- Selective Late-Stage Sulfonyl Chloride Formation from Sulfonamides Enabled by Pyry-BF4
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Reported here is a simple and practical functionalization of primary sulfonamides, by means of a pyrylium salt (Pyry-BF4), with nucleophiles. This simple reagent activates the poorly nucleophilic NH2 group in a sulfonamide, enabling the formation of one of the best electrophiles in organic synthesis: a sulfonyl chloride. Because of the variety of primary sulfonamides in pharmaceutical contexts, special attention has been focused on the direct conversion of densely functionalized primary sulfonamides by a late-stage formation of the corresponding sulfonyl chloride. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides, sulfonates, sulfides, sulfonyl fluorides, and sulfonic acids. The mild reaction conditions and the high selectivity of Pyry-BF4 towards NH2 groups permit the formation of sulfonyl chlorides in a late-stage fashion, tolerating a preponderance of sensitive functionalities.
- Gómez-Palomino, Alejandro,Cornella, Josep
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supporting information
p. 18235 - 18239
(2019/11/13)
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- DSD acid preparation method
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The invention relates to the field of chemical synthesis, in particular to a DSD acid preparation method. The DSD acid preparation method includes the steps that methylbenzene is subjected to sulfonation, purification and separation to obtain OTS, wherein the byproduct is PTS; OTS is subjected to mixed acid nitration to obtain PNTS; PNTS is subjected to chlorine oxidative condensation to obtain DNS; DNS is subjected to catalyzed hydrogeneration reduction to obtain the high-quality target product, namely DSD acid which can be directly used for synthesizing a fluorescent whitening agent. The synthesis method greatly reduces dangerousness of the process, greatly reduces generation of harmful byproducts and waste, particularly, does not generate a lot of carcinogenic intermediate, namely ortho-nitrotoluene, completely solves the nitration safety problem of the old technology, and has the advantages of being simple in step, high in yield and the like.
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Paragraph 0069; 0070
(2017/11/03)
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- Architectural diversity and elastic networks in hydrogen-bonded host frameworks: From molecular jaws to cylinders
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Guest-free guanidinium organomonosulfonates (GMS) and their inclusion compounds display a variety of lamellar crystalline architectures distinguished by different "up-down" projections of the organomonosulfonate residues on either side of a two-dimensional (2D) hydrogen-bonding network of complementary guanidinium ions (G) and sulfonate moieties (S), the so-called GS sheet. Using a combinatorial library of 24 GMS hosts and 26 guest molecules, a total of 304 inclusion compounds out of a possible 624 possible host-guest combinations were realized, revealing a remarkable capacity of the GMS hosts to form inclusion compounds despite the facile formation of the corresponding guest-free compounds and the absence of "predestined" inclusion cavities like those in related guanidinium organodisulfonate host frameworks. The GS sheets in the inclusion compounds behave as "molecular jaws" in which organomonosulfonate groups projecting from opposing sheets clamp down on the guest molecules, forming ordered interdigitated arrays of the host organic groups and guests. Both the guest-free and inclusion compounds display a variety of architectures that reveal the structural integrity of two-dimensional GS sheet and the unique ability of these hosts to conform to the steric demands of the organic guests. Certain GMS host-guest combinations prompt formation of tubular inclusion compounds in which the GS sheet curls into cylinders with retention of the 2D GS network. The cylinders assemble into hexagonal arrays through interdigitation of the organosulfonate residues that project from their outer surfaces, crystallizing in high-symmetry trigonal or hexagonal space groups. This unique example of network curvature and structural isomerism between lamellar and cylindrical structures, with retention of supramolecular connectivity, is reminiscent of the phase behavior observed in surfactant microstructures and block copolymers. The large number of host-guest combinations explored here permits grouping of the inclusion compound architectures according to the shape of the guests and the relative volumes of the organomonosulfonate groups, enabling more reliable structure prediction for this class of compounds than for molecular crystals in general.
- Horner, Matthew J.,Holman, K. Travis,Ward, Michael D.
