- Microwave heating as a new way to induce selectivity between competitive reactions. Application to isomeric ratio control in sulfonation of naphthalene
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Heating rate associated with microwave heating are used to control isomeric ratio in sulfonation of naphtalene. General considerations about use of microwave heating in organic syntheses are also considered. The authors show specificities of microwave heating in term of reactivity, associated with control of very fast heating rate.
- Stuerga,Gonon,Lallemant
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- Micellar Effects upon Rates of SN2 Reactions of Chloride Ion. 2. Effects of Cationic Headgroups
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Observed first-order rate constants for reaction of methyl naphthalene-2-sulfonate with Cl- in micelles of cetyltrialkylammonium chlorides (C16H33NR3Cl, R -= Me, Et, n-Pr, n-Bu, n-Pe) increase with increasing concentrations of surfactant and Cl- and tend to limiting values.These variations can be fitted to a model that describes micelle-ion interactions in terms of Langmuir isotherms.The binding parameters, K'Cl , decrease with increasing headgroup bulk, but second order rate constants at the surface increase.The value of K'Cl is higher with a quinuclidinium as compared with N+R3 headgroup, but the second-order rate constant is similar to that for R = Et.Values of K'Cl are high with hydroxyethyl head groups N+R3 = N+Me2CH2CH2OH or N+(CH2CH2OH)3, but these groups decrease second-order rate constants.Values of K'Cl estimated from 35Cl NMR line widths agree with the kinetic values except with the N+(CH2CH2OH)3 headgroup for which the kinetic values are much higher.The effect of headgroup bulk upon the spontaneous reaction with water was examined by using sulfate as the surfactant counterion.Trends in reactivity are very similar for reactions of H2O and Cl-.
- Bacaloglu, Radu,Bunton, Clifford, A.,Cerichelli, Giorgio,Ortega, Francisco
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- Neopentyl ester protecting groups for arylsulfonic acids
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We report that neopentylsulfonate esters are stable to a variety of standard organic reaction conditions and are easily cleaved to sulfonic acids. We also discuss the use of N-Boc-4-amino-2,2-dimethylbutyl-1-sulfonate esters which may be cleaved under conditions that are suitable for solid phase synthesis.
- Roberts, John C.,Huai, Gao,Gopalsamy, Ariamala,Kongsjahju, Azis,Patch, Raymond J.
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- Synthesis of optically pure 3,3′-diaryl binaphthyl disulfonic acids via stepwise N-S bond cleavage
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We developed a practical synthesis of optically pure 3,3′-diaryl-1, 1′-binaphthyl-2,2′-disulfonic acids (i.e., (R)- or (S)-3,3′-Ar2-BINSAs) from the parent chiral sulfonimides via stepwise N-S bond cleavage of the sulfonimides and the resultant sulfonamides. This unusual synthesis, which provides arylsulfonic acids from arylsulfonamides, is valuable since common methods particularly give amines with the decomposition of sulfone groups during deprotection.
- Hatano, Manabu,Ozaki, Takuya,Nishikawa, Keisuke,Ishihara, Kazuaki
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- The sulfonation of aromatic and heteroaromatic polycyclic compounds
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Relative reactivities of a series of polycyclic carbo- and heteroaromatic compounds to sulfonation by sulfur trioxide in nitrobenzene are measured and discussed. The results show the following reactivity in decreasing order: indole, carbazole, pyrene, perylene, naphthalene, phenanthrene, benzene, benzothiophene, and dibenzothiophene.
- Katritzky, Alan R.,Kim, Myong Sang,Fedoseyenko, Dmytro,Widyan, Khalid,Siskin, Mike,Francisco, Manuel
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- Effects of micellar head group structure on the spontaneous hydrolysis of methyl naphthalene-2-sulfonate. The role of perchlorate ion
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The spontaneous (SN2) hydrolysis of methyl naphthalene-2-sulfonate (MeONs) in water is inhibited by cationic, anionic and zwitterionic micelles of the following surfactants, CTAOMs, n-C16H33N+Me3MeSO3 -; CTPAOMs, n-C16H33N+Pr3MeSO3 -; SDS, C12H25OSO3-Na+; SB3-14, n-C14H29N+Me2(CH2) 3SO3-;-SBBu3-14, n-C14H29N+Bu2(CH2) 3SO3-; DMMAO, n-C14H29N+Me2O-; DPMAO, n-C14H29N+Pr2O-. Rate constants, krel, relative to those in water, are in the range 0.55-0.63 for all the cationic and zwitterionic micelles including the protonated amine oxides. The value of krel in anionic micelles of SDS is 0.22, but NaClO4 sharply decreases krel in SB3-14 from 0.56 to 0.15. These rate effects are not related to variations in substrate binding but depend upon interactions of the head groups with the initial and transition states.
