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CAS No. : | 1813-33-8 | MDL No. : | MFCD00084939 |
Formula : | C8H3ClF3N | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | GEHMLBFNZKJDQM-UHFFFAOYSA-N |
M.W : | 205.56 | Pubchem ID : | 2736476 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338-P310 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H332-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 |
---|---|---|
With triethylamine;tris(dibenzylideneacetone)dipalladium(0) chloroform complex; copper(l) iodide; DavePhos; at 65℃; for 2h; | Example IA. 2-(3.3 -dimethylbut-1-ynyl)-4-(trifluoromethyl)benzonitrile .Pd2dba3:CHCl3 (0.439 g, 0.424 mmol, 1.5%), dicyclohexylphosrhohino-2'-(N,N- dimethylamino)biphenyl (0.640 g, 1.63 mmol, 6%), and CuI (0.155 g, 0.816 mmol, 3%) were placed in a flask and purged with N2. triethylamine (16 mL) was added and the mixture was stirred for 5 minutes followed by the addition of <strong>[1813-33-8]3-chloro-4-cyanobenzotrifluoride</strong> (4.00 mL, 27.0 mmol) and 3,3-dimethylbutyne (4.00 mmol, 1.2 eq). The mixture was heated under N2 at 65 0C for 2 hours, cooled to ambient temperature and diluted with ethyl acetate (~300 mL). The mixture was washed sequentially with ~2% aqueous NH4OH (120 mL) and saturated aqueous NH4CI (10OmL). The organic layer was dried (Na2SO4), filtered, concentrated, and filtered through SiO2 (~90 mL) with 4% diethyl ether/Hex to provide the title compound. 1H- NMR (CDCl3) delta 7.71-7.75 (m, 2H), 7.58 (dd, IH), 1.37 (s, 9H). | |
With copper(l) iodide; triethylamine;tris-(dibenzylideneacetone)dipalladium(0); DavePhos; at 65℃; for 4h;Inert atmosphere; | To a flask was added Pd2dba3 (0.405 g), DavePhos (0.6884 g, 1.75 mmol), and CuI (0.1655 g). This was purged with nitrogen and degassed; triethylamine (100 mL) was then added. <n="43"/>Benzonitrile (XVII) (36.2 g, 176 mmol) was then added, and the mixture was heated to 65 0C. 3,3-dimethylbutyne (23.7 g, 288 mmol) was then slowly added over 2 hours. The mixture was heated an additional 2 hours, and the heat removed. The mixture was diluted with isopropyl acetate (150 mL) and washed twice with water (150 mL) and twice with 10% aqueous citric acid (150 mL). The organics were diluted with methanol (40 mL), and the volume reduced in vacuo to 60 mL. This was repeated twice with 190 mL methanol, the residual material diluted to 250 g with methanol and used in the next step as a solution. An analytical sample was obtained by removing all the solvent in vacuo.1H NMR (CDCl3, 400 mHz) 7.75 - 7.70 (m, 2H), 7.60-7.55 (m, IH), 1.37 (s, 9H); 13C NMR (CDCl3, 100MHz) 132.6, 128.7, 128.6, 123.8, 123.7, 116.24, 107.96, 75.06, 30.73, 28.64. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 2A. (2-isobutyl-4-(trifluoromethyl)phenyl)methanamine. A solution of 2-methylpropenylmagnesium bromide (0.5 M in THF, 6.0 mL, 3.0 mmol) was added to a solution of ZnCh (1 -0 M in diethyl ether, 3.0 mL, 3.0 mmol) at 00C. The mixture was stirred for 10 minutes cold, and an additional 30 min after removing the cooling bath. 2-chloro-4-trifluoromethyI-benzonitrile (0.35mL, 2.4 mmol) was added, followed by a solution containing Pd2dba3.CHCl3 (48.5 mg, 0.047 mmol) and 2- dicyclohexylphophino-2'-(N,N-dimethylamino)biphenyl (56.3 mg, 0.14 mmol) in THF (1 mL). The mixture was stirred at 60 0C for 3 hours, diluted with ethyl acetate and the resulting mixture washed sequentially with 0.1 N aqueous HCl (2x) and brine (Ix). The organic layer was dried (Na2SO4), filtered and concentrated under reduced pressure, and purified by flash chromatography (5% diethyl ether/hexane) to provide 0.264 g of the nitrile as a clear oil which was used without further purification. The oil was dissolved in 4:1 methanol: ethyl acetate (25 mL), shaken in the presence of 10% Pd/C and Ra Ni (catalytic amounts) under H2 (60 psi) overnight. The mixture was filtered and concentrated under reduced pressure, and the residue purified by flash chromatography (20-100% ethyl acetate in dichloromethane as a gradient elution) to provide the title compound. 1H NMR (CDCl3) delta 7.43-7.52 (m, 2H), 7.37 (brs, IH), 3.94 (brs, 2H), 2.57 (d, 2H), 1.87 (m, IH), 1.49 (brs, 2H), 0.94 (d, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; toluene; for 18h;Heating / reflux; | Example 4A. 2-isopropyl-4-(trifluoromethyl)benzonitrile. To a solution of <strong>[1813-33-8]2-chloro-4-trifluoromethyl-benzonitril</strong>e (0.67mL, 4.5 mmol) and [1,1 '-bisfdiphenylphosphinojferroceneldichloropalladiumtll) (110 mg, 0.14 mmol) in 15 mL of dioxane was added Zn(iso-Propyl)2 (IN in toluene, 9 mmol). The mixture was heated to reflux for 18 hours, cooled to ambient temperature and diluted with methanol. The mixture was further diluted with ether and washed sequentially with IN HCl, water and brine. The organic layer was dried over Na2SO4, filtered, and then concentrated under reduced pressure. The crude product was purified by flash column chromatography (0% to 10% ethyl acetate/hexane) to provide the title compound. 1H NMR (CDCl3) delta 7.73 (d, IH), 7.63 (s, IH), 7.55 (d, IH), 3.45 (sept, IH), 1.36 (d, 6H). |
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