- Formation of a potassium coordination polymer based on a novel 2-sulfono-benzene-1,3,5-tricarboxylic acid: Synthesis, characterization, and application of the organocatalyst in CO2 cycloaddition reaction
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In the present work, a new 3D potassium coordination polymer (1) was prepared by oxidation of sulfonated mesitylene. Its novel sulfono-tricarboxylic ligand, 2-sulfono-benzene-1,3,5-tricarboxylic acid (2), which acted as a structure-directing building block, was successfully synthesized by ion exchange of the potassium coordination polymer (1). The 3D coordination polymer and the sulfonate-carboxylate ligand were characterized by FT-IR and 1H and 13C NMR spectroscopies, and their molecular structures were determined by single-crystal X-ray diffraction. In addition, thermal stability and adsorption/desorption behavior of 1 was investigated by TGA-DTA and N2 adsorption/desorption techniques, respectively. The catalytic activities of the ligand, as a novel and simple organocatalyst, and the rarely explored potassium CPs were studied in the CO2 cycloaddition reaction. The results showed 2 is an efficient organocatalyst in the CO2 cycloaddition process. It is suggested that the synergetic effect among Br?nsted acid COOH, Lewis base I? and free water molecules facilitate this reaction.
- Alavijeh, Masoumeh Karimi,Amini, Mostafa M.,Notash, Behrouz,Mohammadnezhad, Gholamhossein
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- Cornforth and Corey-Suggs reagents as efficient catalysts for sulfonation of aromatic and heteroaromatic compounds using NaHSO3 under solvent free and microwave conditions
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Cornforth and Corey-Suggs reagents Pyridinium Dichromate (PDC) and Pyridinium Chlorochromate (PCC) were explored as efficient catalysts for sulfonation of aromatic and heteroaromatic compounds using NaHSO3 in aqueous acetonitrile medium at room temperature within 1–4 h, while microwave assisted reactions took place within 1–4 min under solvent-free conditions. These observations indicate significant rate accelerations in microwave assisted reactions. which were explained due to the bulk activation of molecules induced by insitu generated high temperatures and pressures when microwaves are transmitted through reaction medium.
- Fatima, Touheeth,Duguta, Govardhan,Purugula, Venkanna,Yelike, Hemanth Sriram,Kamatala, Chinna Rajanna
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p. 1001 - 1006
(2020/07/27)
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- Regioselective Sulfonation of Aromatic Compounds over 1,3-Disulfonic Acid Imidazolium Chloride under Aqueous Media
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1,3-Disulfonic acid imidazolium chloride ([Dsim]Cl), as a Bronsted acidic ionic liquid, is introduced for the sulfonation of aromatic compounds by in situ generation of sulfuric acid at 50 °C under mild conditions and in aqueous medium.
- Moosavi-Zare, Ahmad Reza,Zolfigol, Mohammad Ali,Noroozizadeh, Ehsan
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p. 1682 - 1684
(2016/07/06)
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- Isotope Effects in the Solvolysis of Sterically Hindered Arenesulfonyl Chlorides
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Solvent isotope effects in the ethanolysis of sterically hindered arenesulfonyl chlorides ruled out a proton transfer in the rate-determining step and agreed with a SN2 mechanism involving at least a second solvent molecule in the transition state (TS). The lack of a secondary kinetic isotope effect in the o-alkyl groups allows us to disregard the possible contribution of σ-π hyperconjugation. The measured activation parameters are consistent with a SN2 mechanism involving the participation of solvent molecules in the TS, possibly forming a cyclic TS through a chain of solvent molecules.