- Brinchi, Lucia,Di Profio, Pietro,Germani, Raimondo,Savelli, Gianfranco,Spreti, Nicoletta,Bunton, Clifford A.
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- Synthesis and structural elucidation of sulfonated naphthalene-formaldehyde
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The synthesis, characterization, structural elucidation, and application of the dispersant obtained from the condensation of -naphthalene sulfonic acid and formaldehyde are reported. The one-pot synthesis from naphthalene, sulfuric acid, and formaldehyde leads to reproducible polymers with 13 and 14 naphthalene nuclei. The 1H and 13C NMR spectra in D2O (representative spherical shape) and DMSO (representative rod-like shape) are reported. The belching technique led to excellent super pure material.
- Moradian,Mahmoodi,Shemshadi
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- Preparation method of clean product 1, 6 and 1,7 mixed
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The invention relates to a preparation method of a cleaning type product 1,6- and 1,7-Cleve's acid. The method comprises the following steps: performing sulfonation on refined naphthalene to obtain 2-naphthalene sulfonic acid, performing nitration for the formation of a mixture of 1-nitro-6-naphthalenesulfonic acid and 1-nitro-7-naphthalenesulfonic acid, performing neutralization through ammonia water, and finally performing hydrazine hydrate reduction to obtain the 1,6- and 1,7-Cleve's acid. Compared with original production process, the method provided by the invention has no generation of waste residue in the whole process, the purpose of emission reduction is achieved, and the process is more simple and convenient, and has safety and effectiveness. In addition, the overall cost of theprocess provided by the invention is lower than the overall cost of an original process.
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Paragraph 0037-0040
(2020/06/16)
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- Synthetic process of naphthol
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The invention discloses a synthetic process of naphthol. The process comprises the followings steps: sulfonation, neutralization, alkali fusion, and acidification. The sulfonation step comprises the following steps: a sulfonation reaction is carried out for naphthalene and sulfuric acid whose mass fraction is 98% in the existence of a water carrying agent, a characteristic that the water carrying agent and water form an azeotrope is applied, water which is generated in the reaction is separated continuously from a reaction system, and naphthalene and sulfuric acid are nearly reacted completely. Obtained 1-naphthalenesulfonic acid is neutralized, alkali fusion and acidification are directly carried out in order to obtain a naphthol crude product. The process has the advantages of simplified operation, little low of naphthalene and sulfuric acid, high utilization rate, high naphthalene conversion rate which reaches 94% or above, low amount of waste water, and a few amount of sodium sulfate waste water which is only generated after multiple circulations.
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Paragraph 0017; 0018; 0019; 0020; 0021; 0022
(2017/08/29)
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- A dilute sulfuric acid recovery method for using (by machine translation)
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The invention discloses a method for recovering and utilizing dilute sulfuric acid, characterized in that comprises the following steps: in the reaction with rectification, the dilute sulfuric acid and double-ring aromatic hydrocarbon, or/and polycyclic aromatic hydrocarbon in the distillation together with, in the rectification process, the water as the light component, from the rectification tower, the concentration of sulfuric acid in the kettle, the kettle warmly rise; when cauldron mass concentration of sulfuric acid in > 63% time, the temperature of the kettle for 150-175°C, sulfuric acid and double-ring aromatic hydrocarbon, or/and polycyclic aromatic sulfonation reaction occurs, the water is generated at the same time, and the concentration of sulfuric acid in the rectification heating water outlet, so cycle, until complete reaction consumption of sulfuric acid in the kettle. In the invention, the dilute sulfuric acid rectification concentrated use and double ring/multi-ring aromatic sulfonated combination, does not need high-temperature, can be realized by using concentrated and dilute sulfuric acid. (by machine translation)
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Paragraph 0021
(2016/11/24)
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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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- REDUCTION METHOD OF ARENESULFONAMIDE, PRODUCTION METHOD OF ARENESULFONIC ACID AND BINAPHTHYLDISULFONIC ACID
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PROBLEM TO BE SOLVED: To obtain a corresponding reduction body from an arenesulfonamide with good yields. SOLUTION: A N,N-dimethylnaphthalene-2-sulfonamide is reduced with 5 equivalents of Red-Al (NaAlH2(OC2H4OCH3)2), so that a corresponding sulfinic acid is obtained with good yields. The sulfinic acid is oxidized with oxygen (1 atm), so that a corresponding naphthalene-2-sulfonic acid is obtained. COPYRIGHT: (C)2015,JPO&INPIT
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Paragraph 0029; 0031; 0034
(2016/11/17)
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- Synthesis of sulfonyl chlorides and sulfonic acids in SDS micelles
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H2O2/POCl3 is found to be a reactive reagent system that can be used in sodium dodecyl sulfate (SDS) micellar solution in aqueous media for the direct oxidative chlorination of thiol and di-sulfide derivatives to give the desired sulfonyl chlorides. The oxidation of thiols and disulfides to sulfonic acids with this system is also reported. In most cases, these reactions are highly selective, simple, and clean, affording products in excellent yields and high purity. Georg Thieme Verlag Stuttgart · New York.
