- Bimolecular proximity of a ruthenium complex and methylene blue within an anionic porous coordination cage for enhancing photocatalytic activity
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The charge repulsion between a catalyst and substrate will significantly reduce the contact occurring between them, resulting in low reactivity. Herein, we report an anionic porous coordination cage that is capable of encapsulating both a cationic catalyst and cationic substrate in its cavity at the same time. After encapsulating the [Ru(bpy)3]2+Cl2 (bpy = bipyridine) catalyst, the cage/catalyst composite serves as an active heterogeneous catalyst for the photo-degradation of methylene blue (MB). The highly negatively charged cavity of PCC-2 allows for the sequential encapsulation of the cationic methylene blue substrate and the Ru catalyst, which in turn significantly shortens the distance between them, yielding an increased possibility of MB degradation. Moreover, the encapsulated Ru catalyst dramatically outperformed its homogeneous counterpart in terms of overall degradation performance and recyclability.
- Fang, Yu,Xiao, Zhifeng,Kirchon, Angelo,Li, Jialuo,Jin, Fangying,Togo, Tatsuo,Zhang, Liangliang,Zhu, Chengfeng,Zhou, Hong-Cai
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p. 3529 - 3534
(2019/03/28)
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- Method for synthesizing orthanilic acid by hydrogenation method
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The invention discloses a method for synthesizing orthanilic acids by a hydrogenation method. The synthesis method comprises the following steps: performing sulfonation reaction on o-nitrochlorobenzene with nitrosonitric acid and concentrated sulfuric acid, and separating high-purity o-Nitrobenzenesulphonic acid after completion of the reaction; forming a clathrum with nitrogen-doped porous coatedcarbon palladium or platinum catalyst, transferring o-Nitrobenzenesulphonic acid to an atomizer for atomization, and adding o-Nitrobenzenesulphonic acid solid in the bottom of a kettle and liquefying; firstly pumping into dry hydrogen gas, starting stirring and circulation reflux, spraying the atomized o-Nitrobenzenesulphonic acid into the kettle, and stoping the reflux after the reaction is completed; introducing the nitrogen gas firstly to exhaust the gas, then crystallizing orthanilic acid, centrifugally separating liquid solid after crystallization and performing suction filtration, and then baking the solid at high temperature to obtain orthanilic acid. The method for synthesizing orthanilic acids by the hydrogenation method uses nitrogen-doped porous carbon as a catalyst carrier andthe catalyst is made into a lattice for gas-gas reaction, and then the reflux and spraying of liquefied o-Nitrobenzenesulphonic acid is circulated, thus producing a high-purity substrate.
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Paragraph 0027; 0031; 0032; 0033; 0034; 0035; 0036-0047
(2019/01/14)
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- Orthanilic acid synthesizing method
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The invention discloses an orthanilic acid synthesizing method. The method includes steps: step one, taking water as a reaction medium, mixing ortho-nitrochlorobenzene and sodium disulfide solution, and stirring at 60-90 DEG C until reaction is finished, so that bis(dinitrophenyl)disulfide is obtained; step two, taking water as a reaction medium, adding the bis(dinitrophenyl)disulfide while addingan oxidant into a reaction system, stirring at 60-90 DEG C until reaction is finished, so that aqueous solution of o-nitrobenzenesulphonic acid is obtained; step three, taking water as a reaction medium and o-nitrobenzenesulphonic acid as a reaction substrate, adding or not adding auxiliary agents, adding catalysts under conditions of 90-120 DEG C and 0.8-2.0MPa, stirring until reaction is finished, and acidizing to obtain orthanilic acid. The orthanilic acid yield of the method reaches 90% or above and increased by 20% or above as compared with that of an old process, product purity is higher than 99.5%, and great crystal form and freeness of metal ion residues are realized. The method has advantages of high economic benefits, environmental friendliness and the like.
