Fuming Sulfuric Acid Research Articles

Studies on Sulfonated Sites of Quinoline Yellow WS

Sulfonated sites in quinoline Yellow WS, which is distributed under the name of D & C Yellow No.203have not been clarified as yet. Treatment of 2-(2'-quinolyl)-1, 3-indandione with fuming sulfuric acid, gave several sulfonated products and two of product dye were identified as 2-(2'-quinolyl)-1, 3-indandione-6'-sulfonic acid and 2-(2'-quinoly)-1, 3-indandione-5, 6'-disulfonic acid by nuclear magnetic resonance, infrared and mass spectra. Commercial samples of quinoline Yellow WS consist of the disodium 2-(2'-quinolyl)-1, 3-indandione-5, 6'-disulfonate and contain other sulfonated derivatives.

Preparation of oxygen-18 enriched sulfur trioxide

Oxygen-18 enriched sulfur trioxide has been prepared by a simple and relatively inexpensive procedure. This has been occomplished by the addition of sulfur trioxide to oxygen-18 enriched water to form fuming sulfuric acid containing approximately 50 per cent dissolved sulfur trioxide. On distillation of this fuming sulfuric acid, the sulfur trioxide obtained was enriched in oxygen-18. It was isolated and analyzed as its dimethylformamide complex.

Charring with sulfur trioxide for the improved visualization and quantitation of thin layer chromatograms

AbstractContinuous and uniform exposure to an atmosphere of dry SO3 effectively chars chromatograms with convenience, safety and speed. The sandblasted, concave surface of a heat resistant glass lid is coated with fuming sulfuric acid. The lid encloses the thin layer chromatography plate while it is heated by a hot plate. Cholesterol, oleic acid and triolein show SO3 char and char‐fluorescence detection limits much lower and carbon yields more nearly equal than those reported to be obtained with conventional spray char reagents. Liquid reagent does not touch the layer. It remains clean, dry and permanent. Freedom from excess acid lends stability to the intensity of char‐fluorescence spots. Because of lower temperature requirements, SO3 char probably can be extended to include substances which are too volatile for acid spray char. A guide to the selection of conditions for the detection, identification and quantitation of char, charfluorescence and char‐color spots is given. Additional areas of investigation with SO3 as well as other reagent fumes are indicated.

Aromatic sulfonation 28: Degree ofortho‐substitution in the sulfonation of toluene with sulfur trioxide, methanepyrosulfonic acid and fuming sulfuric acid. A mechanistic picture

AbstractThe reaction of neat toluene with a number of different sulfonation reagents at 25° has been studied. With sulfur trioxide vapour as reagent, the reaction leads to monosulfonation only. Theo/(o + m + p)ratio varies with the degree of toluene conversion, the limiting values at zero and high conversion being 0.34 ± 0.03 and 0.11 ± 0.01, respectively. The former value is ascribed to the sulfonation of toluene with sulfur trioxide, the latter to sulfonation in the acid phase with toluenepyrosulfonic acid as the sulfonating entity.The heterogeneous reaction of toluene with a deficient amount of a matured mixture of methanesulfonic acid and sulfur trioxide ‐ i.e. with a methanepyrosulfonic acid reagent — leads to monosulfonation only. Theo/(o + m + p)ratio varies from 0.15 ± 0.01 at zero toluene and zero time conversion to 0.11 ± 0.01 at high toluene conversion. The former value is ascribed to sulfonation in the acid phase of dissolved toluene by methanepyrosylfonic acid, the latter to that by both toluene‐ and methane‐pyrosulfonic acids.Heterogeneous sulfonation with a deficient amount of fuming sulfuric acid takes place mainly ( ∼97 %) in the acid phase. Sulfonation in the toluene phase leads to monosulfonic acids only with 41 ± 2 % ofortho‐substitution. Sulfonation in the sulfuric acid phase yields monosulfonic acids and, at the higher sulfuric acid concentrations, also toluene‐2,4‐disulfonic acid. The degree ofortho‐substitution for sulfonation in the acid phase at 25° changes from 48.5 to 40 % on varying the acid concentration from 100.0 to 106.4% H2SO4.

