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CAS No. : | 443-82-3 | MDL No. : | MFCD00000323 |
Formula : | C8H9F | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | AWLDSXJCQWTJPC-UHFFFAOYSA-N |
M.W : | 124.16 | Pubchem ID : | 96489 |
Synonyms : |
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Signal Word: | Danger | Class: | 3 |
Precautionary Statements: | P210-P403+P235 | UN#: | 1993 |
Hazard Statements: | H225 | Packing Group: | Ⅲ |
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 |
---|---|---|
63.4% | With sodium nitrite In Et3N-3HF; diethyl ether | EXAMPLE 5 Diazotization of 2,3-dimethylaniline in Et3N-3HF 2,3-Dimethylaniline (2.3 g, 0.02 mol) was syringed into Et3N-3HF (30 cm3) at 0° C. The addition of sodium nitrite (2.0 g, 0.03 mol) caused the evolution of gas under the influence of ultrasound, which was significant during the first 25 minutes. The clear reaction mixture gradually turned yellow and progressively darkened with the formation of tar. The brown mixture was poured into water (150 cm3) and extracted with diethyl ether (180 cm3*2). The remaining tarry residue was transferred to a Soxhlet apparatus and extracted repeatedly with diethyl ether (30 cm3) over 24 hours. The ether extracts were dried over magnesium sulphate and fractional removal of diethyl ether afforded a brown oil. Distillation of the oil at 142-143° C. at; atmospheric pressure afforded 1-fluoro-2,3-dimethylbenzene (1.47 g, 63.4percent) as a clear liquid. The 1H n.m.r. spectrum had signals at δ&H (CDCl3) 2.18, 2-CH3 (d, J=2.0 Hz, 3H); 2.28, 3-CH3 (s, 3H); 6.88, 6-H (t, J=7.6 Hz, 1H) and 6.91, 4-H (d, J=7.6 Hz, 1H) and 7.03, 5-H (q, J=8.0 Hz and J=6.0 Hz, 1H). The 19F n.m.r. spectrum had a signal at δF (CDCl3) 118.3, 1-F (tq, J=7.6 Hz and J=2.0 Hz). The mass spectrum produced a molecular ion at m/z 124 and the expected fragmentation pattern for 1-fluoro-2,3-dimethylbenzene at m/z 109, 101, 96, 86, 83 and 77. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90 %Spectr. | With lithium hydroxide monohydrate; silver trifluoromethanesulfonate; Selectfluor In ethyl acetate at 55℃; Sealed tube | General procedure: Trifluoroborate (0.50 mmol, 1.0 equiv), LiOH·H2O (25.2 mg, 0.60 mmol, 1.2 equiv), Selectfluor? (212 mg, 0.60 mmol, 1.2 equiv), AgOTf (386 mg, 1.5 mmol, 3.0 equiv) were weighed into a 20 mL microwave vial. EtOAc (5 mL) was added, and sealed with a microwave cap and the mixture was allowed to stir at 55 °C for 5-15 h. The resulting solution was cooled to room temperature. For the compounds reported with isolated yields (2a, 2b, 2c, 2d, 2e, 2g, 2h, 2j, 2k, 2l, 2m, 2o, 2p, 2t, 2u, 2x, 2v, 2y, 2ab, 2ac, and 2ag) the reaction mixture was diluted with MTBE or hexane (5 mL) and H2O (4.0 mL). Then organic phase was separated, the aqueous phase was extracted with MTBE (2*5 mL). The combined organic phases were dried over anhydrous Na2SO4. The filtrate was concentrated in rotavapor and the residue was purified by column chromatography on Combiflash with hexanes/EtOAc to afford the desired compounds. The volatile and low yielding products were not isolated and their yields were determined only by 19F NMR of the reaction mixture. For the compounds reported with 19F NMR yields, 4-fluorobenzonitrile (0.50 mmol) was added as reference to the reaction mixture, stirred for 5 min, and then diluted with MTBE or hexane (5 mL) and H2O (3.0 mL). The layers were separated and an an aliquote of the organic phase was withdrawn for the 19F NMR measurement in CDCl3. |