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Structure of 443-82-3
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CAS No. : | 443-82-3 |
Formula : | C8H9F |
M.W : | 124.16 |
SMILES Code : | CC1=C(C)C(F)=CC=C1 |
MDL No. : | MFCD00000323 |
InChI Key : | AWLDSXJCQWTJPC-UHFFFAOYSA-N |
Pubchem ID : | 96489 |
GHS Pictogram: |
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Signal Word: | Danger |
Hazard Statements: | H225 |
Precautionary Statements: | P210-P403+P235 |
Class: | 3 |
UN#: | 1993 |
Packing Group: | Ⅲ |
* 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. |
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 deltaH (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 deltaF (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 |
---|---|---|
54% | With nitric acid; acetic anhydride; at 0℃; for 0.583333h; | Example 16 2- (2, 3-D6hyl-4-nitro-phenylamino} 2-methyl-propan-1-ol Fuming nitric acid (1.4 g, 20.3 mmol) was cooled to 0°C and acetic anhydride (2.89 g, 28.4 mmol) was added. This solution was added to a cold (0°C) solution of 3-fluoro-1, 2- dimethylbenzene (1.0 g, 8.1 mmol) in acetic anhydride (4 ml) over 10 min. The reaction mixture was stirred for 25 min, poured slowly over ice and the water solution extracted with EtOAc (x 3). The collected organic phase was washed with diluted saturated aqueous solution of NaHCO3 followed by brine before evaporation to dryness. The residue was flash purified on a silica gel column using hexane as a mobile phase to give 2, 3-dimethyl-4-fluoro-1-nitro-benzene 0.74 g (54percent) as a yellow oil which crystallised upon standing. The fluoride (0.576 g, 3. 4 mmol) was mixed with 2-amino-2-methylpropanol (0.61 g, 6.8 mmol) in a tube, and the tube was sealed before immersing it into an oil bath and heating at 160°C for 5 days. TLC (Hexane) showed remaining starting material. The reaction mixture was cooled and diluted with EtOAc before purification by flash silica gel chromatography (dry application; 6: 4 hexane and EtOAc) to give 0.34 g (59percent recovery) of the starting material 2, 3-dimethyl-4-fluoro-1-nitro-benzene and 0.20 g (61percent based on recovered starting material) of the 2- (2, 3-dimethyl-4-nitro-phenylamino)-2-methyl- propan-1-ol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; at 60 - 90℃; for 16h; | A solution of 1-fluoro-2, 3-dimethylbenzene (30 g, 0.242 mol) and Bz2O2 (3 g, 0.012 mol) in CCI4 (400 mL) was heated to 600C. NBS (88 g, 0.494 mol) was added portionwise. After the addition, the reaction mixture was heated to 9O0C for 16 h and cooled to room temperature, filtered. The filtrate was concentrated and the residue was purified by column chromatography (eluting with petroleum ether) on silica gel to give pale yellow oil (65 g, 95percent). |
74.9% | With N-Bromosuccinimide; (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate; In tetrachloromethane; at 80℃; for 1h; | A mixture of <strong>[443-82-3]1-fluoro-2,3-dimethylbenzene</strong> (1.00 g, 3.37 mmol), NBS (2.87 g, 16.1 mmol) and BPO (19.5 mg) in CCL1 (50 mL) was stirred at 80°C for 1 h. After cooling down to r.t., and TLC (PE) showed the reaction was complete, the mixture was filtered, the filtrate was concentrated under reduced pressure to get the crude product, which was purified by column chromatography on silica gel (PE) to give the title compound (1.7 g, 74.9percent) as a colorless oil. ?HNMR(CDC13, 400 MHz) oe 7.32-7.26 (m, 1 H) 7.17 (d,J= 7.6 Hz, 1 H) 7.08 - 7.01 (m, 1 H) 4.70 (s, 2 H) 4.63 (s, 2 H). |
70% | With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; at 70℃; for 15h; | [0527] Preparation of Compound 2 (Scheme 16): To a suspension of 1- fluoro-2,3-dimethylbenzene (100 g, 0.81 mmol) in carbon tetrachloride(1.5 L) were added N-bromosuccinimide (288 g, 1.62 mmol), benzoyl peroxide (10 g). Themixture was heated to 70°C. After stirring for 15 h, the mixture was cooled to rt, poured into water (1 L) and extracted with DCM (3xlL). The combined organic layers were purified by flash column chromatography with petroleum ether to give the product 2 (161 g, 70percent) as white solid.TLC: PE/EA = 10/1; Rf (Compound 1) = 1; Rf (Compound 2) = 0.8 |
