| 68% |
|
To a stirred solution of <strong>[21423-81-4]3-chloro-4-methylbenzonitrile</strong> (5 g, 25.4 mmol) in carbon tetrachloride (CC14; 50 mL) under an argon atmosphere was added NBS (5.16 g, 29 mmol), and the mixture was degassed for 30 min. To this was added azobisisobutyronitrile (AIBN; 0.3 g, 1.8 mmol), and the resultant reaction mixture was heated at reflux for 4 h. The reaction mixture was cooled to ambient temperature, washed with H20, and extracted with CH2C12. The combined CH2C12 layer was washed with brine, dried over Na2S04, and concentrated under reduced pressure. The crude compound was purified by flash column chromatography (Si02, 100-200 mesh; 5% EtOAc in n-Hexane) to afford the title compound as a white solid (4.8 g, 68%): mp 87-88 C; 1H NMR (400 MHz, CDC13) delta 7.71 (s, 1H), 7.59 ( s, 2H ), 4.60 (s, 2H); ESIMS m/z 229.77 ([M+H]+); IR (thin film) 2235, 752, 621 cm-1. |
| 68% |
|
Example 45 Preparation of 4-(Bromomethyl)-3-chlorobenzonitrile (CI10) To a stirred solution of <strong>[21423-81-4]3-chloro-4-methylbenzonitrile</strong> (5 g, 25.4 mmol) in carbon tetrachloride (CCl4; 50 mL) under an argon atmosphere was added NBS (5.16 g, 29 mmol), and the mixture was degassed for 30 min. To this was added azobisisobutyronitrile (AIBN; 0.3 g, 1.8 mmol), and the resultant reaction mixture was heated at reflux for 4 h. The reaction mixture was cooled to ambient temperature, washed with water, and extracted with CH2Cl2. The combined CH2Cl2 layer was washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The crude compound was purified by flash column chromatography (SiO2, 100-200 mesh; 5% EtOAc in n-Hexane) to afford the title compound as a white solid (4.8 g, 68%): mp 87-88 C.; 1H NMR (400 MHz, CDCl3) delta 7.71 (s, 1H), 7.59 (s, 2H), 4.60 (s, 2H); ESIMS m/z 229.77 ([M+H]+); IR (thin film) 2235, 752, 621 cm-1. |
| 40% |
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; at 20℃; for 12h; |
<strong>[21423-81-4]3-chloro-4-methylbenzonitrile</strong> (2 g, 13.2 mmol) was dissolved in carbon tetrachloride (20 ml), and N-bromosuccinimide (3.5 g, 19.8 mmol) and 2,2-azo-bis-isobutyronitrile (216 mg, 1.32 mmol) were added thereto, followed by stirring at room temperature for 12 hours. After completion of the reaction, the organic layer was separated using CH2Cl2 and H2O, and the separated organic layer was dried with MgSO4 and filtered. The filtrate was subjected to column chromatography (EA/n-Hex = 1:9), thereby obtaining 2-chloro-4-cyanobenzyl bromide (1.2 g, 5.2 mmol, 40 %).[1699] 1H NMR (400 MHz, CDCl3) delta 7.72 (s, 2H), 7.28 (s, 1H), 4.59 (s, 2H). |
| 24% |
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; at 85℃; for 4h; |
A solution of <strong>[21423-81-4]3-chloro-4-methylbenzonitrile</strong> (1.0 g, 6.60 mmol), BS (1.4 g, 7.87 mmol), and azobisisobutyronitrile (1.08 g, 6.57 mmol) in carbon tetrachloride (33 mL) stirred for 4 h at 85 C. The resulting mixture was cooled to room temperature, washed with 30 mL of water and 30 mL of brine, dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum. The residue was purified via column chromatography on silica gel (eluting with ethyl acetate/petroleum ether (1 : 15)) to afford 4-(bromomethyl)-3-chlorobenzonitrile (360 mg, 24%) as yellow oil. |
|
With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; |
A. 2-Chloro-4-cyanobenzyl bromide STR27 A mixture of <strong>[21423-81-4]3-chloro-4-methyl-benzonitrile</strong> (30.0 g, 0.2 mol), N-bromosuccinimide (36.0 g, 0.21 mol) and benzoyl peroxide (100 mg) in 600 mL of CCl4 was refluxed with illumination for 72 h. N-Bromosuccinimide (5.0 g) was added and the reaction was continued for an additional 24 h. The mixture was cooled, filtered and evaporated. Recrystallization from heptane gave pure 2-chloro-4-cyanobenzyl bromide: yield 24.5 g; mp 83-85 C. Anal. calcd for C8 H5 BrClN; C, 41.69; H, 2.19; N, 6.07. Found: C, 41.48; H, 1.80; N, 5.76. |
|
With tetrachloromethane; N-Bromosuccinimide; dibenzoyl peroxide; for 2h;Heating / reflux; |
