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Chemical Structure| 1142943-96-1 Chemical Structure| 1142943-96-1

Structure of 1142943-96-1

Chemical Structure| 1142943-96-1

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Product Details of [ 1142943-96-1 ]

CAS No. :1142943-96-1
Formula : C10H9BrN4O
M.W : 281.11
SMILES Code : O=C(C1CC1)NC2=NN3C(Br)=CC=CC3=N2
MDL No. :MFCD28502349
InChI Key :XLBCMNCPMMPNHH-UHFFFAOYSA-N
Pubchem ID :59179473

Safety of [ 1142943-96-1 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H312-H332
Precautionary Statements:P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P330-P363-P501

Application In Synthesis of [ 1142943-96-1 ]

* 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.

  • Downstream synthetic route of [ 1142943-96-1 ]

[ 1142943-96-1 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 1010120-55-4 ]
  • [ 4023-34-1 ]
  • [ 1142943-96-1 ]
YieldReaction ConditionsOperation in experiment
76% With triethylamine; In 1,2-dichloro-ethane; at 20℃; <strong>[1010120-55-4]5-bromo-[1,2,4]triazolo[1,5-a]pyridin-2-amine</strong> (10 g, 50 mmol) and triethylamine (10 g, 100 mmol) in dichloroethane (200 mL) Cyclopropionyl chloride (5.7 g, 55 mmol) was added and stirred at room temperature overnight. After the reaction mixture was diluted, it was washed with water, washed with saturated brine, dried over anhydrous sodium sulfate and evaporated. Purification by silica gel column chromatography gave white solid (10 g, 76%)
58% Step (Hi)5-bromo-[l,2,4]triazolo[l,5-a]pyridin-2-amine (10.7g, 50mmol) was suspended in acetonitrile (200mL) and DIPEA (9.6mL, 55mmol). Cyclopropanecarbonyl chloride (5.0mL, 55mmol) and 4-(Dimethylamino)pyridine (287mg, 2.35mmol) were added in one portion and the suspension heated at 80C for 18h. After this time the solvents were removed in vacuo and the resulting solid was stirred in ammonia/methanol (2M) for 2h at rt. The solvents were removed in vacuo and the resulting solid was triturated, filtered and washed with diethyl ether (3 x lOOmL) to afford the desired compound as a white solid (8.12g, 58% ). LCMS (method A), (M+H+) 281/283, RT = 0.78min.
56.64% To <strong>[1010120-55-4]5-bromo-[1,2,4] triazolo[1,5-a]pyridin-2-amine</strong>(15.00 g, 70.41 mmol) and triethylamine(21.4 g, 211.2 mmol), dissolved in acetonitrile(150 mL) was added dropwise cyclopropanecarboxylic acid chloride(8.8 g, 84.5 mmol) at 0C. After adding, the mixture was warmed to room temperature for the reaction for 16 hours. After TLC showed that the reaction was completed through monitoring, the reaction mixture was distilled under reduced pressure. The resulting residue was dissolved in an alcoholic solution of methylamine(150 mL), heated to 80C for the reaction for 1 hour, cooled, distilled under reduced pressure. The resulting residue was dissolved in mixed solution of water(100 mL) and ethyl acetate(200 mL), and the layers were separated and extracted. The combined organic phase was dried with anhydrous sodium sulfate and filtered, and the filtrate was distilled under reduced pressure. The resulting crude product was purified through silica gel column chromatography (eluting with ethyl acetate/petroleum ether =0?70%) to give N-(5-bromo-[1,2,4]triazolo[1,5-a] pyridin-2-yl)cyclopropyl carboxamide (7.2 g, 56.64% yield) as a pale yellow solid. 1H NMR (400 MHz, DMSO-d6) delta = 11.20 (br. s., 1 H), 7.68 - 7.73 (m, 1 H), 7.52 - 7.58 (m, 1 H), 7.46 - 7.51 (m, 1 H), 1.96 - 2.09 (m, 1 H), 0.82 (d, J=6.28 Hz, 4 H). MS (ESI) Calcd. for C10H9 BrN4O [M + H]+ 282, Found 282.