53% | With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; at 80℃; for 3h; | To a solution of <strong>[443-82-3]1-fluoro-2,3-dimethylbenzene</strong> (37.1, 5 g, 40.3 mmol) in CCl4 (100 mL) was added NBS (15.3 g, 400 mmol) and AIBN (78 mg, 4 mmol). The mixture was allowed to stir at 80 C for 3 h. The reaction was cooled to room temperature and filtered. The crude product was purified by column chromatography (hexane) to afford 1,2-bis(bromomethyl)-3- fluorobenzene (37.2) (6 g, 53percent). |
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; for 1.75h;Heating / reflux; | EXAMPLE 263; l,2-Bis(bromomethvD- 3-fluorobenzene (263):A magnetically stirred mixture of 3-fluoro-o/t/zo-xylene (5.05g, 40.67 mmol), N- bromosuccinimide (15.23g, 85.56 mmol), AIBN (78mg) and CCl4 (75mL) is heated at reflux temperature for 1.75h, then cooled to RT. The solids are removed by filtration and washed with CCl4. The combined filtrate and wash is concentrated in vacuo on a rotary evaporator to give crude dibromide 263 as a yellow liquid that is dissolved in heptane-0.5percent EtOAc, placed atop a column of silica gel (7.2cm x 18cm) prepared in heptane-0.5percent EtOAc and flash chromatographed taking 20OmL fractions eluting with heptane-0.5percent EtOAc. Product containing fractions are combined and concentrated in vacuo on a rotary evaporator to afford a colorless liquid. On standing crystals form in the liquid. The liquid is separated using a pipette. The process is repeated once more. The resulting liquid is pure 1,2 bis(bromomethyl)-3- fluorobenzene. [J. E. Rice, A. Czech, N, Hussain, E. J. La Voie, J. Org. Chem., 53, 1775-1779 (1988) ; R. A. Aitken, P. K.g. Hodgson, M. J. Morrison, A. O. Oyewale, J. Chem. Soc. (Perkin 1), 402-415 (2002)]209 <n="211"/>1H NMR (CDCl3, 300MHz): delta 4.63 (s, 3H), 4.70 (s, 3H), 7.05 (ddd, IH), 7.17 (d, IH), 7.29 (ddd, IH)F NMR (CDCl3, 300MHz): delta 115.26 (d) LC-MS 3.23 (no parent ion)Anal. Calcd. for C8H7Br2F: C, 34.08;H, 2.50; F, 6.74. Found: C, 34.11;H, 2.28; F, 6.88 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With N2; bromine; acetic acid; | A. 3-Fluoro-6-bromo-o-xylene To a 100 mL round-bottomed flask equipped with N2 inlet were added 2.50 mL (20 mmol) <strong>[443-82-3]3-fluoro-o-xylene</strong>, 10 mL acetic acid, and 1.03 mL (20 mmol) bromine. After 12 hours at room temperature, the solution had turned colorless and was poured into water and extracted into petroleum ether. The organic layer was washed with water and 1 N sodium hydroxide solution, dried over sodium sulfate, and evaporated to a liquid, 4 g (100percent), as a mixture of isomers. 1H-NMR (delta, CDCl3): 2.20, 2.25, 2.30, 2.38 (singlets, 6H), 6.78 (t, J=9, 6.8-7.4 (m, 1H). 13C-NMR (delta, CDCl3): 10.6, 10.7, 19.5, 19.6, 112.2, 112.5, 113.7, 113.9, 125.0, 126.1, 130.2, 138.2, 158.9, 160.0, 161.4, 162.4. | |
189 g | With aluminum (III) chloride; bromine; In dichloromethane; at 20 - 30℃; for 0.5h; | 400g of methylene chloride, 124g of <strong>[443-82-3]2,3-dimethylfluorobenzene</strong>, and 5g of aluminum trichloride are added sequentially to a 1L three-necked reaction flask and stirred at 20°C; 16-32 g of bromine was released from a constant pressure dropping funnel containing 160 g of bromine and added to a three-neck reaction flask, then stirred at 30° C to initiate a reaction and produce a large amount of hydrogen bromide to make the reaction solution red. At this point, the remaining bromine in the constant-pressure dropping funnel was further added dropwise to the three-neck reaction flask, stirred at 20° C, after the addition was completed, the reaction was completed for 0.5 hours. After the reaction was completed, the reaction solution subjected to Post-treatment: 50 ml of saturated aqueous sodium sulfite solution was added dropwise to the three-necked reaction solution, remove a small amount of unreacted bromine. At room temperature, the reaction solution gradually became colorless, indicating that the bromine treatment was complete. The three-necked reaction flask liquid was allowed to stand, and the layers were separated into an aqueous phase and an organic phase, and aqueous phase was additionally retained. The organic phase was dried over anhydrous sodium sulfate and then filtered to obtain a filtrate and a cake and filter