- Bahrami, Kiumars,Khodaei, Mohammad M.,Abbasi, Jamshid
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experimental part
p. 316 - 322
(2012/03/26)
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- A new process for the synthesis of naphthalene based tanning agent
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A new process developed for the preparation of naphthalene catechu tanning agent consisted of sulphonation of naphthalene, condensation with formaldehyde, combining with naturally occurring catechol, followed by neutralization of the reaction mixture. The product was then dried, analyzed and tested for application on wet blue leather which showed excellent tanning properties.
- Mahboob, Sarwat Jahan,Subhopoto, Muhammad Ishaq,Dewani, Rajkumar,Pervez, Muhammad Kashif,Nazir, Farrukh
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experimental part
p. 230 - 232
(2011/10/13)
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- Selective and mild oxidation of thiols to sulfonic acids by hydrogen peroxide catalyzed by methyltrioxorhenium
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Aromatic and aliphatic thiols are oxidized in acetonitrile at 20 °C by hydrogen peroxide in the presence of methyltrioxorhenium as the catalyst to yield the corresponding sulfonic acids in high isolated yields (85-94%).
- Ballistreri, Francesco P.,Tomaselli, Gaetano A.,Toscano, Rosa M.
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p. 3291 - 3293
(2008/09/20)
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- PHARMACEUTICAL COMPOSITIONS CONTAINING SULPHONIC ACID DERIVATIVES
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A naphthalenesulfonic acid or quinolinesulfonic acid of formula (I), wherein A is N or a CR8 formula group, where R8 is H, OH, NR10R11, independently from one another, where R10 and R11 represent H or C1-C6 alkyl or a group of formula NH-CO-R12, where R12 is C1-C6 alkyl or C6-C10 aryl; R1 and R2 represent H or SO3R9, independently from one another, where R9 is H, ammonium or a cation of an alkali or alkaline-earth metal; R3 is H or OH; and R4, R5, R6 and R7 represent H, an NR10R11 or NH-CO-R12 group, independently from one another; on the condition that (i) at least one of R1 or R2 is SO3R9, and (ii) at least one of R4, R5, R6 or R7 is an NR10R11 or NH-CO-R12 group, or their pharmaceutically acceptable salts; and a pharmaceutically acceptable excipient.
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Page/Page column 11
(2008/06/13)
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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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- Exploiting differences in solution vs solid-supported reactivity for the synthesis of sulfonic acid derivatives
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(matrix presented) Quantitative We describe a method herein for the protection of aryl and alkyl sulfonates during synthesis which employs commercially available Wang or MBOH resin, both of which terminate as benzyl alcohols, as both a protecting group and "traceless" linker. Given the known instability of benzylic sulfonate esters to nucleophilic displacement in solution, this linkage is surprisingly stable: no loss of either aryl or alkyl sulfonates is observed when the resin is exposed to a wide variety of organic bases and solvents at room temperature. Further elaboration of the resin-bound sulfonates via Suzuki coupling is also described.
- Hari, Anitha,Miller, Benjamin L.