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p. 14640 - 14660
(2008/09/18)
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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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- Clean-chemistry sulfonation of aromatics
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A solution of TFAA/H2SO4 is an atom-efficient liquid-phase system for rapid sulfonation of aromatic structures; H2SO4 is consumed stoichiometrically and the spent trifluoroacetic anhydride (TFAA) is readily recovered as trifluoroacetic acid (TFA) which can be recycled to TFAA.
- Corby, Brian W.,Gray, Anthony D.,Meaney, Padraig J.,Falvey, Michael J.,Lawrence, Gregory P.,Smyth, Timothy P.
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p. 326 - 327
(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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- Phenylthio-derivatives of α-methylene-γ-lactones as pro-drugs of cytotoxic agents
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A series of substituted phenylthio-derivatives of grosheimin (1), a natural cytotoxic guaianolide, were investigated with the aim of providing insight into their mechanism of action as cytotoxic agents against KB cell lines. Hydrolysis data, kinetics, in the presence and in the absence of H2O2, and the valuation of lipophilicity were correlated with cytotoxicity values and with Hammett-σ-values of substituents (R) at the thiophenol ring. These compounds behave as 'pro-drugs' which release the cytotoxic agent grosheimin by sulphur-oxidation promoted by H2O2 and subsequent retro- elimination which depends on the nature and position of the R substituent.
- Fardella, Giuseppe,Barbetti, Paolo,Grandolini, Giuliano,Chiappini, Ione,Ambrogi, Valeria,Scarcia, Vito,Furlani Candiani, Ariella
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p. 515 - 523
(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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- Sulfonating agent and sulfonation process
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A sulfonating agent represented by the general formula STR1 wherein the groups R1 are the same or different and are each a lower alkyl group having 1 to 3 carbon atoms, n is an integer of 3, 4 or 5, m is an integer of 1 or 2, and n+m≤6, and a process for sulfonating an aromatic compound with use of the sulfonating agent.
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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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- KINETICS AND MECHANISM OF HYDROLYSIS OF AROMATIC SULFONYL CHLORIDES IN AQUEOUS SULFURIC ACID SOLUTIONS
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The kinetics of the hydrolysis of 12 aromatic sulfonyl chlorides were studied by a spectrophotometric method in water and aqueous sulfuric acid solutions ( 1.0 - 60.5 wt.percent ) at 25 deg C and in 50percent sulfuric acid at several temperatures.It was shown that the reaction obeys the single-parameter equation log keff = log k0 + m'X, in which keff and k0 are the first-order rate constants in a solution with "excess acidity" X and in water respectively.The coefficient m' depends on the substituent in the ring and is equal to -0.85 to -0.38.The activity of the water does not enter into the equation for the calculation of keff.For the hydrolysis of nine substituted sulfonyl chlorides in 50percent sulfuric acid a satisfactory correlation is observed between log keff and the Σ?0.Palm induction constants ( ρ = -1.85 +/- 0.12 ).A reaction mechanism is proposed in which the rate-determining stage in the hydrolysis of the ArSO2Cl is the transformation of the complex H2O...SO2(Cl)Ar, in the form of which all the sulfonyl chloride dissolved in the water is present, into the reaction products.
- Gnedin, B. G.,Ivanov, S. N.,Shchukina, M. V.
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p. 731 - 737
(2007/10/02)
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- Acid-catalyzed hydrolysis of benzenesulfonamides. Rate enhancements by ortho-alkyl substituents
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Pseudo-first-order rate constants have been measured for the acid-catalyzed hydrolysis of a series of N,N-dimethyl- and N-methyl-N-phenylbenzenesulfonamides in 70 percent (v/v) CF3CO2H/H2O at 99 deg C.Analysis of the effect of the alkyl substituents in the benzene ring shows a remarkable rate enhancement by ortho-alkyl groups, in the contrast with a rate retardation of similar substituents in the corresponding benzamides.The rate enhancement in the sulfonamides is attributed to relief of initalstate strain in the transition state for hydrolysis.When the sulfonamide moiety is contained in a five-membered ring fused to a phenyl ring, the rate of hydrolysis is markedly reduced by an ortho-methyl substituent.
- Wagenaar, Anno,Kirby, Anthony J.,Engberts, Jan B. F. N.