cake was washed with a little methylene chloride. The resulting liquid phase was combined with the filtrate to obtain an organic phase. The organic phase was concentrated under reduced pressure at 50-55°C to essentially free of liquid, and product 189g was obtained. The hydrogen bromide gas generated during the reaction was led through a pipe connected to a three-necked reaction flask and led to an exhaust gas absorption treatment system where it was absorbed by an aqueous solution of sodium hydroxide. The GC spectrum is shown in Fig. 2. In Fig. 2, 6.8 min was <strong>[443-82-3]2,3-dimethylfluorobenzene</strong> raw material , 3.8 min was 3-bromo-6-fluoro-o-xylene, and 8.9min is the reaction product of ortho-substituted by-products, The data calculation results show: The purity of the product was 88.4percent, the by-reaction product was very small (about 3.3percent), and the remainder was mainly raw, and the calculated yield was 87percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With HF; | Example 2 1-Fluoro-2,3-dimethylbenzene The reaction was carried out using the method of Example 1, except that 220 g of 2,3-dimethylphenyl chloroformate, 500 ml of 1,2,4-trichlorobenzene and 600 ml of HF were heated to 140° C. and the gases formed were released at 2.8*106 Pa. Yield: 113 g (76percent of theory) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | EXAMPLE 4 2-(2-Fluoro-3,4-dimethylbenzoyl)-5-nitrothiazole Analogously to Example 1, 5-nitrothiazole-2-carboxylic acid chloride and <strong>[443-82-3]1-fluoro-2,3-dimethylbenzene</strong> are reacted with each other. Yield: 60percent; m.p. 139°-141° C. (methanol/chloroform). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
...presented by the following formula (4) which can respectively correspond to the formula (1) can be obtained.(D) Fluorine substituted aromatic compound represented by the formula (4) corresponding to the hydroxy compound wherein X1 is a substituent of the group (a) in the formula(1):2-methylfluorobenzene, 3-methylfluorobenzene, 4-methylfluorobenzene,2-ethylfluorobenzene, 3-ethylfluorobenzene, 4-ethylfluorobenzene,2,3-dimethylfluorobenzene, 2,4-dimethylfluorobenzene,2,5-dimethylfluorobenzene, 2,6-dimethylfluorobenzene,3,4-dimethylfluorobenzene, 3,5-dimethylfluorobenzene,2-methoxyfluorobenzene, 3-methoxyfluorobenzene,4-methoxyfluorobenzene, 2-ethoxyfluorobenzene,3-ethoxyfluorobenzene, 4-ethoxyfluorobenzene,2,3-dimethoxyfluorobenzene, 2,6-dimethoxyfluorobenzene,... |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
3-Fluoro-o-xylene (5.7 g, 46 mmol) was added to a round-bottom flask with a stir bar and dissolved in 150 mL dichloroethane. N-Bromosuccinimide (33.1 g, 186 mmol) and a small scoop of AIBN (2,2'-azobis(2-methylpropionitrile)) were added, a reflux condenser was attached, and the mixture was refluxed for 6 hr until analysis by GC-MS indicated that the primary product was the tribrominated adduct. After cooling, water and dichloromethane were added, and the organic layer was separated, then washed with water and dilute hydrochloric acid, dried over magnesium sulfate, and rinsed through a thin pad of silica gel using dichloromethane. Removal of solvent yielded 16.1 g of the product mixture. To a 100 mL round-bottom flask equipped with a condenser and stir bar, 12 mL dimethylformamide was added, followed by 1.1 g (-4.1 mmol) of the tribrominated product from above and 0.22 g (2.0 mmol) benzoquinone. Nitrogen was bubbled through the solution for 20 minutes, then 2.1 g (12 mmol) potassium iodide was added, and the reaction was heated at HO0C for 3 days. The reaction was allowed to cool and the precipitate was collected by filtration, then rinsed sequentially with water, acetone and diethyl ether. The resulting solid was air-dried, yielding 0.15 g (0.42 mmol, 21percent) of an isomer mixture of difluoropentacenequinone as a light brown solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | 3-Fluoro-o-xylene (1.2 g, 9.7 mmol) was added to a round-bottom flask with a stir bar and dissolved in 30 mL dichloroethane. N-Bromosuccinimide (7.0 g, 39 mmol) and a small scoop of AIBN (2,2'-azobis(2-methylpropionitrile)) were added, a reflux condenser was attached, and the mixture was refluxed for 6 