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Paragraph 0053; 0056; 0067; 0077; 0087; 0098; 0109
(2018/03/25)
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- Method for preparing aniline-2-sulfonic acid
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The invention relates to a method for preparing aniline-2-sulfonic acid, in particular to a method for preparing aniline-2-sulfonic acid through aniline catalysis and sulfonation. With metal hydrogen sulfate serving as a catalyst, aniline is directly catalyzed and sulfonated to prepare aniline-2-sulfonic acid in a transposition mode. According to the method, aniline is directly catalyzed and sulfonated to prepare aniline-2-sulfonic acid in the transposition mode, so that aniline-2-sulfonic acid is prepared from aniline through a one-step method, and the total yield of aniline-2-sulfonic acid reaches 95% or above; the process route is short, the quantity of the three wastes is small, and the cost is low.
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Paragraph 0017; 0018; 0019; 0020
(2016/12/16)
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- Design and mechanism of iron catalyzed carbon-carbon bond cleavage and N-oxidation processes of hazardous dyes for selective synthesis of nitroarenes and aminoarenecarboxylic acids
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An efficient iron catalyzed oxidative degradation process has been developed for selective conversion of environmentally hazardous azo and indigo dyes into nitroarenes and aminoarenecarboxylic acids (anthranilic acids) respectively, using polymer supported tribromide reagent at an alkaline pH. The in situ generated and the isolated (defined) chloro-iron(II)-terpyridine- pyridine carboxylate [Fe(tpy)(pic)Cl] catalyst system has been developed and its catalytic function was invented for the degradation process. The different nitrogenous and oxygen ligands have been screened out for the development of best catalyst system, and eventually we explored pyridine 2-carboxylic acid and terpyridine ligands together, were found to be the best. Notably, the in situ generated and the defined catalyst systems have found to be more effective with similar catalytic activities towards the oxidative degradation of both the dyes. As a result, the whole oxidative degradation process has been carried out with Fe(tpy)(pic)Cl catalyst system and the general process utilizes the efficient catalytic method for the selective oxidation of -NN- and -CC- bonds of azo and indigo dyes respectively. The detailed catalysis, mechanistic and kinetic investigations have been made for the reactions. Interestingly, both the dyes proceed with a common oxidative degradation mechanism under identical kinetic patters. A common oxidative degradation mechanism which operates in both the dyes has been proposed and an identical related kinetic model was designed. The main interesting aspect of the present work pertains to the catalytic conversion of environmentally hazardous compounds into useful molecules; such are anthranilic acids and nitrobenzenes. Other special aspect related to catalytic activity of iron and potentially, iron catalyst accelerates the reaction rates with 15-20-fold faster. The reactions were also carried out with different polymer supported trihalide and inter-halide reagents. Notably, trichloride and inter-halide regents were found to be more reactive. The catalytic method developed for the degradation process was found to be very efficient and the involvement of cost-effective reagents makes the reaction simple, and can be conveniently scalable to industrial/technological operations with suitable modifications.
- Jagadeesh, Rajenahally V.,Kiran,Bhagat, Pundlik R.,Kumar, S. Senthil,Nithya,Khan, F. Nawaz,Sivakumar
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experimental part
p. 92 - 104
(2011/05/05)
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- The efficient palladium-catalyzed selective t synthesis of benzenesulfonic acids
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Palladium-catalyzed synthetic methodology has been developed for the synthesis of 2-aminobenzenesulfonic acids from benzothiazoles in good to excellent yields using chloramine-B in alkaline (pH 12) acetonitrile/water (1:1) at 80C.
- Jagadeesh, Rajenahally V.,Sandhya, Y. Sree,Karthikeyan,Reddy, S. Sudhakar,Reddy, P. Pradeep Kumar,Kumar, M. Viniod,Charan, K. T. Prabhu,Narender,Bhagat
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experimental part
p. 2343 - 2349
(2011/09/12)
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- Development of an efficient ruthenium catalyzed synthetic process and mechanism for the facile conversion of benzothiazoles to orthanilic acids
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Ruthenium-Schiff base complex catalyzed efficient protocol has been developed for the synthesis of orthanilic acids from benzothiazoles in good to excellent yields using N-haloamines. Hexa-coordinated ruthenium complex with Schiff base and triphenylphosphine ligands has been prepared and its catalytic function was invented for the synthesis of orthanilic acids. The synthetic process utilizes our efficient method for the selective and preferential oxidation of thiazole ring of benzothiazoles using N-haloamines without effecting phenyl ring. The detailed catalytic, mechanistic and kinetic investigations have been made for the synthetic reactions. Solvent isotope studies have been made in H2O-D2O and the reactions were carried out at different temperatures. Under the identical set of conditions, the kinetics of catalyzed reactions has been compared with uncatalyzed reactions and found that the catalyzed reactions are 9-11 folds faster. The catalytic constants (KC) have been calculated for each N-haloamine at different temperatures and the values of activation parameters with respect to the catalyst have been evaluated. Spectroscopic evidence for the formation of 1:1 complex between N-haloamine and ruthenium has been obtained. The observed results have been explained by a plausible mechanism and the related rate law has been deduced.
