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Chemical Structure| 228710-82-5 Chemical Structure| 228710-82-5

Structure of 228710-82-5

Chemical Structure| 228710-82-5

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Product Details of [ 228710-82-5 ]

CAS No. :228710-82-5
Formula : C11H11BrN2
M.W : 251.12
SMILES Code : BrC1=CN=C(C=C1)[N]2C(=CC=C2C)C
MDL No. :MFCD01125286
InChI Key :QWMFKVNJIYNWII-UHFFFAOYSA-N
Pubchem ID :12043622

Safety of [ 228710-82-5 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H332-H335
Precautionary Statements:P280-P305+P351+P338-P310

Application In Synthesis of [ 228710-82-5 ]

* 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 [ 228710-82-5 ]

[ 228710-82-5 ] Synthesis Path-Downstream   1~3

  • 1
  • [ 228710-82-5 ]
  • [ 67442-07-3 ]
  • [ 228710-83-6 ]
YieldReaction ConditionsOperation in experiment
67% With n-butyllithium; In tetrahydrofuran; hexanes; at -78℃; for 1.2h; To a solution of bromo pyridine from example 38 (2g, 8. 0mmol) at-78°C, in dry THF (30ml), was added butyllithium (2.5M in hexanes) (3. 5ml 8. 8MMOL), dropwise over 20 minutes. The reaction mixture was stirred for 30 minutes +, HEN <strong>[67442-07-3]2-chloro-N-methoxy-N-methylacetamide</strong> (1.2g, 8. 8MMOL) in dry THF (20ml) was added dropwise keeping the temperature AT-78°C. Stirring was continued for 30 minutes at this temperature before 1 M HCI (aq) (50ml) was added and the reaction mixture warmed to room temperature. The organic layer was separated and the aqueous layer washed with ethyl acetate (56ml). The organic layers were combined then washed with 3M NAOH (aq) (1 OML) and brine (20ml) before being dried over anhydrous magnesium sulphate, filtered and concentrated in vacuo to give crude title compound as a brown oil (1.34g, 5. 4mmol, 67percent). 1H NMR (CDCI3, 400MHZ) 6 : 2.20 (s, 6H), 4.68 (s, 2H), 5.92 (s, 2H), 7.32 (d, 1 H), 8.38 (d, 1 H), 9.16 (s, 1 H). LRMS: m/z 249 (M-H+).
67% To a solution of bromo pyridine from example 38 (2g, delta.Ommol) at -780C, in dry THF (30ml), was added butyllithium (2.5M in hexanes) (3.5ml 8.8mmol), dropwise over 20 minutes. The reaction mixture was stirred for 30 minutes then <strong>[67442-07-3]2-chloro-N-methoxy-N-methylacetamide</strong> (1.2g, 8.8mmol) in dry THF (20ml) was added dropwise keeping the temperature at -780C. Stirring was continued for 30 minutes at this temperature before 1 M HCI (aq) (50ml) was added and the reaction mixture warmed to room temperature. The organic layer was separated and the aqueous layer washed with ethyl acetate (50ml). The organic layers were combined then washed with 3M NaOH (aq) (10ml) and brine (10ml) before being dried over anhydrous magnesium sulphate, filtered and concentrated in vacuo to give crude title compound as a brown oil (1.34g, 5.4mmol, 67percent). 1H NMR (CDCI3, 400MHz) delta: 2.20 (s, 6H), 4.68 (s, 2H), 5.92 (s, 2H), 7.32 (d, I H), 8.38 (d, 1 H), 9.16 (s, 1 H). LRMS: m/z 249 (M-H+).
Example 140 2-Chloro-1-[6-(2,5-dimethyl-pyrrol-1-yl)-pyridin-3-yl]-ethanone Magnesium turnings (7.26 g, 0.30 mol) were placed in 2 L three neck flask equipped with a dropping funnel and reflux condenser. The system was purged with argon and heated for ten minutes. After cooling the flask to room temperature under argon, tetrahydrofuran (500 mL) and a crystal of iodine were added. A portion of a solution of 5-bromo-2-(2,5-dimethyl-pyrrol-1-yl)-pyridine (Example 138; 75 g, 0.30 mol) in tetrahydrofuran (200 mL) was added to initiate the reaction. The flask was heated to maintain reflux as the remainder of the solution was added. After three hours the mixture was cooled in an ice-water bath. A solution of N-methoxy-N-methylchloroacetamide (Example 139; 49.3 g, 0.35 mol) in tetrahydrofuran (200 mL) was transferred to the suspension via cannula. The mixture was warmed to ambient temperature. After 18 hours the mixture was quenched with two-thirds saturated aqueous ammonium chloride solution and extracted with ethyl acetate (3x). The combined organic phase was dried (MgSO4) and concentrated to an oil. Silica gel chromatography (75:25 hexane / ethyl acetate) afforded an oil (67 g). The oil was a 7:3 mixture of the title compound and 2-(2,5-dimethyl-pyrrol-1-yl)-pyridine. 1H NMR (CDCl3, 300 MHz; peaks corresponding to the title compound) delta 9.16 (dd, 2.6 Hz, 0.7 Hz, 1 H), 8.40 (dd, 8.5 Hz, 2.6 Hz, 1 H), 7.35 (dd, 8.5 Hz, 0.7 Hz, 1 H), 5.96 (s, 2 H), 4.71 (s, 2 H), 2.21 (s, 6 H); Rf = 0.2 (5:1 hexane / ethyl acetate).
A solution of 2.5 M n-butyl lithium in hexane (35ml, 87.6mmol) was added to a solution of the bromide from preparation 50 (20.0g, 79.7mmol) in terf-butyl methylether (300ml) at -78°C under nitrogen over a 10 minutes. The reaction was stirred for a further 10 minutes and <strong>[67442-07-3]2-chloro-N-methoxy-N-methyl-acetamide</strong> (12.1g, 87.6mmol) in ferf-butyl methylether (40ml) was added slowly. The reaction was stirred at -78°C for 20 minutes and then 1M hydrochloric acid (200ml) was added. The mixture was allowed to warm to room temperature, stirred for 2 hours and the organic phase separated. The aqueous phase was extracted with te/f-butyl methylether and the combined organic extracts were washed with water (100ml), saturated aqueous sodium chloride (100ml) and 1M sodium hydroxide (100ml). The organic phase was dried (sodium sulfate), concentrated in vacua and the residual oil purified by flash column chromatography on silica gel eluting with pentane:dichloromethane:methanol (75:25:0 changing tp 0:99:1, by volume). Recrystallisation (pentane:dichloromethane) gave the title compound as a yellow solid (11.97g).
A solution of 2.5 M n-butyl lithium in hexanes (35ml, 87.6mmol) was added to a solution of the bromide from preparation 29 (20.0g, 79.7mmol) in ferf-butyl methylether (300ml) at -78°C under nitrogen over 10 minutes. The reaction was stirred for a further 10 minutes and <strong>[67442-07-3]2-chloro-N-methoxy-N-methyl-acetamide</strong> (12.1g, 87.6mmol) in terf-butyl-methylether (40ml) was added slowly. The reaction was stirred at -78°C for 20 minutes and then 1M hydrochloric acid (200ml) was added. The mixture was allowed to warm to room temperature, stirred for 2 hours and the organic phase separated. The aqueous phase was extracted with fe/f-butyl methylether and the combined organic extracts were washed with water (100ml), saturated aqueous sodium chloride (100ml) and 1M sodium hydroxide (100ml). The organic phase was dried (sodium sulfate), concentrated in vacua and the residual oil purified by flash column chromatography on silica gel eluting with pentane:dichloromethane:methanol (75:25:0 changing to 0:99:1, by volume). The residue was recrystallised from pentane:dichloromethane to give the title compound as a yellow solid.1H NMR (400MHz, CDCI3): 5 = 9.11 (1H, s), 8.34-8.33 (1H, d), 7.32-7.30 (1H,d), 5.91 (2H, s), 4.66 (2H, s), 2.17 (6H, s) ppm.LRMS (electrospray): m/z [M-H]+ 247.