- Iazykov, Mykyta,Canle L., Moisés,Santaballa, J. Arturo,Rublova, Ludmila
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p. 744 - 750
(2015/10/06)
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- Formation of the bisulfite anion (HSO3 -, m/z 81) upon collision-induced dissociation of anions derived from organic sulfonic acids
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In the negative-ion collision-induced dissociation mass spectra of most organic sulfonates, the base peak is observed at m/z 80 for the sulfur trioxide radical anion (SO3 -·). In contrast, the product-ion spectra of a few sulfonates, such as cysteic acid, aminomethanesulfonate, and 2-phenylethanesulfonate, show the base peak at m/z 81 for the bisulfite anion (HSO3 - ). An investigation with an extensive variety of sulfonates revealed that the presence of a hydrogen atom at the β-position relative to the sulfur atom is a prerequisite for the formation of the bisulfite anion. The formation of HSO3 - is highly favored when the atom at the β-position is nitrogen, or the leaving neutral species is a highly conjugated molecule such as styrene or acrylic acid. Deuterium-exchange experiments with aminomethanesulfonate demonstrated that the hydrogen for HSO3 - formation is transferred from the β-position. The presence of a peak at m/z 80 in the spectrum of 2-sulfoacetic acid, in contrast to a peak at m/z 81 in that of 3-sulfopropanoic acid, corroborated the proposed hydrogen transfer mechanism. For diacidic compounds, such as 4-sulfobutanoic acid and cysteic acid, the m/z 81 ion can be formed by an alternative mechanism, in which the negative charge of the carboxylate moiety attacks the α-carbon relative to the sulfur atom. Experiments conducted with deuterium-exchanged and deuterium-labeled analogs of sulfocarboxylic acids demonstrated that the formation of the bisulfite anion resulted either from a hydrogen transfer from the β-carbon, or from a direct attack by the carboxylate moiety on the α-carbon. Copyright
- Jariwala, Freneil B.,Wood, Ryan E.,Nishshanka, Upul,Attygalle, Athula B.
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experimental part
p. 529 - 538
(2012/08/28)
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- A novel method for sulfonation of aromatic rings with silica sulfuric acid
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Direct and chemoselective sulfonation of aromatic compounds with silica sulfuric acid in 1,2-dichloeoethane or under solvent-free conditions.
- Hajipour, Abdol R.,Mirjalili, Bi Bi F.,Zarei, Amin,Khazdooz, Leila,Ruoho
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p. 6607 - 6609
(2007/10/03)
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- Nonmonotonic dependences of the activation parameters of hydrolysis of methyl-substituted benzenesulfonyl bromide on the composition of the dioxane-water binary solvent. The effect of hydrophobic interactions
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Pseudo-first-order rate constants and activation parameters (ΔH≠ and ΔS≠) were determined for hydrolysis of 2-CH3- and 2,4,6-(CH3)3-substituted benzenesulfonyl bromide over wide ranges of temperature and compositions of the dioxane-water solvent. The dependences of the activation parameters on the mole fraction of dioxane (X2) are nonmonotonic, like those for the earlier studied hydrolysis of 4-toluenesulfonyl bromide. The X2 values (ranging from 0 to 0.13) corresponding to maximum Δ≠ and ΔS≠ are different for different methyl-substituted benzenesulfonyl bromides. Selective hydrophobic interactions water-sulfonyl bromide make the activation parameters reach maxima at such compositions of the binary solvent that allow each of the substrates to hydrolyze inside an individual quasi-clathrate solvation shell.
- Kislov,Ivanov,Gnedin
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p. 460 - 467
(2007/10/03)
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- Reactivity of sterically hindered aromatic sulfonic acid derivatives: VII.* hydrolysis of arenesulfonyl chlorides in aqueous acetonitrile
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Hydrolysis of sterically hindered arenesulfonyl chlorides in aqueous acetonitrile is accelerated by both electron-acceptor and some electron-donor substituents in the benzene ring. A multifactor kinetic model of the process is proposed. 1998 MAHK Hayka/Interperiodica Publishing.
- Rubleva,Krut'ko,Mitchenko
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p. 1006 - 1009
(2007/10/03)
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- Sulphonyl Transfer Reactions: Solvolysis of Arenesulphonyl Chlorides in Aqueous Trifluoroethanol
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Activation parameters for the solvolysis in aqueous trifluoroethanol of arenesulphonyl chlorides with electron-supplying substituents have been determined; the results are not in accord with earlier proposals that such compounds reacts by an SN1 mechanism.
- Forbes, Rowena M.,Maskill, H.