hr, at which point analysis by GC-MS showed the predominant component to be the tribrominated product. After cooling, water and dichloromethane were added, and the organic layer was separated, then washed with water and dilute hydrochloric acid, dried over magnesium sulfate, and rinsed through a thin pad of silica gel using dichloromethane as an eluent. Removal of solvent yielded 3.4 g of the product mixture. To a 100 mL round-bottom flask equipped with a condenser and stir bar, 12 mL dimethylformamide was added, followed by 0.54 g (2.07 mmol) of the tribrominated product from above and 0.43 g (2.1 mmol) 1,4-anthraquinone. Nitrogen was bubbled through the solution for 20 minutes, then 2.1 g (12 mmol) potassium iodide was added, and the reaction was heated at HO0C for 3 days. The reaction was allowed to cool and the precipitate was collected by filtration, then rinsed sequentially with water, acetone and diethyl ether. The resulting solid was air-dried, yielding 0.29 g (0.88 mmol, 42percent) of 1-fluoropentacenequinone as a light brown solid. | |
42% | Example 19 - Synthesis of 6,13-Bis(3,3,4,4,5,5,6,6,6-nonafluorohexyldiisopropyl- silylethynyl)- 1 -fluoropentaceneSynthesis of l-Fluoropentacene-6,13-dione3-Fluoro-o-xylene (1.2 g, 9.7 mmol) was added to a round-bottom flask with a stir bar and dissolved in 30 mL dichloroethane. N-Bromosuccinimide (7.0 g, 39 mmol) and a small scoop of AIBNu were added, a reflux condenser was attached, and the mixture was refluxed for 6 hr, at which point analysis by GC-MS showed the predominant component to be the tribrominated product. After cooling, water and dichloromethane were added, and the organic layer was separated, then washed with water and dilute hydrochloric acid, dried over MgSO4, and rinsed through a thin pad of silica gel using dichloromethane as an eluant. Removal of solvent yielded 3.4 g of a product mixture. To a 100 mL round-bottom flask equipped with a condenser and stir bar, 12 mL dimethylformamide was added, followed by 0.54 g (2.07 mmol) of the tribrominated product from above and 0.43 g (2.1 mmol) 1,4- anthraquinone. Nitrogen was bubbled through the solution for 20 minutes, then 2.1 g (12 mmol) potassium iodide was added, and the reaction was heated at H0°C for 3 days. The reaction was allowed to cool, and the precipitate was collected by filtration, then rinsed sequentially with water, acetone and diethyl ether. The resulting solid was air-dried, yielding 0.29 g (0.88 mmol, 42percent) of l-fluoropentacene-6,13-dione (or 1-fluoropentacenequinone) as a light brown solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
19% | With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; | Step Atert-butyl (4-fluoro-1,3-dihydro-2H-isoindol-2-yl)methylcarbamate3-Fluoro-ortho-xylene (1.99 g, 16.03 mmol), N-bromosuccinimide (6.98 g, 39.22 mmol) and benzoyl peroxide (0.24 g) were added to carbon tetrachloride (60 ml), and the mixture was heated under reflux for 45 min.The reaction mixture was cooled, diluted with hexane, and the insoluble material was filtered off.The obtained solution was concentrated under reduced pressure.Using the obtained oil, the reaction was performed according to the method of Reference Example 17, step B.After completion of the reaction, 10percent aqueous citric acid solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate-hexane=1:1 mixed solvent, washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over anhydrous magnesium sulfate.The insoluble material was filtered off, and the solution was concentrated under reduced pressure.The obtained oil was purified by silica gel column chromatography (ethyl acetate-hexane) to give the title compound (826 mg, yield 19percent) as a pale-yellow oil.1H-NMR (300 MHz, CDCl3); delta(ppm) 1.41 (s, 9H), 3.09 (s, 3H), 4.47 (s, 2H), 4.48 (s, 2H), 6.87 (t, J=8.6, 1H), 6.94 (d, J=7.2, 1H), 7.1-7.2 (m, 1H). |
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. |
Tags: 443-82-3 synthesis path| 443-82-3 SDS| 443-82-3 COA| 443-82-3 purity| 443-82-3 application| 443-82-3 NMR| 443-82-3 COA| 443-82-3 structure
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Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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