To a solution of the 2-amino-triazolopyridine (3) (7.10 g, 33.3 mmol) in dry CH3CN (150 mL) at 50C is added Et3N (11.6 mL, 83.3 mmol) followed by the appropriate acid chloride (83.3 mmol). The reaction mixture is then allowed to warm to ambient temperature and stirred until all starting material (3) is consumed. If required, further Et3N (4.64 mL, 33.3 mmol) and acid chloride (33.3 mmol) may be added to ensure complete reaction. Following solvent evaporation in vacuo the resultant residue is treated with 7 N methanolic ammonia solution (50 mL) and stirred at ambient temp, (for 1-16 h) to hydrolyse any bis-acylated product. Product isolation is made by removal of volatiles in vacuo followed by trituration with Et2O (50 mL). The solids may be collected by filtration, washed with H2O (2x50 rnL), acetone (50 rnL) and Et2O (50 rnL), then dried in vacuo to give the required intermediate (4). In some cases column chromatography (petrol/EtOAc) may be required to obtain pure compounds.
To a solution of the 2-amino-triazolopyridine (3) (7.10 g, 33.3 mmol) in dry CH3CN (150 mL) at 5 C. is added Et3N (11.6 mL, 83.3 mmol) followed by the appropriate acid chloride (83.3 mmol). The reaction mixture is then allowed to warm to ambient temperature and stirred until all starting material (3) is consumed. If required, further Et3N (4.64 mL, 33.3 mmol) and the acid chloride (33.3 mmol) may be added to ensure complete reaction. Following solvent evaporation in vacuo the resultant residue is treated with 7 N methanolic ammonia solution (50 mL) and stirred at ambient temp. (for 1-16 h) to hydrolyse any bis-acylated product. Product isolation is made by removal of volatiles in vacuo followed by trituration with Et2O (50 mL). The solids may be collected by filtration, washed with H2O (2×50 mL), acetone (50 mL) and Et2O (50 mL), then dried in vacuo to give the required acyl intermediate (4). In some cases column chromatography (petrol/EtOAc) may be required to obtain pure compounds.
1.1.3 General Procedure for Mono-Acylation to Afford Intermediate (4) To a solution of the 2-amino-triazolopyridine (3) (7.10 g, 33.3 mmol) in dry CH3CN (150 mL) at 5 C. is added Et3N (11.6 mL, 83.3 mmol) followed by cyclopropanecarbonyl chloride (83.3 mmol). The reaction mixture is then allowed to warm to ambient temperature and stirred until all starting material (3) is consumed. If required, further Et3N (4.64 mL, 33.3 mmol) and cyclopropanecarbonyl chloride (33.3 mmol) is added to ensure complete reaction. Following solvent evaporation in vacuo the resultant residue is treated with 7 N methanolic ammonia solution (50 mL) and stirred at ambient temp. (for 1-16 h) to hydrolyse any bis-acylated product. Product isolation is made by removal of volatiles in vacuo followed by trituration with Et2O (50 mL). The solids are collected by filtration, washed with H2O (2*50 mL), acetone (50 mL) and Et2O (50 mL), then dried in vacuo to give the required bromo intermediate (4).
With triethylamine; In acetonitrile; at 5 - 20℃; Step iii : Cyclopropanecarboxylic acid (5-bromo-[1,2,4]triazolo[1,5-a]pyridin-2-yl)-amide To a solution of the 2-amino-triazolopyridine obtained in the previous step (7.10 g, 33.3 mmol) in dry MeCN (150 mL) at 5 C. is added Et3N (11.6 mL, 83.3 mmol) followed by cyclopropanecarbonyl chloride (83.3 mmol). The reaction mixture is then allowed to warm to ambient temperature and stirred until all starting material is consumed. If required, further Et3N (4.64 mL, 33.3 mmol) and cyclopropanecarbonyl chloride (33.3 mmol) is added to ensure complete reaction. Following solvent evaporation in vacuo the resultant residue is treated with 7 N methanolic ammonia solution (50 mL) and stirred at ambient temp. (for 1-16 h) to hydrolyse any bis-acylated product. Product isolation is made by removal of volatiles in vacuo followed by trituration with Et2O (50 mL). The solids are collected by filtration, washed with H2O (2*50 mL), acetone (50 mL) and Et2O (50 mL), then dried in vacuo to give the desired compound.