Sulfur modification of polyethylene surfaces. II. Modification of polyethylene surfaces with fuming sulfuric acid

AbstractPrevious work has shown that atomic sulfur irreversibility modifies polyethylene, presumably through an insertion reaction into carbon—hydrogen bonds with formation of surface thiol groups. The thiol groups were then oxidized to sulfonic acid surface groups, which were further reacted chemically as shown by wettability measurements. In this work the thiol group was bypassed and the surface sulfonic acid groups were obtained by exposing the polyethylene surface directly to fuming sulfuric acid. The sulfonic acid groups were reacted further. Critical surface tension values identical with those in the previous work with atomic sulfur were obtained, thus substantiating the previous work.

L-α, β-Diaminopropionic Acidの新合成法

L-α, β-Diaminopropionic acid was obtained in 92% yield from L-aspartic acid by the Schmidt reaction using 30% fuming sulfuric acid and sodium azide.

Studies on Isothiazoles. II. Nitration of 3-Phenylisothiazoles

Nitration of 4-substituted-3-phenyliosthiazoles (I, II, III, and IV) with fuming nitric acid and sulfuric acid yielded exclusively the corresponding 3-m-nitrophenyl derivatives (VI, VII, VIII and IX), while nitration of 3-phenylisothiazole (V) gave 3-p-nitrophenylisothiazole (Xa) and 3-m-nitrophenylisothiazole (Xb). Reduction of 5-methyl-3-m-nitrophenylisothiazole-4-carboxylic acid (IX) afforded the corresponding amino derivative (VII), which was diazotized and subjected to the Sandmeyer Reaction to give the corrsponding 3-m-chlorophenyl (XIV) and 3-m-bromophenyl (XV) derivatives. Preparation of the 3-m-methoxyphenyl derivative (XVII) was also described.

Poly‐1.3.4‐oxadiazoles. IV. Poly‐1.3.4‐oxadiazoles containing pyridine rings

AbstractIn order to obtain tractable aromatic poly(1.3.4‐oxadiazoles), the polycondensation of pyridinedicarboxylic dihydrazides has been investigated according to the solution polycondensation procedure using fuming sulfuric acid or polyphosphoric acid as solvent and condensing agent. The resulting polymers were not wholly composed of the 1.3.4‐oxadiazole structure, and their molecular weights were rather low (ηsp/c up to 0.18 dl/g).Some properties of the polymers, such as IR‐ and UV‐spectra, solubility, and thermal stability, were compared with those of authentic poly(pyridine‐1.3.4‐oxadiazoles).

A Solvatochromic Dye as a Convenient Indicator of the Solubility Parameter of Petroleum Solvents

The solvent power of petroleum solvents is highly dependent upon the percentage of aromatic compounds present in the mixture. In alkyl benzenes, it is dependent upon the proportion of aromatic character in the compounds. Suppliers of petroleum solvents frequently state the aromatic content of their solvents or provide figures for the Kauri-Butanol number, mixed aniline point, or related indicators of solvent power. When these data are not readily available, aromatic content in the petroleum solvents can be estimated by extraction with fuming sulfuric acid (R. L. Feller in Application of Science in the Examination of Works of Art, Museum of Fine Arts, Boston, 1959, p. 51; Feller, Stolow, anWiJnes, On Picture Varnishes and Their Solvents, Intermuseum Conservation Association, Oberlin, 195).

The aromatization of cyclohexanedione dioximes

The aromatization of cyclohexane-1,2-dione dioxime (nioxime), 4-methylcyclohexane-1,2-dione dioxime and nickel (II)bis(N,N′-4-methylcyclohexane-1,2-dione dioximate) takes place in polyphosphoric acid (PPA) to the corresponding o-phenylenediamine derivatives. The mechanism is analogous to the Semmler-Wolff aromatization. Aromatization, in addition to the normal Beckmann rearrangement, takes place with cyclohexane 1,4-dione dioxime in both conc and fuming sulfuric acids.

