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CAS No. : | 130723-13-6 | MDL No. : | MFCD00042498 |
Formula : | C7H3BrF4 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | LIGBGEJPUQBLTG-UHFFFAOYSA-N |
M.W : | 243.00 | Pubchem ID : | 2736323 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
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 |
---|---|---|
81% | With triethylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; at 20 - 80℃; for 24h; | 6-(3-Fluoro-5-trifluoromethylphenyl)-hex-5-ynoic Acid Methyl Ester (41). Pd(PPh3)2Cl2 (236 mg, 0.336 mmol) was added to a mixture of bromide 38 (1.677 g, 6.70 mmol) and methyl 5-hexynoate (1.025 g, 8.12 mmol) in triethylamine (5.0 mL) at room temperature. Cu(I)I (136 mg, 0.714 mmol) was added. The resulting mixture was stirred at room temperature for 1.5 h and at 80 C. for 22.5 h. The reaction mixture was cooled to room temperature, filtered through a short column of silica gel (5 g), and the column was washed with ethyl acetate. The organic solution was concentrated. The residue was purified by column chromatography on silica gel (40 g), eluting with EtOAc-hexanes (2%) to afford the product 41 (1.564 g) as a white solid in 81% yield: mp 44-45 C. IR (KBr) 3084, 2955, 2848, 2238, 1740, 1619, 1599, 1467, 1439, 1363, 1253, 1240, 1224, 1171, 1133, 1093, 1046, 995, 973, 924, 911, 875, 695 cm-1; 1H NMR (300 MHz, CDCl3) delta 7.40 (s, 1H), 7.21 (m, 2H), 3.66 (s, 3H), 2.47 (t, J=7.2 Hz, 4H), 1.90 (m, 2H); 13C NMR (75 MHz, CDCl3) delta 173.3, 163.7, 160.4, 132.8, 132.3, 126.8, 126.7, 124.7, 124.3, 121.8, 121.5, 112.3, 111.9, 79.1, 51.6, 32.7, 23.5, 18.7; ESIMS m/z (rel intensity) 288.96 (MH+, 51). Anal. (C14H12F4O2) C, H, F. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | 2-(3-Fluoro-5-trifluoromethyl-phenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane The title compound was obtained according to example 342 as a colorless oil (48% yield) using <strong>[130723-13-6]3-bromo-5-fluorobenzotrifluoride</strong> and bis(pinacolato)diboron as the starting materials MS: m/e=290 (M+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran; water; dimethyl sulfoxide; | 1-(3-Bromo-5-trifluoromethyl-phenyl)-piperazine A solution of <strong>[130723-13-6]1-bromo-3-fluoro-5-(trifluoromethyl)-benzene</strong> (100 g, 0.41 moles), piperazine (194.9 g, 2.26 moles) in DMSO (800 ml) was heated at 100 C. for 5 hours, cooled at room temperature and stirred overnight. The mixture was poured into water and the yellow solid which separeted was filtered. The solid was suspended in a 5% THF solution in water (300 ml) water/THF, stirred for 1 hour and filtered again. 120 g, light beige solid, m.p. 74-77 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | In para-thiocresol; | The 4-[3-(4-(2-cyanoprop-2-yl)phenylthio)-5-trifluoromethylphenyl]-4-hydroxytetrahydropyran used as a starting material was obtained as follows: Using a similar procedure to that described in the 1st paragraph of Note a. above 4-toluenethiol was reacted with <strong>[130723-13-6]1-bromo-3-fluoro-5-trifluoromethylbenzene</strong> to give 3-bromo-5-trifluoromethylphenyl 4-tolyl sulphide in 63% yield as an oil. |
63% | In para-thiocresol; | The 4-[3-(4-(2-cyanoprop-2-yl)phenylthio)-5-trifluoromethylphenyl]-4-hydroxytetrahydropyran used as a starting material was obtained as follows:- Using a similar procedure to that described in the 1st paragraph of Note a. above 4-toluenethiol was reacted with <strong>[130723-13-6]1-bromo-3-fluoro-5-trifluoromethylbenzene</strong> to give 3-bromo-5-trifluoromethylphenyl 4-tolyl sulphide in 63% yield as an oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | In 2,4-dichlorophenoxyacetic acid dimethylamine; mineral oil; | The 4-hydroxy-4-[3-(naphth-2-ylthio)-5-trifluoromethylphenyl]tetrahydropyran used as a starting material was obtained as follows: Sodium hydride (60% w/w dispersion in mineral oil; 0.5 g) was added portionwise to a mixture of 2-naphthalenethiol (1.42 g) and DMA (30 ml) and the mixture was stirred at ambient temperature for 1 hour. A solution of <strong>[130723-13-6]1-bromo-3-fluoro-5-trifluoromethylbenzene</strong> (2.43 g) in DMA (10 ml) was added and the mixture was stirred at ambient temperature for 16 hours. The mixture was partitioned between ethyl acetate and water. The organic layer was washed with brine (50 ml), dried (MgSO4) and evaporated. The residue was purified by column chromatography using hexane as eluent. There was thus obtained 3-bromo-5-trifluoromethylphenyl 2-naphthyl sulphide (1.37 g, 40%), as an oil. A solution of the product so obtained in THF (10 ml) was cooled to -60 C. and n-butyl-lithium (1.6M in hexane; 2.3 ml) was added dropwise. |