Step iii : Cyclopropanecarboxylic acid (5-bromo-[1,2,4]triazolo[1,5-a]pyridin-2-yl)-amide To a solution of the 2-amino-triazolopyridine obtained in the previous step (7.10 g, 33.3 mmol) in dry MeCN (150 mL) at 5 C. is added Et3N (11.6 mL, 83.3 mmol) followed by cyclopropanecarbonyl chloride (83.3 mmol). The reaction mixture is then allowed to warm to ambient temperature and stirred until all starting material is consumed. If required, further Et3N (4.64 mL, 33.3 mmol) and cyclopropanecarbonyl chloride (33.3 mmol) is added to ensure complete reaction. Following solvent evaporation in vacuo the resultant residue is treated with 7 N methanolic ammonia solution (50 mL) and stirred at ambient temp. (for 1-16 h) to hydrolyse any bis-acylated product. Product isolation is made by removal of volatiles in vacuo followed by trituration with Et2O (50 mL). The solids are collected by filtration, washed with H2O (2*50 mL), acetone (50 mL) and Et2O (50 mL), then dried in vacuo to give the desired compound.
With triethylamine; In acetonitrile; at 5 - 20℃; [0167] To a solution of the 2-amino-triazolopyridine obtained in the previous step (7.10 g, 33.3 mmol) in dry MeCN (150 mL) at 5C is added Et3N (11.6 mL, 83.3 mmol) followed by cyclopropanecarbonyl chloride (83.3 mmol). The reaction mixture is then allowed to warm to ambient temperature and stirred until all starting material is consumed. If required, further Et3N (4.64 mL, 33.3 mmol) and cyclopropanecarbonyl chloride (33.3 mmol) is added to ensure complete reaction. Following solvent evaporation in vacuo the resultant residue is treated with 7 N methanolic ammonia solution (50 mL) and stirred at ambient temp, (for 1 h-16 h) to hydro lyse any bis-acylated product. Product isolation is made by removal of volatiles in vacuo followed by trituration with Et20 (50 mL). The solids are collected by filtration, washed with H20 (2x50 mL), acetone (50 mL) and Et20 (50 mL), then dried in vacuo to give the desired compound
4.5 g With pyridine; at -50℃; for 0.166667h; Add 50mL pyridine to the reaction flask,Cyclopropane chloride (2.9 g, 28 mmol) was added dropwise to the reaction flask at -50C.Stir for 10 minutes,5-Bromo-[1,2,4]triazolo[1,5-a]pyridin-2-amine (5 g, 23 mmol) was then added to the reaction flaskin,The reaction was stirred overnight at room temperature.After the reaction is completed,Add 100 mL of petroleum ether to the reaction solution.FilteringFilter cake washed twice with petroleum ether, Each time 100mL,Then wash once with 100mL of waterTo get the title product,Earth gray solid 4.5g
4 g With N-ethyl-N,N-diisopropylamine; In dichloromethane; at 0℃; for 5h; 100 ml of 6 dichloromethane and 9 g of 12 diisopropylethylamine were added to 5 g of the product of Step 2. The mixture was cooled to 0 C in an ice bath. 6.1 g of 15 cyclopropanecarbonyl chloride was added dropwise. The mixture became clear after 1 hour of reaction. After the reaction was continued for 4 hours, the reaction system was concentrated to dryness to give an oily 16 solid. Then, a mixed solution of 7 ml of ammonia water and 43 ml of methanol was added to the oily solid under cooling in an ice salt bath, and stirred for about 3 hours. The system became a brown turbid liquid. After filtration by suction, the solid was washed with water and dried to obtain 4 g of the target.

  • 2
  • [ 1142943-96-1 ]
  • [ 628692-15-9 ]
  • [ 1142936-59-1 ]
 

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