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p. 2109 - 2111
(2008/02/10)
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- Modelization and kinetic simulation of naphthalene sulfonation by 20percent oleum
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This study represents a modelization procedure for the kinetic analysis of naphthalene sulfonation using 20percent oleum at temperature 393 K.The sulfonation involves many consecutive, parallel and reversible reactions.Representative samples of the reaction mixture are analyzed by high-performance liquid chromatography for quantitative determination of the produced sulfonic acid isomers as well of the remaining naphthalene.The kinetics obtained this way allow to suggest a model describing the concentration evolution of four components in the reaction mixture.Therefore, six main reactions are taken into account, the kinetic parameters of which are estimated by the fitting of experimental data, using a weighed least-squares method based on minimizing the deviation between calculated and experimental data. - Keywords: modelization; naphthalene sulfonation; 20percent oleum; kinetics; naphthalenesulfonic acid
- Aleboyeh, Hamid,Kille, Gerard,Walter, Serge,Aleboyeh, Azam,Ladhari, Neji
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p. 677 - 682
(2007/10/03)
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- Sulfonation and Desulfonation of Naphthalene under Conditions of Microwave Activation
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Microwave activation sharply curtails the time required for sulfonation of naphthalene and allows this reaction to be performed with less concentrated sulfuric acid. The consumption of sulfuric acid is decreased. Moreover, under certain conditions the ratio of isomeric sulfonic acids can be changed toward α or β isomer. Microwave radiation also accelerates desulfonation of β-naphthalenesulfonic acid in solutions with low pH.
- El'tsov,Sokolova,Dmitrieva
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p. 295 - 299
(2007/10/03)
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- The positional reactivity order in the sulfur trioxide sulfonation of benzene and naphtalene derivatives containing an electron-withdrawing substituent
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The reaction of sulfur trioxide with derivatives of benzene and naphthalene containing an electron-withdrawing substituent, viz.-SO3H, -SO2Ph, -NO2, -CHO, -COPh, -CO2H, and -CO2Me, in dichloromethane as solvent at ca. 22 deg C has been studied by analysis of the resulting mixtures of the sulfo derivatives with 1H-NMR.The initial sulfonation of the benzene derivatives yields the corresponding 3-sulfonic acid (3-S) and subsequently, with the exception of nitrobenzene and methyl benzoate, small amounts of 3,5-S2.Benzenesulfonic acid in addition undergoes sulfonylation giving 3,3'-di- and 3,5,3'-trisulfodiphenyl sulfone.Monosulfonation of naphtalene-1-S yields the 1,5-S2, 1,6-S2 and 1,7-S2 derivatives in a ratio of 71:20:9.On using a large excess of SO3, the eventual products are 1,3,5-S3, 1,3,6-S3 and 1,3,5,7-S4.Monosulfonation of naphthalene yields 5-S, 6-S, 7-S and 8-S in a 55:9:6:30 ratio, that of 1-benzoylnaphthalene 5-S, 6-S and 7-S in a ratio of 83:11:6, and 1-nitronaphtalene only the 5-S.The absence of peri sulfonation with 1-sulfo-, 1-benzoyl- and 1-nitronaphthalene is due to prohibitive steric hidrance. 1-Naphthoic acid and its methyl ester upon SO3 sulfonation and aqueous work-up both yield 5- and 8-sulfonaphthoic acid in a ratio of 65:35 and 77:21, respectively.The initially formed peri-substituted product is the intramolecular anhydride of 8-sulfo-1-naphthoic acid (5).All the 2-substituted naphthalenes yield 5-S and 8-S upon SO3 sulfonation of which the former sulfo isomer is far in excess.The positional reactivity orders for the SO3 sulfonation of the monosubstituted naphthalene derivatives are discussed in terms of the difference in reactivity of the α- and β-positions, and the steric and electronic effects of the deactivating substituent.
- Cerfontain, Hans,Zou, Yousi,Bakker, Bert H.