40% | In 2,4-dichlorophenoxyacetic acid dimethylamine; mineral oil; | The 4-hydroxy-4-[3-(naphth-2-ylthio)-5-trifluoromethylphenyl]tetrahydropyran used as a starting material was obtained as follows:- Sodium hydride (60% w/w dispersion in mineral oil; 0.5 g) was added portionwise to a mixture of 2-naphthalenethiol (1.42 g) and DMA (30 ml) and the mixture was stirred at ambient temperature for 1 hour. A solution of <strong>[130723-13-6]1-bromo-3-fluoro-5-trifluoromethylbenzene</strong> (2.43 g) in DMA (10 ml) was added and the mixture was stirred at ambient temperature for 16 hours. The mixture was partitioned between ethyl acetate and water. The organic layer was washed with brine (50 ml), dried (MgSO4) and evaporated. The residue was purified by column chromatography using hexane as eluent. There was thus obtained 3-bromo-5-trifluoromethylphenyl 2-naphthyl sulphide (1.37 g, 40%), as an oil. A solution of the product so obtained in THF (10 ml) was cooled to -60C and n-butyl-lithium (1.6 M in hexane; 2.3 ml) was added dropwise. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With iodine; magnesium; In tetrahydrofuran; water; | Step A Synthesis of 3-fluoro-5-trifluoromethylphenylboronic acid as an intermediate A crystal of iodine and 0.5 gram (0.021 mole) of magnesium turnings were placed in a reaction vessel containing 10 mL of tetrahydrofuran. To this was added dropwise 2 mL of a solution of 5.0 grams (0.021 mole) of <strong>[130723-13-6]3-fluoro-5-trifluoromethylphenyl bromide</strong> in 65 mL of tetrahydrofuran. The Grignard formation was initiated by warming the reaction vessel to about 45 C. The remaining <strong>[130723-13-6]3-fluoro-5-trifluoromethylphenyl bromide</strong>--tetrahydrofuran solution was added portionwise at a rate which maintained gentle reflux of the reaction mixture. In a second reaction vessel, 40 mL of tetrahydrofuran was cooled to -78 C., and 2.3 mL (0.021 mole) of trimethyl borate was added dropwise as the Grignard reagent of <strong>[130723-13-6]3-fluoro-5-trifluoromethylphenyl bromide</strong> prepared above was transferred into the second reaction vessel using a cannula. The temperature of the reaction mixture was maintained below -60 C. during the additions. Upon completion of the additions, the reaction mixture was again cooled to -78 C., where it was stirred for about 45 minutes. After this time, the reaction mixture was allowed to warm to ambient temperature. The reaction mixture was then poured into about 200 mL of water and was made acidic with aqueous 5% hydrochloric acid. The mixture was extracted with four 100 mL portions of ethyl acetate. The combined extracts were dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, yielding 3.3 grams of 3-fluoro-5-trifluoromethylphenylboronic acid, mp 167-168 C. The NMR spectrum was consistent with the proposed structure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With magnesium; In tetrahydrofuran; water; | Step A Synthesis of 3-fluoro-5-trifluoromethylphenylboronic acid as an intermediate A crystal of iodine and 0.5 gram (0.021 mole) of magnesium turnings are placed in a reaction vessel containing 10 mL of tetrahydrofuran. To this is added dropwise 2 mL of a solution of 5.0 grams (0.021 mole) of <strong>[130723-13-6]3-fluoro-5-trifluoromethylphenyl bromide</strong> (commercially available) in 65 mL of tetrahydrofuran. The Grignard formation is initiated by warming the reaction vessel to about 45 C. The remaining <strong>[130723-13-6]3-fluoro-5-trifluoromethylphenyl bromide</strong>-tetrahydrofuran solution is added portionwise at a rate which maintained gentle reflux of the reaction mixture. In a second reaction vessel, 40 mL of tetrahydrofuran is cooled to -78 C., and 2.3 mL (0.021 mole) of trimethyl borate is added dropwise as the Grignard reagent of <strong>[130723-13-6]3-fluoro-5-trifluoromethylphenyl bromide</strong> prepared above is transferred into the second reaction vessel using a cannula. The temperature of the reaction mixture is maintained below -60 C. during the additions. Upon completion of the additions, the reaction mixture is again cooled to -78 C., where it is stirred for about 45 minutes. After this time, the reaction mixture is allowed to warm to ambient temperature. The reaction mixture is then poured into about 200 mL of water and is made acidic with aqueous 5% hydrochloric acid. The mixture is extracted with four 100 mL portions of ethyl acetate. The combined extracts are dried with magnesium sulfate and filtered. The tiltrate is concentrated under reduced pressure, yielding 3.3 grams of 3-fluoro-5-trifluoromethylphenylboronic acid, mp 167-168 C. The NMR spectrum is consistent with the proposed structure. |
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