Aromatic sulfonation XII: Kinetics of the sulfonation of p‐ and o‐toluenesulfonic acid in aqueous and fuming sulfuric acid

AbstractThe kinetics of the sulfonation of p‐ and o‐toluenesulfonic acid have been measured at 25.0° in aqueous and fuming sulfuric acid, the concentrations varying from 93.3‐103.3 wt‐% H2SO4. The reaction is first order with respect to the sulfonic acid.The observed variation in the apparent first order rate constants is of the order of 106. The sulfonation kinetics are shown to be consistent with the sulfonation mechanisms previously proposed for aqueous1 and fuming2 sulfuric acid. In aqueous sulfuric acid varying in composition from 93.3‐98.8 wt‐% H2SO4 isomerization was shown to be a reaction of minor importance.

Formation of Oil Soluble Petroleum Sulfonic Acid by Treatment of Mineral Oil with Fuming Sulfuric Acid

The sulfonation of a pretreated fraction of spindle oil by 20% SO3-fuming sulfuric acid has been studied, and the effect of the reaction variables on the yield of mahogany acids has been investigated, in addition, their structure has been discussed.It has been found that with the more fuming sulfuric acid, at the higher temperature, and for the longer reaction time the yield of mahogany acid decreases, and with the higher velocity of stirring, the reaction rate increases.In our experiments the most favourable condition of sulfonation of mineral oil may be as follows: quantity of fuming sulfuric acid is 20-30% (by volume) per oil, tempera-ture is at 30°Cand time is for 15minutes.However, the most important factor deter-mining the yield of mahogany acid is indeed the constituent of oil rather than reaction conditions.From the ultraviolet and infrared absorption spectrum analyses, it is deduced that mahogany acid may be hydroxy aromatic monosulfonic acid with long paraffinic chain, of which hydroxy and sulfonic group are probably attached to aromatic ring. Mahogany acid may be produced by dehydrogenation of naphthene ring with following sulfonation.The unreacted fraction contains some isomerized or intramolecular cyclized oil which are produced by the action of fuming sulfuric acid.

Thin cation-exchange foils

Treatment of commercial polystyrene sheets with fuming sulfuric acid produces a thin layer of cation exchanger. The ion exchange capacity of the layer is measured by an isotope dilution procedure which utilizes Th 228 and Th 232. At the same time the thickness is found from the yield of Ra 224 which escapes from the foils as α-decay recoils. A specific capacity of 5.6 milliequivalents per gram can readily be obtained, and the thickness can be varied from a few to several hundred micrograms/cm 2. The foils have been used for simple and fast preparation of α sources.

STUDIES ON THE DYEING OF POLYPROPYLENE FIBRE

Though it has been known that polypropylene can easily be sulfonated with fuming sulfuric acid, ClSO H etc, practical method is little known.This study was carried out for the purpose of improving the dyeing properties of polypropylene fibres, especially with regard to sulfonation. In this report, polypropylene fibres were treated as follows.(1) Fibre was treated in the solution of mixture CH3Cl and ClSO3H.(2) Fibre was treated in variously concentrated fuming sulfuric acid solutions and washed with CCl4(3) Fibre was treated with ClSO3H dissolved in the mixture of CH3Cl, CCl4.(4) Fibre was treated in the upper layer of the mixed solution of CCl4 and ClSO3H, or of fuming sulfuric acid solution.In all cases, the treated fibres neither coloured nor fused, but a little colouring was observed at high temperature. And the physical properties of the sulfonated fibres decreased slightly in tensile strength and elongation increased. Those fibres have affinity to basic dyes and dispersed dyes.

Preparation of tagged sodium dodecylbenzenesulfonate of high purity and specific radioactivity

Radioactive tagging of a surface active agent, commonly known as a “surfactant” is described. Sodium dodecylbenzenesulfonate was chosen because it is one of the principal surfactants used in household detergents. To increase the radiochemical yield, the tagged sulfuric acid was concentrated and the minimum amount of non-radioactive 30% fuming sulfuric acid needed to complete the sulfonation determined. The dodecylbenzene used was fractionated from “Neolene-400” using chromatographic methods. The difference in isomers was detected by infrared spectra and refractive indices. Two methods of introducing the radioactive sulfur were employed. The purity of the products obtained was determined from their respective infrared spectra. The final product had a specific radioactivity of 1.24 millicuries per gram of surfactant. Its purity was about 99%. Some experiments using the product are described.