- Jagadeesh,Karthikeyan,Nithya,Sandhya, Y. Sree,Reddy, S. Sudhaker,Reddy, P. Pradeep Kumar,Kumar, M. Vinod,Charan, K.T. Prabhu,Narender,Bhagat
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experimental part
p. 99 - 107
(2010/12/18)
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- Benzene tricarboxylic acid derivatives as insulin receptor activators
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Compounds of Formula I, and pharmaceutical compositions containing these compounds, activate the insulin receptor kinase, which leads to an increased sensitivity to insulin and an increase in glucose uptake, and are therefore useful for the treatment of animals, especially humans, with hyperglycemia, especially for the treatment of type 2 diabetes. Processes for preparation of the compounds, and their use in assays, are also disclosed.
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- High temperature process for preparing fiber reactive dyes
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A process for preparing monoazo dyes by coupling a aromatic diazonium salt with an amino-4-hydroxy-naphthalene sulfonic acid derivative at a temperature of 40°-85° C. The process of the invention provides a isomerically purer dye.
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- Photoisomerization and Photodegradation of Metanilic Acid
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The photolysis of metanilic acid (1) as the sodium metanilate, through quartz under helium at λ = 254 nm leading to the isomeric anilinesulphonic acids (2 and 3) and aniline (4) has been studied in water.The effects of pH and solvents on products, the acid-base catalysis of the photoreaction (pH-product profile) and the effects of substrate concentration, radical scavenging, triplet sensitization and quenching studies are reported. A mechanism involving a single triplet and a series of ?-complexes is proposed.
- Lally, John M.,Spillane, William J.
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p. 333 - 338
(2007/10/02)
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- The Photochemistry of para-Substituted Phenylsulphamates - Photo-Fries Rearrangements
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The photolysis (254 nm) of a series of para-substituted phenylsulphamates, XC6H4NHSO3Na in degassed methanolic solutions has been examined.For 1a and 1b photo-Fries type rearrangements to sulphonic acids and photodegradation to anilines have been observed.The halogenosulphamates 1c-1e do not rearrange but degrade to anilines and are photosolvolysed to p-methoxyphenylsulphamic acid.No notable spectral changes took place during the irradiation of 1f over relatively long period.Substrate concentration studies, radical scavenging and sensitization and quenching experiments on 1b indicate that, as previously found for 1a, its photolysis involves an intramolecular radical mechanism with the participation of two triplet states.
- Lally, John M.,Spillane, William J.
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p. 803 - 807
(2007/10/02)
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- Solid phase acylation of aminosulfonic acids
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This invention is directed to the acylation of aminosulfonic acids in the solid phase. Two discrete, sequential chemical reactions occur, i.e. (1) the neutralization of the aminosulfonic acid, and (2) the subsequent amine acylation, to produce an improved neutralized acyl-aminosulfonic acid at a reduced cost. Aminosulfonic acids having the general formula HO3 S-A-NH2 are acylated to neutralized acyl-aminosulfonic acids having the general formula RCONH-A-SO3 M, where A is an unsubstituted or substituted aliphatic, aromatic or heteroaromatic group and M is a neutralizing agent moiety. The yield is virtually quantitative.