A mixture of <strong>[21423-81-4]3-chloro-4-methylbenzonitrile</strong> (4.8 g), Lambda/-bromosuccinimide (5.5 g), dibenzoyl peroxide (0.43 g) and carbon tetrachloride (30 mL) was heated a reflux for 2 hours. The mixture was cooled to room temperature, filtered and washed with dichloromethane. The filtrated was washed with water, dried over sodium sulfate and the solvent removed under reduced pressure. Purification of the residue by column chromatography on silica gel, eluting with a mixture of cyclohexane and ethyl acetate (1:0 to 19:1 by volume) gave title compound, 4.1 g.1H NMR (CDCI3): delta 4.55 (s, 2H), 7.55 (m, 2H), 7.70 (m, 1H). |
|
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; for 25h;Heating / reflux; |
Step 1 : 4-(bromomethyl')-3-chlorobenzonitrile; A mixture of <strong>[21423-81-4]3-chloro-4-methylbenzonitrile</strong> (7.5 g, 50 mmol, 1.0 equiv), N- bromosuccinimide (9.14 g, 52 mmol, 1 .1 equiv), and azobisisobutyronitrile (AIBN, 0.82 g, 5 mmol, 0.1 equiv) in carbon tetrachloride was heated to reflux temperature for 25 h. Water (50 ml_) was added, and the product was extracted with CH2CI2. The organic layers were washed with water, dried with MgSO4, and evaporated to provide 11 .3 g of the title compound. This material was used in the next step without purification. |
|
With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; |
A. 4-Bromomethyl-3-chlorobenzonitrile (cas No. 2192483-4) 3-Chloro-4-methylbenzonitrile (2.34 g, 15.4 mmol), NBS (3.0 g, 16.9 mmol) and benzoyl peroxide (0.37 g, 1.54 mmol) are taken up in carbon tetrachloride (50 mL, 0.3M) and refluxed until the reaction is judged complete by TLC. The mixture is then allowed to cool to room temperature and is filtered. The filtrate is concentrated and purified via flash column chromatography (0-5% EtOAc/hexanes) to give 4-bromomethyl-3-chlorobenzonitrile as a white solid. HRMS (ESI) m/z 229.9133 (229.9193 calcd for C8H6ClBrN, M+H). |
|
With N-Bromosuccinimide; azobisisobutyronitrile; In tetrachloromethane; hexane; ethyl acetate; |
Example 45 Preparation of 4-(Bromomethyl)-3-chlorobenzonitrile (CI10) To a stirred solution of <strong>[21423-81-4]3-chloro-4-methylbenzonitrile</strong> (5 g, 25.4 mmol) in CCl4 (50 mL) under an argon atmosphere was added NBS (5.16 g, 29 mmol), and the mixture was degassed for 30 min. To this was added AIBN (0.3 g, 1.8 mmol), and the resultant reaction mixture was heated at reflux for 4 h. The reaction mixture was cooled to ambient temperature, washed with water, and extracted with CH2Cl2. The combined CH2Cl2 layer was washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The crude compound was purified by flash column chromatography (SiO2, 100-200 mesh; 5% EtOAc in n-Hexane) to afford the title compound as a white solid (4.8 g, 68%): mp 87-88 C.; 1H NMR (400 MHz, CDCl3) delta 7.71 (s, 1H), 7.59 (s, 2H), 4.60 (s, 2H); ESIMS m/z 229.77 ([M+H]+); IR (thin film) 2235, 752, 621 cm-1. |
|
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; hexane; ethyl acetate; |
Example 45 Preparation of 4-(Bromomethyl)-3-chlorobenzonitrile (CHO) To a stirred solution of <strong>[21423-81-4]3-chloro-4-methylbenzonitrile</strong> (5 g, 25.4 mmol) in carbon tetrachloride (CCl4; 50 mL) under an argon atmosphere was added NBS (5.16 g, 29 mmol), and the mixture was degassed for 30 min. To this was added azobisisobutyronitrile (AIBN; 0.3 g, 1.8 mmol), and the resultant reaction mixture was heated at reflux for 4 h. The reaction mixture was cooled to ambient temperature, washed with H2O, and extracted with CH2Cl2. The combined CH2Cl2 layer was washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The crude compound was purified by flash column chromatography (SiO2, 100-200 mesh; 5% EtOAc in n-Hexane) to afford the title compound as a white solid (4.8 g, 68%): mp 87-88 C.; 1H NMR (400 MHz, CDCl3) delta 7.71 (s, 1H), 7.59 (s, 2H), 4.60 (s, 2H); ESIMS m/z 229.77 ([M+H]+); IR (thin film) 2235, 752, 621 cm-1. |
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