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Chemical Structure| 116759-33-2 Chemical Structure| 116759-33-2

Structure of 116759-33-2

Chemical Structure| 116759-33-2

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Product Details of [ 116759-33-2 ]

CAS No. :116759-33-2
Formula : C7H7ClFN
M.W : 159.59
SMILES Code : NC1=CC(C)=C(Cl)C=C1F
MDL No. :MFCD09062485
InChI Key :KENAMMSVUHVEOL-UHFFFAOYSA-N
Pubchem ID :14157495

Safety of [ 116759-33-2 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 116759-33-2 ]

* 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 [ 116759-33-2 ]

[ 116759-33-2 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 112108-73-3 ]
  • [ 116759-33-2 ]
YieldReaction ConditionsOperation in experiment
93% With hydrogenchloride; iron; In ethanol; water; at 80℃; for 1.5h; To a solution of <strong>[112108-73-3]1-chloro-5-fluoro-2-methyl-4-nitrobenzene</strong> (5a) (23.0 g, 121 mmol) in EtOH/H2O (200 mL, 1:1) was added 12 M HCl (10.1 mL, 121 mmol). The mixture was heated to 80 C. and Fe (23.7 g, 425 mmol) was added slowly over a period of 30 minutes. The mixture was stirred at the same temperature for 1 h. LCMS analysis indicated the starting material was consumed and the desired product was formed. The mixture was cooled to 25 C., diluted with ethyl acetate (300 mL), and basified to pH=8?9 with saturated aqueous NaHCO3. The layers were filtered separated, and the aqueous layer was extracted with ethyl acetate (2*300 mL). The combined organics were washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure to provide 4-chloro-2-fluoro-5-methylaniline (5b) as a yellow solid (18.0 g, 93% yield). 1H NMR (400 MHz, DMSO-d6) delta 7.08 (d, J=11.1 Hz, 1H), 6.69 (d, J=9.6 Hz, 1H), 5.20 (s, 2H), 2.15 (s, 3H). LCMS (ESI) m/z 160, 162 (M+H).
93% With hydrogenchloride; iron; In ethanol; water; at 80℃; for 1.5h; To a solution of <strong>[112108-73-3]1-chloro-5-fluoro-2-methyl-4-nitrobenzene</strong> (54) (23.0 g, 121 mmol) in EtOH/H2O (200 mL, 1:1) was added 12 M HCl (10.1 mL, 121 mmol). The mixture was heated at 80 C. and Fe (23.7 g, 425 mmol) was added slowly over a period of 30 minutes. The mixture was stirred at the same temperature for 1 hour. LCMS indicated the starting material was consumed and the desired product was formed. Then, the mixture was cooled to 25 C., diluted with EtOAc (300 mL) and acidified to pH=8-9 with saturated aqueous NaHCO3. The layers were filtered, separated and the aqueous layer was extracted with EtOAc (2*300 mL). The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure and gave 4-chloro-2-fluoro-5-methylaniline (55) as a yellow solid (18.0 g, 93% yield). 1H NMR (400 MHz, DMSO-d6) delta 7.08 (d, J=11.1 Hz, 1H), 6.69 (d, J=9.6 Hz, 1H), 5.20 (s, 2H), 2.15 (s, 3H). LCMS (ESI) m/z 160, 162 (M+H).
32% With hydrogenchloride; iron; In ethanol; for 3.0h;Reflux; 4-Chloro-2-fluoro-5-methylaniline To a suspension of <strong>[112108-73-3]1-chloro-5-fluoro-2-methyl-4-nitrobenzene</strong> (1 equiv) in EtOH (2 M) was added Fe (5 equiv.), followed by concentrated HCl(2 M). The reaction was refluxed for 3 h. The reaction was filtered through a pad of celite. The filtrate was concentrated. The resulting residue was purified by column chromatography to afford 4-chloro-2-fluoro-5-methylaniline (32%) as a purple solid. 1H NMR (400 MHz, CDCl3) delta ppm: 7.41 (d, J=7.03 Hz, 1H), 6.97-7.13 (m, 2H), 2.33 (s, 3H).
With hydrogen; In acetic acid; Step B Synthesis of 4-chloro-2-fluoro-5-methylaniline A solution of <strong>[112108-73-3]2-chloro-4-fluoro-5-nitrotoluene</strong> (30.0 g, 0.158 mole) in glacial acetic acid (150 ml) was added to a 250 ml Parr bottle which contained platinum IV oxide (0.4 g). The Parr bottle was placed on a Parr hydrogenation apparatus and charged with hydrogen. The reaction mixture was allowed to shake until hydrogen absorption ceased. The catalyst was removed by vacuum filtration. The filtrate containing 4-chloro-2-fluoro-5-methylaniline was used in the following step. This reaction was repeated several times.

 

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