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- Alkanol substituted disazo orange dye for nylon
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The specification describes a new group of alkanol substituted disazo compounds that are useful in dyeing polyamide textile fibers in orange hues. The new compounds are compatible with several acid blue dyes and several acid red dyes that are commercially important as dyes for nylon. The new compounds are particularly well suited for use as the "yellow" component in trichromatic systems for dying polyamide carpeting and other textiles. The new compounds are relatively inexpensive to make and have outstanding application and fastness properties. Other aspects of the specification are concerned with a method of making the new compounds and with a method of dyeing polyamides with said compounds and to the novel dyed polyamides resulting from the use of the new group of compounds as dyes.
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- KINETICS OF SULFONATION OF AMINES OF THE BENZENE SERIES WITH SULFUR TRIOXIDE
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The sulfonation of amines of the benzene series with sulfur trioxide in dichloroethane is described by a third-order kinetic equation for an irreversible process, and first order is observed with respect to the compound being sulfonated and second with respect to the sulfur trioxide.The unprotonated molecules of the amines undergo sulfonation, and this leads to the production of the para-aminosulfonic acids with small amounts of the ortho isomers.The reaction mechanism involves electrophilic reaction of the unprotonated amine molecule with the sulfur trioxide dimer S2O6 and subsequent dissociation of the obtained pyrosulfonate with the production of the amino sulfonic acid and sulfur trioxide.
- Khelevin, R. N.
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p. 535 - 539
(2007/10/02)
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- Conversion of o-Nitrothiophenols into o-Aminobenzenesulphonic Acids
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The mechanism of conversion of o-nitrothiophenols into o-aminobenzenesulphonic acids in aqueous dioxane has been investigated with particular reference to evidence for the rate-determining formation of a cyclic intermediate.This intermediate is susceptible to interception by both external and internal nucleophilic functions, and the sulphonic acid is shown by isotope labelling experiments to take two oxygen atoms from H2(18)O in the reaction mixture, under conditons in which neither starting materials nor products exchange with H2(18)O.A tentative pathway is advanced.
- Bamfield, Peter,Greenwood, David,Lotey, Harvinder,Stirling, Charles J. M.
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p. 691 - 696
(2007/10/02)
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- KINETICS OF THE SULFONATION OF AMINES OF THE BENZENE SERIES BY CHLOROSULFONIC ACID
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The kinetics of the sulfonation of amines of the benzene series by an equimolar amount of chlorosulfonic acid in o-dichlorobenzene were studied.It was shown that the sulfonation of aniline and N-alkylanilines is described by a second-order kinetic equation for irreversible reactions.The sulfonation of N,N-dialkylanilines by chlorosulfonic acid is described by a first-order kinetic equation for irreversible reactions.The observed relationships are explained by different mechanism for the sulfonation of amines of the benzene series by chlorosulfonic acid.The sulfonation of aniline and N-alkalynilines takes place by direct reaction between the unprotonated molecules of the amines and the HSO3(1+) ion, whereas in the reaction of chlorosulfonic acid with N,N-dialkylanilines complexes of the N,N-dialkylanilines with sulfur trioxide (dialkylanilinesulfotrioxides) are formed initially and then rearrange to the corresponding para-aminosulfonic acids.
- Khelevin, R. N.
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p. 1709 - 1713
(2007/10/02)
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- The Photochemistry of Phenylsulphamic Acid: Photorearrangement and Photodegradation
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Photolysis of the sodium salt of phenylsulphamic acid (1,Na) yields the isomeric aniline sulphonic acids (2)-(4) and aniline (5); the involvement of an intramolecular radical rearrangement and two triplet states in the photoreaction are supported.
- Lally, John M.,Spillane, William J.
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- The Photochemistry of Metanilic Acid: Photoisomerization and Photodegradation
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In the photolysis of sodium metanilate (1,Na) a single triplet and a series of ?-complexes give rise to the isomeric aniline sulphonic acids (2) and (3) and aniline (4).
- Lally, John M.,Spillane, William J.
