- Nucleophilic Aromatic Substitution. Part XV. Phase-Transfer Catalysis of Sulfodechlorination and Identification of a Primary Product of Sulfite Ion with 1-Chloro-2,4-dinitrobenzene
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With conventional phase-transfer catalysis using quaternary ammonium salts, yields of 2,4-dinitrobenzenesulfonic acid (2) in the sulfodechlorination of 1-chloro-2,4-dinitrobenzene (1) with sulfite ions are no better than those obtained with the classical method in aqueous ethanol (80-82percent).Yields up to 97percent and a very pure product are obtained, however, by using protonated tertiary amines as catalysts.The optimum chain-lenght of the amine is found with tributylamine.On mixing solutions of the reagents and catalysts a strong bluish-red colour develops immediately, but dis appears within ca. 1 h.Comparison of the NMR. spectrum of this primary product with model adducts of sulfite ions and di- and trinitrobenzene derivatives demonstrates that the primary addition of the nucleophile to 1-chloro-2,4-dinitrobenzene does not take place at C(1), but at C(5).It is shown that the increments calculated for a C(sp3)-SO3- group and for the 1,3-dinitro- and 1,3,5-trinitropentadienyl ring moieties can be employed for the approximate calculation of 1H-chemical shifts using Clerc and Pretschs's modification of the Shoolery rules.
- Bunnett, Joseph F.,Gisler, Markus,Zollinger, Heinrich
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- SULFONATE COMPOUND AND FLUORESCENT PROBE USING THE SAME
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The present invention provides a sulfonate compound, including a structure represented by a general formula (I) below, where, in the formula (I), an atomic group A-O is an atomic group that forms a fluorescent compound upon cleavage of a covalent bond between the atomic group A-O and a sulfonyl group, one or a plurality of atomic groups B-SO3- are bonded to an atomic group A, B is a ring that is substituted by one or a plurality of electron-withdrawing groups, the electron-withdrawing group is at least one selected from the group consisting of an alkyl halide group, a nitro group and a cyano group, and B may be the same or different in kind in the case where the plurality of B exist.
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(2008/06/13)
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- SYNTHESIS OF TETRAPHENYLSTIBONIUM ALKYL- AND ARYLSULPHONATES. CRYSTAL STRUCTURE OF TETRAPHENYLSTIBONIUM BENZENESULPHONATE HYDRATE
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The tetraphenylstilbonium sulphonates Ph4SbO3SR*nH2O (n = 1, R = C6H5; n = 0, R = CH3, CF3, CH2CH2OH, 4-CH3C6H4, 2,4-(NO2)2C6H3) have been obtained by neutralization of tetraphenylstibonium hydroxide with the appropriate alkyl- or aryl-sulphonic acid.The crystal structure of tetraphenylstibonium benzenesulfonate hydrate has been determined by single crystal X-ray diffraction.The sulphonate group is unidentately coordinated to antimony, which has a distorted trigonal bipyramidal environment.The rather long Sb-O bond, (2.506(4) Angstroem) and the distortion of the polyhedron around Sb, and the IR data for the sulphonate group are consistent with the assumption of a large ionic bond character in the Sb-O bond.From IR data analogous molecular structures are inferred for the other tetraphenylstibonium sulphonates.
- Ruether, Robert,Huber, Friedo,Preut, Hans
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