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p. 854 - 856
(2007/10/02)
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- Limitations of the Transition State Variation Model. Part 2. Dual Reaction Channels for Solvolyses of 2,4,6-Trimethylbenzenesulphonyl Chloride
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Rate constants for solvolyses of 2,4,6-trimethylbenzenesulphonyl chloride (1) are reported for aqueous binary mixtures with acetone, acetonitrile, dioxane, ethanol and methanol.Kinetic solvent isotope effects in water and in methanol and product selectivities in alcohol-water mixtures are also reported.Additional YCl values have been determined for aqueous acetonitrile and dioxane from rate constants for solvolyses of 1-adamantane chloride.Contrary to earlier reports, correlations between logarithms of rate constants for solvolyses of 1 vs.Y or YCl are approximately bilinear.From these plots the rate data are dissected into contributions from two competing reaction channels, and this interpretation is supported for alcohol-water mixtures by the trends of product selectivities, which show maxima close to the solvent compositions where there are breaks in the rate-rate profiles.Greater rate constants for 40 percent v/v ethanol-water than for 97 percent w/w trifluoroethanol-water ( solvents of approximately equal ionizing power) show the importance of nucleophilic solvent assistance (SN2 character) even for the reaction channel favoured in more polar media.Hence, in agreement with an earlier consensus, neither of the reaction channels corresponds to an SN1 mechanism.From the kinetic solvent isotope effect of 1.68 in methanol, it is proposed that the reaction channel favoured in less polar media is general-base catalysed and/or is possibly an addition-elimination pathway.
- Koo, In Sun,Bentley, T. William,Kang, Dae Ho,Lee, Ikchoon
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p. 175 - 179
(2007/10/02)
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- REACTIVITY OF STERICALLY HINDERED DERIVATIVES OF AROMATIC SULFONIC ACIDS II. EFFECTS OF SUBSTRATE STRUCTURE AND MEDIUM POLARITY ON THE HYDROLYSIS OF BENZENESULFONYL CHLORIDES
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The kinetics of the hydrolysis of substituted benzenesulfonyl chlorides XArSO2ClN2 mechanism.
- Vizgert, R. V.,Rubleva, L. I.,Maksimenko, N. N.
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p. 2259 - 2262
(2007/10/02)
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- REACTIVITY OF STERICALLY HINDERED DERIVATIVES OF AROMATIC SULFONIC ACIDS. I. EFFECT OF SUBSTITUENTS ON RATE AND MECHANISM OF HYDROLYSIS OF SOME SUBSTITUTED BENZENESULFONYL CHLORIDES
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The kinetics of the hydrolysis of substituted benzenesulfonyl chlorides XArSO2Cl in 70percent aqueous dioxane at 303, 313, and 323 K were studied by acid-base titration.The effect of the investigated set of substituents cannot be described by a single linear relationship of the Hammett type.The substrates containing methyl groups at the ortho positions of the aromatic ring exhibit enhanced reactivity.The effect of the structural changes in the sulfonyl chlorides on the nature of bond formation and cleavage in the transition state is discussed in terms of the SN2 mechanism.An attempt is made to explain the V-shaped form of the relationship between log k and ? from the standpoint of the hyperconjugation effect, the contribution from which amounts to about 10percent of the ρ value.
- Vizgert, R. V.,Rubleva, L. I.,Maksimenko, N. N.
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p. 727 - 730
(2007/10/02)
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- BIOMIMETIC REDUCTION OF SULFURIC ACID.
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Sulfuric acid and sodium sulfate were readily reduced to elemental sulfur and hydrogen sulfide upon treatment with a mixture of either one of polyphosphoric acid derivatives, PPE, PPA, and P//4O//1//0, which can form a mixed anhydride having -P-O-S- linkage, and iodide or thiol. Sulfur dioxide, which is undoubtedly one of the important intermediates, was trapped by p-tolyllithium to afford p-toluenesulfinic acid which was converted to p-tolyl methyl sulfone upon treatment with methyl iodide, though the yield was low. Sulfur trioxide which has been postulated as the key intermediate in the biological reduction of inorganic sulfate, was also trapped by mesitylene to give mesitylenesulfonic acid in a high yield. The reduction of sulfate to elemental sulfur and hydrogen suylfide is considered to proceed through the course which resembles the biological reaction path involved in the assimilatory metabolism of inorganic sulfate in microorganisms and plants.