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p. 1571 - 1572
(2007/10/02)
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- REARRANGEMENT OF PHENYL- AND N-ALKYLPHENYLAMMONIUM HYDROGEN SULFATES IN ORGANIC SOLVENTS
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The kinetics of the rearrangement of phenyl- and N-alkylphenylammonium hydrogen sulfates in halogen-containing organic solvents were investigated in closed systems and with the removal of the water produced in the reaction.The isomeric composition of the obtained aminobenzenesulfonic acids was also studied.The rearrangement is described by a second-order kinetic equation.The reaction mechanism involves thermal dissociation of the phenyl- and N-alkylphenylammonium hydrogen sulfates at high temperatures to amines (bases) and sulfuric acid, followed by direct sulfonation of the amines (bases) by the sulfuric acid with the formation mostly of para-aminosulfonic acids of the benzene series.
- Khelevin, R. N.
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p. 1906 - 1911
(2007/10/02)
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- Insertion of Sulfur Trioxide into the N-Si bond of Anilinotrimethylsilane. An Improved Method for the Preparation of Free Phenylamidosulfuric Acid
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The reaction between anilinotrimethylsilane (1) and a variety of sulfonating agents has been studied.With SO3, 5, or a dioxane-sulfur trioxide complex a sulfur trioxide molecule was inserted selectively into the N-Si bond of 1 to yield trimethylsilyl phenylamidosulfate (2), which on treatment with acetic acid, trifluoroacetic acid, or methanol gave free phenylamidosulfuric acid (3).The reaction of 1 with ClSO3H afforded 3 directly, but the product was contaminated with slight amounts of anilinium hydrogensulfate and anilinium chloride.The reaction of 1 with 10 yielded a mixture containing dianilinium (4-sulfonatophenylamido)sulfate, 4-aminobenzenesulfonic acid, and ethyl phenylamidosulfate as major products (after desilylation).The reaction of 1 with 5 has been found to provide an improved method for preparing 3.
- Kanetani, Fujio,Okada, Eiji,Negoro, Kenji
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p. 2517 - 2520
(2007/10/02)
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- KINETIC OF THE SULFONATION OF AMINES OF THE BENZENE SERIES WITH SULFURIC ACID
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The kinetics of the sulfonation of primary, secondary, and tertiary amines of the benzene series with 80-99.7percent sulfuric acid were investigated.It was shown that the unprotonated and protonated forms of the amines, which are present in equilibrium, undergo sulfonation.The effective reaction rate constants and the activation energies for the sulfonation of the unprotonated and protonated molecules of the amines were calculated.The reaction mechanism and the structure of the transition state are discussed.
- Khelevin, R. N.
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p. 339 - 347
(2007/10/02)
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- FORMATION OF ANILINE MONOSULFONIC ACIDS
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The isomeric composition of the sulfonation mixtures during the sulfonation of aniline sulfate with oleum under various conditions varies in relation to the acidity of the sulfonating agent; mixtures with increased contents of metanilic acid are formed during sulfonation with oleum containing tetrabisulfatoboric acid.The sulfonation rate increases with increase in the acidity of the sulfonating agent, and this provides evidence for the mechanism of sulfonation with the participation of the HSO3(1+) and H3S2O7(1+) ions as electrophiles.
- Khelevin, R. N.
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p. 112 - 116
(2007/10/02)
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- MECHANISM OF THE SULFONATION OF AROMATIC AMINES BY SULFURIC ACID AT HIGH TEMPERATURES
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The kinetics of the rearrangement of unsubstituted and N-substituted phenylammonium hydrogen sulfates to the corresponding aminosulfonic acids of the benzene series were studied.The isomeric composition of the reaction products formed during the sulfonation of amines of the benzene series by various amounts of 100percent H2SO4 was also studied.The rearrangement is described by a second-order kinetic equation.Its effective rate constant at various temperatures and the activation energies were calculated.It is suggested that the sulfonation of aromatic amines by an equimolar amount of sulfuric acid at high temperatures takes place through the dissociation of the arylammonium hydrogen sulfates with the formation of arylamines and sulfuric acid and subsequent direct sulfonation of the arylamines by the sulfuric acid.
- Khelevin, R. N.
