Structure of 874-27-1
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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| CAS No. : | 874-27-1 |
| Formula : | C8H7ClO |
| M.W : | 154.59 |
| SMILES Code : | O=CC1=CC=CC(Cl)=C1C |
| MDL No. : | MFCD11047716 |
| InChI Key : | WMDHVKYUOKHNQK-UHFFFAOYSA-N |
| Pubchem ID : | 13162662 |
| GHS Pictogram: |
|
| Signal Word: | Warning |
| Hazard Statements: | H302-H315-H319-H335 |
| Precautionary Statements: | P261-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 |
|---|---|---|
| 69% | With hydrogenchloride; In dichloromethane; | A. 3-Chloro-2-methylbenzaldehyde To 3-chloro-2-methylbenzonitrile (5 g, 33 mmol) in dichloromethane (150 mL) at -78 C. was added DiBAL (1M in dichloromethane, 41 mL). The reaction mixture was stirred at -78 C. for 2 h then quenched with methanol. The mixture was warmed to 0 C and HCl (10%) was added. The ice-water bath was removed and the mixture was stirred at room temperature for 10 min. The two phases were separated and aqueous phase was extracted with dichloromethane. Combined dichloromethane was washed with brine, dried over sodium sulfate and concentrated. Column chromatography (5% ethyl acetate/hexane) gave 3-chloro-2-methylbenzaldehyde (3.5 g, 69%). 1H NMR (300 MHz, CDCl3) delta 2.64 (s, 3H), 7.21-7.26 (m, 1H), 7.50-7.53(m, 1H), 7.63-7.66 (m, 1H), 10.20 (s, 1H) |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| These aldehydes and ketones are set forth for exemplification and are not to be construed as limiting the scope of this invention. benzaldehyde, ... 1,1-biphenyl-4-carboxaldehyde, 2-naphthylaldehyde, 6-methoxy-2-naphthaldehyde, 1,1-biphenylacetaldehyde, 2-methyl-3-chlorobenzaldehyde, 4-trifluoromethylbenzaldehyde, and benzene acetaldehyde, 4-pyridylaldehyde, 2,4-difluorobenzaldehyde, ... |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| In tetrahydrofuran; hexane; | PREPARATION 1 (Witting reaction) Methyltriphenylphosphonium bromide (6.9 g, 0.019M) was suspended in dry tetrahydrofuran (100 ml) at -40 C. under an atmosphere of dry nitrogen. n-Butyllithium (13.5 ml. of a 1.55M solution in hexane, 0.021M) was added dropwise during 10 minutes and the mixture was stirred at -40 C. for 30 minutes. <strong>[874-27-1]3-Chloro-2-methylbenzaldehyde</strong> (3.0 g, 0.019M) in dry tetrahydrofuran (10 mls) was then added. The mixture was maintained at -40 C. for 30 minutes and then allowed to warm to room temperature. Hexane (150 ml) was added and the mixture was filtered. The hexane was evaporated to give crude 3-chloro-2-methylstyrene which was used directly without further purification. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 60% | With hydrogenchloride; lithium hexamethyldisilazane; In tetrahydrofuran; methanol; dichloromethane; ethyl acetate; | B. 1-(3-Chloro-2-methylphenyl)-2-phenylethanamine To <strong>[874-27-1]3-chloro-2-methylbenzaldehyde</strong> (2.85 g, 18.5 mmol) in THF (5 mL) at 0 C. was added lithium bis(trimethylsilyl)amide (1M in THF, 22.2 mL). The ice-water bath was removed and the reaction mixture was stirred from 0 C. to room temperature for 2 h. The reaction mixture was then cooled back to 0 C. and benzylmagnesium chloride (1M in THF, 22.2 mL) was added. The reaction mixture was stirred from 0 C. to room temperature for 1 h then quenched with NH4Cl (Sat.), extracted with ethyl acetate. Combined ethyl acetate was washed with brine, dried over sodium sulfate and concentrated. HCl (1.25M in methanol) was added until a pH of 2. Methanol was removed to give yellow solid. To the solid was added dichloromethane. The suspension was filtered and washed with dichloromethane to yield white solid. The white solid was dissolved in methanol, basified with NaOH (1N) and extracted with ethyl acetate. Combined ethyl acetate was washed with brine, dried over sodium sulfate and concentrated to produce 1-(3-chloro-2-methylphenyl)-2-phenylethanamine (22.73 g, 60%) as a light yellow oil. 1H NMR (300 MHz, CDCl3) delta 2.37 (s, 3H), 2.67-2.75 (m, 1H), 2.95-3.01 (m, 1H), 4.46-4.50 (m, 1H), 7.17-7.19 (m, 3H), 7.24-7.33(m, 4H), 7.46-7.49 (m, 1H). |
[ 1816-92-8 ]
[ 874-27-1 ]
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With methanol; sodium methylate; at -20 - 20℃; for 11.0h;Inert atmosphere; | Step 3 - Methyl (Z)-2-azido-3-(3-chloro-2-methylphenyl) prop-2-enoate (0827) [00486] To a solution of sodium methoxide (2.34 g, 43.2 mmol) in methanol (140 mL) was added <strong>[874-27-1]3-chloro-2-methyl-benzaldehyde</strong> (5.80 g, 43.3 mmol) and methyl 2-azidoacetate (16.8 g, 129 mmol,) dropwise at -20 C under nitrogen. The mixture was stirred at 20 C for 11 hours. On completion, the mixture was poured into ice-water (100 mL) and extracted with ethyl acetate (3 x 100 mL). The combined organic phase was washed with saturated brine (2 x 100 mL), dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate = 500:1 to 5:1) to give the title compound. 1H NMR (300MHz, CDCl3) delta = 8.98 (br. s., 1H), 7.37 - 7.10 (m, 3H), 3.98 (s, 3H), 2.60 (s, 3H). |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With manganese(IV) oxide; In dichloromethane; at 20 - 40℃; for 12.0h;Inert atmosphere; | Step 2 - 3-Chloro-2-methyl-benzaldehyde (0825) [00485] To a solution of (3-chloro-2-methyl-phenyl)methanol (400 mg, 2.55 mmol) in dichloromethane (20 mL) was added manganese dioxide (2.22 g, 25.5 mmol) in one portion at 20 C under nitrogen. The mixture was stirred at 30-40 C for 12 hours. On completion, the mixture was filtered and concentrated, the residue was purified by silica gel chromatography (petroleum ether:ethyl acetate = 500:1 to 200:1) to give the title compound.1H NMR (400MHz, CDCl3) delta = 10.28 (s, 1H), 7.73 - 7.71 (d, J = 7.6 Hz, 1H), 7.61 - 7.60 (d, J = 6.8 Hz, 1H), 7.33 - 7.29 (m, 1H), 2.72 (s, 3H). |
[ 874-27-1 ]