Structure of 152362-01-1
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CAS No. : | 152362-01-1 |
Formula : | C7H7ClN2O |
M.W : | 170.60 |
SMILES Code : | ClC1=C(C(=O)N)C(=CC=N1)C |
MDL No. : | MFCD09033826 |
Boiling Point : | No data available |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302 |
Precautionary Statements: | P280-P305+P351+P338 |
* 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 |
---|---|---|
98% | With sodium hypobromide; bromine; sodium hydroxide; In water; at 65 - 75℃; for 4h; | Bromine (1.6 g) was added to a solution of sodium hydroxide (1.6 g) in fresh water or sea water (11.8 g) at 0-5C. 2-Chloro-4-methyl nicotinamide (1.7 g) was added to cold sodium hypobromite solution in 1.5 h. The ice bath was removed, and the reaction mixture was allowed to warm to room temperature. The resulting yellow solution was heated to 65C for 2 h, and warmed to 75C for 2 h. When the solution cooled to room temperature, the product was extracted three times with chloroform (30 mL). The combined extract was dried over anhydrous sodium sulfate, filtered, and concentrated to a solid. Recrystallization with n-hexane yielded a coarse white crystal product. The product yield using zinc powder-treated sea water as raw material was 98%, mp 70-71C. (Literature [7]: Yield 92.3%, mp 69-70C). The synthesis route of 3-amino-2-chloro-4-methylpyridine is shown in Scheme 2. |
96.9% | With bromine; sodium hydroxide; In water; toluene; at 0 - 60℃; | 1. COMAD (10,3 g) was added to a 3-neck flask fitted with a thermocouple, a dropping funnel, and a heating and cooling system.2. Water (15 g) was added to the reactor and the suspension was agitated.3. The mixture was cooled to 0-5C.4. The NaOBr solution of vessel I was added to the COMAD suspension in vessel 2 slowly while maintaining the temperature between 0-5C.5. Afier charging was complete, the temperature of the reaction mixture was held at0-5C for 15-20 minutes. A clear yellow solution resulted; no solid or suspension was formed.6. The reactor contents were allowed to warm to 15C and were held at this temperature for 15-20 minutes.7. The reaction mixture was heated to 25C and maintained at a temperature between22-25C for 1.5 hours, or until the evolution of heat subsided.8. 10 ml of water was added to the reaction mixture which was then heated to 80C and held for 1 hour.9. The reaction mixture was then cooled to 50-60C and toluene (21.62 g) was added; the mixture was agitated for 15-20 minutes.10. The top organic layer was separated.11. Toluene (10.3 g) was added to the aqueous layer and the mixture was agitated for15-20 minutes. The agitation was stopped and the top organic layer was separated.12. The organic layers were combined and washed with water (10 g) and the water layer was decanted.13. Toluene (25.0 g) was removed via distillation under reduced pressure.14. The reactor temperature was adjusted to 55-60C and hexane (6.5 g) was added slowly with agitation over 15 minutes. The solution because cloudy and a white precipitate started to appear.15. The mixture was cooled slowly to room temperature and then to 0-5C.16. The mixture was held at 0-5C for 1 hour.17. The solid precipitate was retrieved by filtered and washed once with hexanes (6.6 g).18. The product was dried under vacuo at 25C to a constant weight.In an exemplary synthesis, the isolated yield was 8.34 g (96.9%) of off white to white crystalline product. |
90.6% | With sodium hydroxide; bromine; In water; at 0 - 75℃; for 3h; | Example 11 Synthesis of 3-amino-2-chloro-4-methylpyridine (1) A solution of 11.7g (0.293 mole) of sodium hydroxide in 11 ML of water was stirred and cooled to 0C. bromine 14.2g (0.293 mole) was added dropwise maintaining the temperature at 0C. To a pale yellow solution was added 13.2g (0.077 mole) of 2-Chloro-4-methylnicotinamide (10) in portions at 0-5C. The ice-bath was removed and the reaction mixture warmed to 75C over one hour and maintained at 60-75C for an additional 2 hours.. The mixture was cooled overnight and the crystalline product collected by filtration to give 10g (90.6%) of the title compound [mp: 62-64C]. NMR and MS was identical to data reported by Hargrave, et al., J. Heterocyclic Chem., 34, 223 (1991). |
90.6% | Example 6 Synthesis of 3-amino-2-chloro-4-methylpyridine (1) A solution of 11.7g (0.293 mole) of sodium hydroxide in 11 mL of water was stirred and cooled to 0C. Bromine 14.2g (0.293 mole) was added dropwise maintaining the temperature at '0C. To a pale yellow solution was added 13.2g (0.077 mole) of 2-chloro-4-methylpyridine-3-carboxamide (9) in portions at 0-5C. The ice-bath was removed and the reaction mixture warmed to 75C over one hour and maintained at 60-75C for an additional 2 hours. The mixture was cooled overnight and the crystalline product collected by filtration to give 10g (90.6%) of the title compound [mp: 62-64C]. NMR and MS was identical to data reported by Hargrave et al., J. Heterocyclic Chem., 34, 223 (1991). | |
10 g (90.6%) | With sodium hydroxide; bromine; In water; | EXAMPLE 6 Synthesis of 3-amino-2-chloro-4-methylpyridine (1) A solution of 11.7 g (0.293 mole) of sodium hydroxide in 11 mL of water was stirred and cooled to 0 C. Bromine 14.2 g (0.293 mole) was added dropwise maintaining the temperature at 0 C. To a pale yellow solution was added 13.2 g (0.077 mole) of 2-chloro-4-methylpyridine-3-carboxamide (9) in portions at 0-5 C. The ice-bath was removed and the reaction mixture warmed to 75 C. over one hour and maintained at 60-75 C. for an additional 2 hours. The mixture was cooled overnight and the crystalline product collected by filtration to give 10 g (90.6%) of the title compound [mp: 62-64 C.]. NMR and MS was identical to data reported by Hargrave et al., J. Heterocyclic Chem., 34, 223 (1991). |
41.5 g | With calcium hypochlorite; calcium oxide; In water; at 10℃; | To the above mixture, 61.5 g of calcium hypochlorite was added in portions,After the addition was complete, the heat was kept stirring for 30 minutes,50 mL of an aqueous solution of 40 wt% calcium oxide was further added in portions,Control temperature does not exceed 10 ,The reaction was continued for 2 to 3 hours to obtain a reaction mixture.The resulting cold reaction mixture was added dropwise to water (150 mL)Control temperature of 100 degrees or less; dropping finished,70 ~ 80 C to continue the reaction 2 hours; cooling to 5 C,With concentrated hydrochloric acid adjusted pH value of 6.5 to 7; suction filtration,The filter cake was washed with ice water; the filter cake was added to 75 mL of water,Heated to 60 to 70 C, stirred for 30 minutes,Slowly cooled to 0 ~ 5 , the precipitation of crystals, filtration,The filter cake was washed with ice water, dried in vacuo,To obtain 41.5 g of 2-chloro-3-amino-4-methylpyridine,HPLC purity was 99.9%. |
Tags: 152362-01-1 synthesis path| 152362-01-1 SDS| 152362-01-1 COA| 152362-01-1 purity| 152362-01-1 application| 152362-01-1 NMR| 152362-01-1 COA| 152362-01-1 structure
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