid reaction mixture. The mixture was allowed to warm to room temperature and diluted with water. The mixture was distilled at ambient pressure, until the distillate ran clear (1.5 L collected). The distillate was extracted with EtOAc (3*500 mL) and the combined extracts were washed with brine (100 mL), dried (MgSO4), and concentrated to provide 5-bromo-2,3-dichloropyridine as a solid. 1H NMR (CDCl3, 300 MHz) delta 7.94 (d, J=3 Hz, 1H), 8.38 (d, J=3 Hz, 1H). | |
EXAMPLE 2D 5-bromo-2,3-dichloropyridine A 5 L flask with mechanical stirrer, thermocouple, and addition funnel was charged with the product of Example 2C (70 g, 429 mmol) and 48% HBraq (240 mL). The suspension was maintained at 0-5 C. as a solution of NaNO2 (32.0g, 464 mmol) in water (100 mL) was added dropwise over 1 hour. Additional water (200 mL) was added and the mixture was stirred for 10 minutes at 0-5 C. The mixture was treated with CuBr (32.6 g, 227 mmol) in portions over 20 minutes followed by additional water to maintain a fluid reaction mixture. The mixture was allowed to warm to room temperature and diluted with water. The mixture was distilled at ambient pressure, until the distillate ran clear (1.5 L collected). The distillate was extracted with EtOAc (3*500 mL) and the combined extracts were washed with brine (100 mL), dried (MgSO4), and concentrated to provide 5-bromo-2,3-dichloropyridine as a solid. 1H NMR (CDCl3, 300 MHz) delta 7.94 (d, J=3 Hz, 1 H), 8.38 (d, J=3 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tert.-butylnitrite; In ice-water; hexane; dichloromethane; | Precursor alpha: 2,3-Dichloro-5-methylthiopyridine A solution of 50.6 g (0.3 mol) of <strong>[98121-41-6]3-amino-5,6-dichloropyridine</strong> in 700 ml of methylene chloride was slowly added dropwise at 40 C. to a solution of 56.6 g (0.6 mol) of dimethyl disulfide and 46.7 g (0.45 mol) of tert-butyl nitrite in 320 ml of dry methylene chloride. The mixture was then stirred for 1 hour at 40 C. and subsequently for another approximately 15 hours at approximately 20 C., whereupon 500 ml of ice-water were added to the reaction mixture. The organic phase which was separated off was washed once with 1 N hydrochloric acid and once with water, dried over sodium sulfate and finally concentrated. After the crude product had been stirred with n-hexane, 21 g of a dark solid were obtained (purity 94% according to GC). After the hexane solution was concentrated, a further 21.3 g of product of value remained which had a purity of 77% (according to GC). Total yield: 62%; m.p.: 66-67 C.; 1H-NMR (in d6 dimethyl sulfoxide): delta [ppm]=2.6 (s, CH3); 8.1 and 8.3 (2*d, pyr H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With tert.-butylnitrite; In dichloromethane; | Precursor alpha: 2,3-Dichloro-5-ethylthiopyridine 24.45 g (0.15 mol) of <strong>[98121-41-6]3-amino-5,6-dichloropyridine</strong> in 280 ml of methylene chloride were reacted with 36.6 g (0.3 mol) of diethyl disulfide and 23.2 g (0.225 mol) of tert-butyl nitrite in 130 ml of methylene chloride by a method similar to Example 1, Precursor alpha. After working up and subsequently washing the crude product with ethanol, 13.3 g of product of value were obtained. Yield: 42%; 1H-NMR (in d6 dimethyl sulfoxide): delta [ppm]=1.25 (t, CH3); 3.10 (d, CH2); 8.15 and 8.3 (2*d, pyr H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With tert.-butylnitrite; In dichloromethane; | Precursor alpha: 2,3-Dichloro-5-isopropylthiopyridine 13.1 g (0.08 mol) of <strong>[98121-41-6]3-amino-5,6-dichloropyridine</strong> in 120 ml of methylene chloride were reacted with 25 g (0.16 mol) of diisopropyl disulfide and 12.4 g (0.12 mol) of tert-butyl nitrite in 70 ml of methylene chloride by a method similar to Example 1, Precursor alpha. This gave 30 g of the dark oil (approximately 40% of product of value) which was further reacted without further purification. 1H-NMR (in d6 dimethyl sulfoxide): delta [ppm]=1.25 (d, 2*CH3); 3.7 (m, CH); 8.2 and 8.3 (2*d, pyr H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluoroborane diethyl ether; In hexane; dichloromethane; | <strong>[98121-41-6]5-Amino-2,3-dichloropyridine</strong> (0.80 g) in dichloromethane (10 ml) was added to boron trifluoride etherate (0.92 ml) at -15 C. under nitrogen. Dichloromethane (15 ml) was added followed by t-butylnitrite (0.71 ml) in dichloromethane (5 ml). After 15 minutes the mixture was allowed to warm to -5 C. over 20 minutes. Hexane was added and the resulting solid was filtered, air-dried and washed with ether and stored at approximately -20 C. overnight. The solid was then heated until gas evolution had ceased and the product kugelrohr distilled to give 2,3-dichloro-5-fluoropyridine (0.104 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With magnesium sulfate; In water; acetic acid; ethyl acetate; | EXAMPLE 10 3-amino-5,6-dichloropyridine 77.2 g (0.4 mol) of 2,3-dichloro-5-nitropyridine were dissolved in 135 ml of glacial acetic acid, and 800 ml of water were added with stirring. 111.7 g (2 mol) of iron powder were introduced in portions into the mixture (temperature?50 C.). After completion of the reaction, the mixture is filtered under suction and the product extracted using ethyl acetate. The organic phase was washed with water until neutral, dried using MgSO4 and concentrated by evaporation. The product was recrystallized from toluene. Yield 85% Melting point 107 C. |
In water; ethyl acetate; | 2,3-Dichloro-5-nitropyridine (3.9 g) and iron powder (3.0 g) were added to isopropyl alcohol (40 ml) and water (8 ml) and the mixture refluxed for 4 hours. The mixture was then cooled to room temperature and filtered (celite). The filtrate was evaporated under reduced pressure and chromatographed ?SiO2; hexane:ethyl acetate (80:20) to[(50:50)] to give 5-amino-2,3-dichloropyridine (1.71 g). |
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