- Synthesis of α-(trifluoromethyl)phenylacetonitrile. Anomalous reactions of α-tosyloxy-α-(trifluoromethyl)phenylacetonitrile with sodium borohydride
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The hitherto unknown α-(trifluoromethyl)phenylacetonitrile has been synthesized by reduction of the cyanohydrin of α,α,α-trifluoroacetophenone.Sodium borohydride reduction of the corresponding cyanohydrin tosylate resulted in reductive decyanation in dimethyl sulphoxide and in reduction of the nitrile group in t-butanol. - Keywords: Synthesis; α-(Trifluoromethyl)phenylacetonitrile; Anomalous reactions; Sodium borohydride; NMR spectroscopy; IR spectroscopy, Mass spectrometry
- Nemeth, Gabor,Poszavacz, Laszlo,Bozsing, Daniel,Simig, Gyula
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- Monofluorovinyl tosylate: A useful building block for the synthesis of terminal vinyl monofluorides via suzuki-Miyaura coupling
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Monofluorovinyl tosylate was developed as a practical vinyl fluoride building block to couple with a variety of arylboronic acids in the presence of a palladium catalyst. The high stereoselectivity of 2-aryl-1-fluoroethene derivatives was achieved. This a
- Zhang, He,Zhou, Chang-Bing,Chen, Qing-Yun,Xiao, Ji-Chang,Hong, Ran
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p. 560 - 563
(2011/04/23)
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- Profiling sulfonate ester stability: Identification of complementary protecting groups for sulfonates
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(Figure presented) Sulfonation is prized for its ability to impart water-solubility to hydrophobic molecules such as dyes. This modification is usually performed as a final step, since sulfonated molecules are poorly soluble in most organic solvents, which complicates their synthesis and purification. This work compares the intrinsic lability of different sulfonate esters, identifying new sulfonate protecting groups and mild, selective cleavage conditions.
- Miller, Stephen C.
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supporting information; experimental part
p. 4632 - 4635
(2010/09/17)
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- Solvolysis of 1-Aryl-2,2,2-trifluoroethyl Sulfonates. Kinetic and Stereochemical Effects in the Generation of Highly Electron-Deficient Carbocations
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Solvolysis rates of sulfonates XC6H4CH(O3SR)CF3 (R = p-Tol or CF3) correlate with ?+(X) with values of ρ+ between -6.7 and -11.9 depending upon solvent.For the tosylates the rates depend on the solvent parameter YOTs with
- Allen, Annette D.,Ambidge, I. Christopher,Che, Claudius,Micheal, Hany,Muir, Ronald J.,Tidwell, Thomas T.
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p. 2343 - 2350
(2007/10/02)
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- Proton-Transfer Reactions. 2. Effects of Internal Return on Reactivity Difference between Alkoxide-Promoted Eliminations in tert-Butyl alcohol and Ethyl Alcohol
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Kinetics of alkoxide-promoted dehydrofluorination reactions are reported for the series C6H5CH2CH2F (I), C6H5CH2CHF2 (II), C6H5CH2CF3 (III), and C6H5CH2CF2CF3 (V).Rates and activation parameters 3 (M-1 s-1)(50 deg C), ΔH* (kcal mol-1), and ΔS*, (eu)> are respectively: (a) using potassium tert-butoxide in tert-butyl alcohol, I (1.88 * 10-4, 19.1, -16.8), II (1.18 * 10-3, 20.3, -9.3), III (2.15 * 10-3, 22.1, -2.4), V (3.93 * 10-2, 16.9, -12.7); and (b) using sodium ethoxide in ethanol, I (1.32 * 10-6, 25.6, -6.5), II (5.28 * 10-7, 29.7, 3.0), III (3.45 * 10-7, 32.6, 12.5), V (5.41 * 10-5, 27.7, 7.6).The variation in tert-butoxide:ethoxide ratios of 140 (I), 2200 (II), 6200 (III), and 730 (V) are discussed in terms of a two-step mechanism with varying amounts of internal return for II, III, and V.Differences in reactivity for groups attached to the benzylic carbon (-CF3, -CF2Cl, -CHF2, -CF2CF3) and variation of ΔS* values for these reactions are also discussed in terms of a two-step mechanism.
- Koch, H. F.,Tumas, W.,Knoll, R.
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p. 5423 - 5429
(2007/10/02)
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