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p. 1173 - 1178
(2007/10/02)
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- KINETICS OF THE SULFONATION OF AMINES OF THE BENZENE SERIES BY OLEUM IN THE PRESENCE OF MERCURIC SULFATE
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Sulfonated mixtures with increased contents of the meta isomers are formed during the sulfonation of amine sulfates of the benzene series with oleum containing mercuric sulfate.The following mechanism is proposed for the sulfonation of the amines by oleum in the presence of mercuric sulfate.Two fast reactions take place initially, i.e., sulfonation of the unprotonated molecules of the amines of the benzene series and electrophilic mercuration of the protonated molecules of the amines with the formation of the meta-mercurio derivatives.Electrophilic substitution of the mercury by the sulfo group with formation of the meta-mercuric derivatives then occurs under the influence of the oleum.
- Khelevin, R. N.
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p. 1723 - 1726
(2007/10/02)
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- ISOMERIZATION OF AMINOSULFONIC ACIDS OF THE BENZENE SERIES
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The isomerization of aminosulfonic acids of the benzene series was investigated in 85, 90, and 95percent sulfuric acid at 180, 190, and 200 deg C.It was established that the transformation of the ortho and para isomers into the meta isomers takes place almost irreversibly.The effective rate constants for the isomerisation of the aminosulfonic acids and the activation energies of the reactions were calculated.It was shown that in 85-95percent sulfuric acid the protonated molecules of the aminosulfonic acids undergo hydrolysis in addition to the unprotonated molecules.
- Khelevin, R. N.
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p. 1651 - 1656
(2007/10/02)
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- Studies of Reactions of Amines with Sulfur Trioxide. VI. Thermal Reactions of Anilinium, Dimethylanilinium, and Trimethylanilinium Salts of Butylamidosulfuric Acid
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When the title compounds were heated in an evacuated reaction vessel, both transsulfonation and rearrangement occurred.At lower temperatures (80-120 deg C) the corresponding phenylamidosulfates and sulfophenylamidosulfates (transsulfonation products) were the main products.Increasing temperature led to the formation of ring mono- and disulfonates (rearrangement products) at the expense of the transsulfonation products.The sulfonate group always migrated to the ortho and/or para position(s) to the amino group.In no case was any meta-product detected.There was no significant difference in the ease of transsulfonation among the anilinium salts studied exept 2,6-dimethyl- and 2,4,6-trimethylanilinium salts.On the other hand, the ease of rearrangement and the orientation of ring sulfonation depended strongly on the structure of the substrate anilines.The thermal reactions of 2,4,6-trimethylanilinium butylamidosulfate produced (2,4,6-trimethylphenylimido)bis(sulfate) in addition to (2,4,6-trimethylphenylamido)sulfate.This is the first isolation of an arylimidobis(sulfate) from such reactions.Mechanisms of the transsulfonation and rearrangement have been discussed.
- Kanetani, Fujio,Yamaguchi, Hachiro
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p. 3048 - 3058
(2007/10/02)
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- Process for monoacylating water-soluble organic amino compounds
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A process for the monoacylation of water-soluble organic amino compounds with 2,4,6-trifluoro-s-triazine, which comprises introducing all reactants simultaneously and continuously in the amounts necessary for the required throughput into the reaction space and removing the resultant reaction products continuously therefrom.
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- Red copper complexes of disazo compounds containing triazine groups
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Lightfast and waterfast azo dyes suitable for dyeing fibers and paper, particularly cellulosic materials, and having the following formula: STR1 wherein A is a group selected from 4-methoxy-2-sulfophenyl, 4-methoxy-3-sulfophenyl, 2- or 3-sulphonyl, tolyl, 4-nitro-2,2'-disulfostilbyl, sulfonaphthyl and 4-(4-sulfophenylazo)-2-sulfophenyl; B is selected from monoethanolamino, diethanolamino, morpholino, and N-methylamino; W is hydrogen or sulfonic acid; and Z is sulfonic acid attached at the meta or para position relative to the pendant diazo.
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- Barium laked phenylazonaphthalene dye containing sulfonic acid groups
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Azo dyes containing sulfonic acid groups laked with barium and derived from an anilinesulfonic acid as diazo component and a β-naphtholsulfonic acid as coupling component for example a dye of the formula STR1 The dyes are eminently suitable as pigments for coloring surface coating compositions, printing inks and particlarly resins.
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