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CAS No. : | 78775-11-8 | MDL No. : | MFCD07787170 |
Formula : | C8H7BrO | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | YBXGUHGVNUFFJU-UHFFFAOYSA-N |
M.W : | 199.04 | Pubchem ID : | 10921521 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-H332-H335 | 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 |
---|---|---|
Preparation of Intermediate 4-Bromo-3-methyl-benzaldehvde (l-2a):The starting material (4-bromo-3-methyl-benzonitrile, 12.8g, 65.3 mmol) was dissolved in toluene (120 ml_) and dichloromethane (20 mL) and cooled to -600C as a 1.5M diisobutylaluminum hydride in toluene (67 mL, 100 mmol) was added dropwise over 30 minutes keeping the temperature between -60 and -500C. The reaction was allowed to warm slowly to room temperature and stirred for an additional 3 hours. The reaction was quenched by adding ethyl acetate and stirring for 20 minutes before the addition of 1 N aqueous hydrochloric acid at 0°C. The reaction mixture was then allowed to warm slowly to room temperature before extractive workup in the usual manner using ethyl acetate (2 times). The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by chromatography on silica eluting with 5percent ethyl acetate in heptane to yield 5.6 g of the title compound (l-2a).1H NMR (CDCI3): delta 2.47 (s, 3H), 7.54 (dd, 1 H), 7.69-7.72 (m, 2H), 9.94 (s, 1H) | ||
Example II: Preparation of 4-bromo-3-methyl-benzaldehvde; A solution of 4-bromo-3-methyl-benzonitrile (500 mg) in dichloromethane was added at 0°C to a solution of diisobutylaluminium hydride ("DIBAL-H") in hexanes (IM) (2.6 ml). The reaction mixture was stirred at 0°C for 2 hours. The reaction mixture was poured on a mixture of ice (10 g) and aqueous hydrobromic acid (6M) (10 ml). The mixture was allowed to warm to ambient temperature and then extracted twice with dichloromethane. The combined organic phases were washed with water, dried over sodium sulfate, and concentrated to give 4-bromo-3-methyl-benzaldehyde (0.419 g) as a colorless oil. 1H-NMR (400 MHz, CDCl3): 9.95 (s, IH), 7.72 (m, 2H), 7.55 (d, IH), 2.50 (s, 3H) ppm. | ||
Example Il : Preparation of 4-bromo-3-methyl-benzaldehyde; A solution of 4-bromo-3-methyl-benzonitrile (commercially available) (500 mg) in dichloromethane was added at 0°C to a solution of diisobutylaluminium hydride ("DIBAL- H") (2.6.ml) in hexanes (IM). The mixture was stirred at 0°C for 2 hours. The reaction mixture was poured on a mixture of ice (10 g) and aqueous hydrobromic acid (6M) (10 ml). The mixture was allowed to warm to ambient temperature and then extracted twice with dichloromethane. The combined organic phases were washed with water, dried over sodium sulfate, and concentrated to give 4-bromo-3-methyl-benzaldehyde (0.419 g) as a colorless oil. 1H-NMR (400 MHz, CDCl3): 9.95 (s, IH), 7.72 (m, 2H), 7.55 (d, IH), 2.50 (s, 3H) ppm. |
A solution of 4-bromo-3-methyl-benzonitrile (commercially available) (500 mg) in dichloromethane (7.5 ml) was added at 00C to a solution of diisobutylaluminium hydride ("DIBAL-H") (2.6. ml) in hexanes (IM). The reaction mixture was stirred at 00C for 2 hours. The reaction mixture was poured on a mixture of ice (10 g) and aqueous hydrobromic acid (6M) (10 ml). The mixture was allowed to warm to ambient temperature and then extracted twice with dichloromethane. The combined organic phases were washed with water, dried over sodium sulfate, and concentrated to give 4-bromo-3-methyl-benzaldehyde (0.419 g) as a colorless oil. 1H-NMR (400 MHz, CDCl3): 9.95 (s, IH), 7.72 (m, 2H), 7.55 (d, IH), 2.50 (s, 3H) ppm. | ||
With diisobutylaluminium hydride; In hexane; at -40 - 20℃; for 1.5h; | To a solution of 4-bromo-3-methylbenzonitrile (0.975 g; 5.00 mmol) in anhyd CH2Cl2(7.5 mL) at ?40° C. was added DIBAL-H (7.5 mL of a 1M solution in hexanes; 7.5 mmol), dropwise over 5 min. The mixture was stirred 30 min at ?40° C., removed from the cooling bath and stirred 1 h at rt. The mixture was cooled in an ice bath, and excess hydride was quenched by dropwise addition of MeOH. After stirring 20 min, Rochelle's salt (satd aq. solution) was added, the mixture was stirred at rt overnight, and the layers were separated. The aqueous layer was extracted with CH2Cl2(×2), combined organics were washed (H2O, brine), dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by flash chromatography (EtOAc/hexanes), affording the title compound as a colorless solid (Note 1). Note 1 The title compound was oxidized rapidly on standing in air to a mixture of benzaldehyde and benzoic acid. |