- Oae,Togo
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p. 3818 - 3823
(2007/10/02)
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- STUDIEN ZUM VORGANG DER WASSERSTOFFUEBERTRAGUNG.61. Chemische Reaktivitaet und Halbstufenpotential Vergleichende Versuche am Beispiel einiger Arylsulfonsaeurederivate
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In arylsulfonyl halides, the half-wave potentials of the corresponding chlorides and fluorides differ by more than 1000 mV, the fluoride being more negative; the influence of para-substituents is small for the chlorides, large for the fluorides.In agreement with the half-wave potentials, arylsulfonyl chlorides are considerably more reactive chemically than the corresponding fluorides.The O-selectivity found for P(O)F compounds is not observed in arylsulfonyl fluorides.Studies of competitive ester formation using primary and secondary alcohols and various arylsulfonyl chlorides yielded no clear analogy to the half-wave potentials.The primary alcohol is always sulfonated in preference to the secondary alcohol, whether the hydroxy functions are present in different molecules or the same molecule.In the latter case, the secondary hydroxyl function is then attacked in a further step by a second, different, arylsulfonyl chloride, giving the compounds 4-8.The further electroreduction of these diesters may be carried out in high yields, giving selective fission of one ester linkage only (that with the more positive potential) provided the difference in the half-wave potentials of the different ester linkages is sufficiently large.In the electroreductive fission the monosulfinic acid and the corresponding alcohol are liberated (see table II).In the competition reaction between phenol and 1:1 mixtures of tosyl chloride (A) and p-carboxyethyl-benzenesulfonyl chloride (B), the chloride with the more positive potential (B), E1/2=72 mV reacts quicker by a factor of 2.5.In competitive Finkelstein reactions, the selectivity was 1:11 at a difference in half-wave potentials of 760 mV (table IV).Arylsulfonates with free secondary alcohol functions may be oxidized smoothly and in high yield to the corresponding ketone using Na2Cr2O7 (3), without effecting the sulfonate linkage.The alkali hydrolysis of n-hexyl para-substituted arylsulfonates follows the Hammett relation but shows a lesser selectivity than was observed in the electroreductive fission of the same esters at the required potentials.Tables VI, VII and VIII concentrate on the preparative importance of the potential-controlled electroreductive fission of aliphatic and aromatic arylsulfonates.The corresponding hydroxy compounds are liberated in yields of up to over 90percent: N-alkyl- and N-aryl arylsulfonamides give analogous results. (table IX)
- Horner, Leopold,Schmitt, Rolf-Erhard
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p. 189 - 212
(2007/10/02)
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- Kinetics of Protiodeacylation of Mono- and Di-acylmesitylenes in 89.8percent Sulphuric Acid
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Rate and activation data have been obtained for the protiodeacylation in 89.8percent (w/w) sulphuric acid of 10 alkyl mesityl ketones, with straight chain or branched chain alkyl groups, and of four diacylmesitylenes.The reactions have been analysed in terms of a sequence of two or three component ψ-first-order processes.
- Gore, Peter H.,Nassar, Ahmed M. G.,Saad, Esmat F.
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p. 983 - 986
(2007/10/02)
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- Sulfosilylation of Aromatic Hydrocarbons by Trimethylsilyl Chlorosulfonate
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Aromatic hydrocarbons 2 ,6 ,8 ,9 ,13 ,16 ,18 ,19 ,22 react with trimethylsilyl chlorosulfonate (1) to give trimethylsilyl arenesulfonates 5, 7, 11, 12, 15, 23 or sulfonic acids 17, 20, 21.If trimethylsilyl sulfonates are obtained, working up of the sulfonation mixtures is possible by distillation.By hydrohalogenolysis of trimethylsilyl sulfonates 5 at 0-5 deg C anhydrous sulfonic acids 3 result.The pathways to diphenylsulfone (25a) in the reaction of benzene (2a) with 1 were investigated.In this connection we succeeded in synthesizing benzenepyrosulfonic acid (28) and trimethylsilyl benzenepyrosulfonate (29).