  • 2
  • [ 228710-82-5 ]
  • [ 67442-07-3 ]
  • ammonium chloride [ No CAS ]
  • [ 228710-83-6 ]
YieldReaction ConditionsOperation in experiment
With iodine; magnesium; In tetrahydrofuran; EXAMPLE 140 STR93 2-Chloro-1-[6-(2,5-dimethyl-pyrrol-1-yl)-pyridin-3-yl]-ethanone Magnesium turnings (7.26 g, 0.30 mol) were placed in 2 L three neck flask equipped with a dropping funnel and reflux condenser. The system was purged with argon and heated for ten minutes. After cooling the flask to room temperature under argon, tetrahydrofuran (500 mL) and a crystal of iodine were added. A portion of a solution of 5-bromo-2-(2,5-dimethyl-pyrrol-1-yl)-pyridine (Example 138; 75 g, 0.30 mol) in tetrahydrofuran (200 mL) was added to initiate the reaction. The flask was heated to maintain reflux as the remainder of the solution was added. After three hours the mixture was cooled in an ice-water bath. A solution of N-methoxy-N-methylchloroacetamide (Example 139; 49.3 g, 0.35 mol) in tetrahydrofuran (200 mL) was transferred to the suspension via cannula. The mixture was warmed to ambient temperature. After 18 hours the mixture was quenched with two-thirds saturated aqueous ammonium chloride solution and extracted with ethyl acetate (3*). The combined organic phase was dried (MgSO4) and concentrated to an oil. Silica gel chromatography (75:25 hexane/ethyl acetate) afforded an oil (67 g). The oil was a 7:3 mixture of the title compound and 2-(2,5-dimethyl-pyrrol-1-yl)-pyridine. 1 H NMR (CDCl3, 300 MHz; peaks corresponding to the title compound) delta 9.16 (dd, 2.6 Hz, 0.7 Hz, 1 H), 8.40 (dd, 8.5 Hz, 2.6 Hz, 1 H), 7.35 (dd, 8.5 Hz, 0.7 Hz, 1 H), 5.96 (s, 2 H), 4.71 (s, 2 H), 2.21 (s, 6 H); Rf =0.2 (5:1 hexane/ethyl acetate).
  • 3
  • [ 228710-82-5 ]
  • [ 10167-97-2 ]
 

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