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p. 403 - 410
(2007/10/02)
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- Novel 6-alkyl and 6.8-dialkylbicyclo(4.2.0)octane derivatives
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Compounds useful in treating or preventing gastrointestinal ulcers and in treating cardiovascular disorders such as thrombosis, hypertension and atherosclerosis are depicted in formulas (1), (2) and (3): STR1 wherein: A is --C C--, trans --HC=CH--, trans --CH=CHCH2 -- or --CH2 CH2 --; X is lower alkyl of 1-6 carbon atoms; Y is hydrogen, exo-(lower alkyl) or endo-(lower alkyl); n is an integer from 2-4; R1 is --CH2 OH, --CHO, --CO2 R or --CO2 H, and the olefin formed by the R1 (CH2)n CH= moiety is either (E) or (Z); R2 is hydrogen or methyl, or optionally --CH=CH2 when A is trans --CH=CHCH2 --; and R3 is linear or branched alkyl, alkenyl or alkynyl having 5-10 carbon atoms, STR2 --(CH2)m -phenyl or CH2 O-phenyl; in which each phenyl may be optionally substituted with lower alkyl, lower alkoxy, trifluoromethyl, or halogen. in which: a is an integer of 0, 1 or 2; b is an integer of 3-7; m is an integer of 0, 1 or 2; and R is STR3 wherein X' is STR4 in which each R4 is independently hydrogen or lower alkyl having 1-6 carbon atoms, or a pharmaceutically acceptable, non-toxic salt or ester thereof.
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- APPLICATION OF MICROWAVE ENERGY TO ORGANIC SYBNTHESIS: IMPROVED TECHNOLOGY
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The application of microwave energy to the sulfonation of naphthalene and anthraquinone, to the amination of p-chloronitrobenzene, and to the hydrosilylation of 2- and 4-vinylpyridine has been studied.Though faster (5-360-fold) reactions were observed problems were encountered with the available microwave technology.These were overcome by using a microwave oven equipped with stirring facility and both temperature and pressure control.
- Abramovitch, R. A.,Abramovitch, D. A.,Iyanar, K.,Tamareselvy, K.
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p. 5251 - 5254
(2007/10/02)
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- Linear Free Energy Relationship in Naphthalene System: Kinetics of Hydrolysis of 4-Substituted 1-Naphthalenesulphonyl Chlorides
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The kinetics of hydrolysis of several 4-substituted 1-naphthalenesulphonyl chlorides have been studied in aqueous acetone at three temperatures.The reaction is first order in sulphonyl chloride.Presence of electron-withdrawing substituents in the naphthyl ring enhances the rate while that of opposite ones retards it.The small ρ-values obtained in the correlation analysis using the Hammett and dual substituent parameter equations are consistent with either an SN2 or an SAN mechanism.
- Perumal, S.,Selvaraj, S.,Viswanathan, T. K.,Arumugam, N.
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p. 436 - 438
(2007/10/02)
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- Dyeing assistants and their use in dyeing synthetic fibre material
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A dyeing assistat containing at least (a) an alkylbenzene or tetrahydronaphthalene (tetralin) or a mixture thereof, (b) an anionic surfactant, (c) a non-aromatic and water-immiscible solvent and optionally also (d) a polar solvent and/or (e) a non-ionic surfactant; this dyeing assistant can be used to promote the migration of the dyes and thus to improve the levelness and dye yield when dyeing synthetic fibre material, preferably polyester, in particular in the temperature range from 80° to 130° C.
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- Spray-drying method for the preparation of water-dispersible pulverulent disperse dye formulations
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Easily water-dispersible pulverulent formulations of disperse dyes are prepared by spray-drying a dye solution which comprises (a) one or more disperse dyes, (b) one or more water-soluble anionic dispersants, (c) from 0 to 20% by weight, based on (a+b+c+d), of other surfactants and (d) from 0 to 20% by weight, based on (a+b+c+d) of agents which serve as protective colloids (the proportion of (c+d) being at most 20% by weight). Suitable solvents (e) are formic acid, formamide, N-methylformamide, butyrolactone, ethylene glycol and propylene glycol, which may in addition contain up to 100% by weight, based on (e), of N,N-dimethylformamide or acetic acid or mixtures of these. The formulations obtained by the above process contain the dye in very fine dispersion.
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- 6-Acylamido-2,2-dimethyl-3-(pyrimidin-4,6-dione-2-yl)-penams and intermediates therefor
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Antibacterial 6-acylamido-2,2-dimethyl-3-(pyrimidin-4,6-dione-2-yl)-penams, intermediates therefor, including 6-amino-2,2-dimethyl-3-(pyrimidin-4,6-dione-2-yl)penam, and processes for their preparation.
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