- Hofmann, Karin,Simchen, Gerhard
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p. 282 - 297
(2007/10/02)
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- Reactions of overcrowded polymethylbenzenedisulfonic acids in concentrated aqueous sulfuric acid; protiodesulfonation and intramolecular sulfonic anhydride formation
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The reaction of the three tetramethylbenzenedisulfonic acids and some lower homologues in concentrated aqueous sulfuric acid has been studied at 25 deg C. 3,4,5,6-Tetramethylbenzene-1,2-disulfonic acid undergoes both intramolecular disulfonic anhydride formation (the rate of which strongly increases upon increasing the sulfuric acid acidity) and protiodesulfonation (the rate of which decreases slightly with increasing acidity) while the other disulfonic acids only undergo protiodesulfonation.The observed rate order for protiodesulfonation within the tetramethylbenzenedisulfonic acids 1,3- >> 1,4-(SO3H)2> differs strongly from that predicted on the basis of the additivity principle of substituent effects > 1,4- > 1,2-(SO3H)2>.The strongly enhanced reactivity of the 1,2-disulfonic acid is ascribed to a greater releif of steric strain in the 1,2- than in the other disulfonic acids, the sulfo group being more bulky than the methyl.Also, within the group of tri- and tetra-methylbenzene-1,3-disulfonic acids, the rate of desulfonation increases with an increase in the degree of overcrowding around the sulfo group which is desulfonating.Mechanisms for the two types of reaction of the tetramethylbenzenedisulfonic acids are proposed, based on the variation of the rate constants with the sulfuric acid acidity.It is concluded that the substrate entity undergoing protiodesulfanation is the disulfonate dianion and further that the entity undergoing cyclization to the 1,2-disulfonic anhydride is the monoprotonated 1,2-disulfonic acid.
- Koeberg-Telder, Ankie,Cerfontain, Hans
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- Electrophilic Aromatic Substitution. Charge-Transfer Excited States and the Nature of the Activated Complex
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Transient charge-transfer (CT) absorption bands are observed for various benzene derivatives interacting with typical electrophiles, such as the halogens and mercuric trifluoroacetate.The second-order rate constants k for the kinetics of the disappearance of these spectral bands coincide with the rate constants for electrophilic halogenation and mercuration of the aromatic ring.The relative reactivities (log k/k0) of the arenes in electrophilic aromatic substitution are linearly related to the reactive CT transition energies ΔhνCT, using benzene as the reference arene.This remarkable correlation thus relates the transition state for electrophilic aromatic substitution to the CT excited state +E->* of the arene-electrophile pair.Such a direct relationship requires that the solvation energies remain constant for various aromatic cations, since the transition state is attained by an adiabatic process whereas the CT excitation involves a vertical (Franck-Condon) process.Indeed, independent measurements of the cyclic voltammetric peak potentials in acetonitrile and trifluoroacetic acid in comparison with tha gas-phase ionization potentials support the constancy of the solvation terms.The latter provides a ready explanation for the previously puzzling observations that the relative reactivities log k/k0 are insensitive to solvent polarity, yet the absolute rates of electrophilc aromatic substitution are highly dependent.The CT formulation for electrophilic aromatic substitution also provides a physical interpretation of the linear free energy relationship (LFER) which has been established between the ?+ substituent constants and the relative reactivities of arenes.The slope of the LFER correlation ρ is shown to be a measure of the mean separation in the transition state.Other LFER's found between electrophilic aromatic substitution and such parameters as the proton affinities and the ? and the ? basisities of arenes are similarly interpreted.The prediction of the isomeric product distribution resulting from electron-releasing X and electron-withdrawing Y substituents is an important, natural consequence of the CT formulation.It provides unusual insight into the transition from the electron-poor arenes (Ph-Y) producing predominantly meta-substituted products to those (Ph-X) affording the para isomers.
- Fukuzumi, S.,Kochi, J. K.
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p. 7240 - 7252
(2007/10/02)
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- Kinetics of Sulphodeacylation of Dimesityl Ketone: a Dual-path Sequence of First-order Reactions
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The kinetics of the conversion in 89.8percent (w/w) sulphuric acid of 2,2',4,4',6,6'-hexamethylbenzophenone (A) into 2,4,6-trimethylbenzenesulphonic acid (D) were measured, and analysed in terms of the dual-path first-order reaction sequence , where (B) and (C) are, respectively, 2,4,6-trimethylbenzoic acid and 1,3,5-trimethylbenzene.
- Farooqi, Jameel A.,Gore, Peter H.,Saad, Esmat F.,Waters, David N.,Moxon, Gerald F.
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p. 835 - 837
(2007/10/02)
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