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p. 203 - 205
(2007/10/02)
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- HYDROLYSIS OF AROMATIC SULFONIC ACIDS UNDER THERMODYNAMIC CONTROL OF THE REACTION
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Linear mathematical models which describe the hydrolysis of alkyl- and halobenzenesulfonyl acids under the conditions for their isomerization in sulfuric acid have been obtained by the method of mathematical experiment planning.The value of the effective rate constants of hydrolysis calculated according to the models for comparative conditions (150 deg C, 3 moles of 85percent sulfuric acid) were used to obtain the correlation between log kh and the ? constants of the substituents.The correlation corresponds the electrophilic nature of the hydrolysis process (ρ = -4.69).The strong influence of the electronic effects of the substituents on the rate of hydrolysis is an indication of the development of a considerable positive charge on the reaction center in the transition state.
- Krylov, E. N.,Volgina, L. V.,Isaeva, G. Yu.
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p. 1129 - 1133
(2007/10/02)
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- SULFONATION DU BENZENE ET DU TOLUENE PAR LE TRIOXYDE DE SOUFRE. PROPOSITION D'UN MECANISME
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Benzene and Toluene sulfonation kinetics have been studied in two solvents (CH3Cl and CCl4).Mechanisms are given to represent competitive kinetics between the two hydrocarbons and isomer distribution of toluene sulfonic acids.Only chain mechanism using pyrosulfonic acid seems to fit the experimental data.
- Homsi, A. el,Guiglion, C.,Guiraud, R.
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p. 383 - 390
(2007/10/02)
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- ISOMERIZATION OF TOLUENESULFONIC ACIDS IN THE PRESENCE OF SULFURIC ACID
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The isomerization of p- and o- toluenesulfonic acids was investigated in relation to the temperature (160 - 200 deg C), concentration (66 - 92 percent), and amount of sulfuric acid (1-5 moles per mole of sulfonic acid).It was shown that the formation rate of the meta isomer from the ortho and para isomers is described by a pseudofirst-order equation for irreversible processes.The isomerization rate depends on the amount of sulfuric acid, which plays the role of active medium.The transformation of the ortho and para isomers to meta-toluenesulfonic acid takes place fairly quickly in a medium with a sulfuric acid content (70 - 85percent) of up to 2 -3 moles per mole of sulfonic acid at 180 - 200 deg C.This makes it possible to obtain a mixture of toluenesulfonic acids with a predominating content of the meta isomer after times in the order of 2 - 3 h.
- Kozlov, V. A.,Popkova, I. A.
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p. 764 - 768
(2007/10/02)
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- Aromatic sulfonation 85. Halogen directing and steric effects in the sulfonation of the twelve halogenotoluenes and some related compounds
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The isomer distributions for the sulfonation of the twelve halogenotoluenes and some trisubstituted halogenomethylbenzenes, with both 98.4 percent H2SO4 at 25 deg C and sulfur trioxide in nitromethane at 0 deg C, have been determined and found to be very similar.The predominantly para-directing effect of the halogen substituent dominates over that of the methyl substituent: with the 2-halogenotoluenes, the degree of 5-substitution decreases from >/= 90 percent for the fluoro to 50 percent for the iodo compound.The 2- to 3-sulfonation ratio of the 4-halogenotoluenes strongly increases on going from fluorine (0.5) to iodine (7).The ratio of the partial rate factors for the sulfonation of a halogenobenzene ortho and meta to halogen varies from 17 +/- 1 for the fluoro to 1.5 +/- 0.4 for the iodo substituent.In competition to the sulfonation, 2- and 4-iodotoluene undergo deiodination, The latter process is more important with the 4-isomer and with the protic sulfonating reagent.With the aprotic reagent, the reaction proceeds by direct sulfodeiodination, whereas with the sulfuric acid reagent, it proceeds by initial protiodeiodination and sulfodeprotonation.
- Cerfontain, Hans,Koeberg-Telder, Ankie,Laali, Khosrow,Lambrechts, Hans J. A.,Wit, Peter de
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p. 390 - 392
(2007/10/02)
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