樟脳誘導体の合成研究 (第9報)

It was shown in the previous paper that α-trans-π-dihalo-d-camphor underwent peculiar isomerization by fuming sulfuric acid and formed 6-trans-π-dihalo-l-camphor. From the assumption of the racemization mechanism of camphor by sulfuric acid forwarded by Asahina, it was assumed that the above reaction passed through an intermediate of 5-trans-π-dihalo-d-camphor. Therefore, 5-bromo-trans-π-chloro-d-camphor was prepared from trans-π-chlorocamphor through trans-π-chloro-d-camphoquinone, trans-π-chlorodiazo-d-camphor, and trans-π-chloro-β-pericyclocamphanone. Application of fuming sulfuric acid to the 5-bromo derivative unexpectedly revealed that it is extremely stable to this acid and no change was found to occur. The same reaction of α-bromo-6-trans-π-dichloro-l-camphor showed that this substance is also stable to fuming sulfuric acid.

化学療法剤の研究 第30報

Amstutz, et al. assumed that the substance obtained on the reduction of 2, 8-dinitro-thiaxanthone 5-dioxide with zinc powder and acetic acid was 2, 8-diaminothiaxanthene 5-dioxide (I) but the reëxamination of this reaction revealed that the reduction product was not (I) but 2, 8-diaminothiaxanthenol 5-dioxide (II), since the reduction of (II) with hydriodic acid and red phosphorus yielded (I). (I) can also be obtained by the application of fuming sulfuric acid on 3, 3′-diaminodiphenylmethane, or by the sulfonation of 3, 3′-diacetaminodiphenylmethane with chlorosulfonic acid followed by hydrolysis.

Cationic polymerization of butadiene and copolymerization of butadiene and styrene

Abstract The cationic polymerization of butadiene with several Friedel‐Crafts catalysts has been described. Aluminum chloride and chlorosulfonic acid are active catalysts at −75°. The rate of polymerization at −75° is much faster than at the higher temperatures. Except for boron trifluoride etherate, which catalyzes the polymerization at −30°, the other catalysts (sulfuric acid, fuming sulfuric acid, stannic chloride, and boron trifluoride hydrate) produce appreciable amounts of polymer only at 0° or higher. The effect of variables, such as catalyst concentration, catalyst solvent, dilution, reaction time, etc., differs with each individual catalyst. In some cases, results were not conclusive due to lack of reproducibility. It was found that the presence of moisture is mainly responsible for this lack of reproducibility. Traces of water promote the polymerization with stannic chloride or boron trifluoride etherate, but inhibit the polymerization when an ethyl bromide solution of aluminum chloride is used as catalyst. Rubberlike polyhutadienes can be obtained with all catalysts except sulfuric and fuming sulfuric acids. However, the physical properties of these polymers show that the molecular weight is very low and that the polymer is not suitable as a rubber. Polymers ranging from viscous liquids to hard, brittle solids have also been obtained. In general, the solubility of the polymers is low. Approximately 60% of the butadiene enters the polymer chain by 1,4 addition. The copolymerization of butadiene and styrene at −75° with an ethyl bromide solution of aluminum chloride has also been studied. At conversions between 20 and 30% a soluble, rubberlike copolymer having a low molecular weight is formed. An insoluble, brittle polymer is obtained a t higher conversions. The soluble, cationic copolymer has a characteristic ultraviolet absorption curve which is different from that of GR‐S. It has a styrene content of approximately 50% by weight which demonstrates that the styrene is more active in cationic copolymerization than is butadiene.

Repair of Cranial Defects with Tantalum

UTOGENOUS bone transplant repair of cranial defects is not completely satisfactory. I t entails an extended or separate operative procedure to secure bone, the size and contour of which leaves something to be desired. A crows-nest appearance may result from a multiple fragment repair and there is some question of the survival of the bone fragments as osseous tissue. An ideal substitute material has yet to be discovered. Such a substance should be readily available, easily worked, preferably workable when cold, strong enough to withstand ordinary trauma, and above all, inert in tissue. Until 1936, when Venable, Stuck and Beach s found that vitallium caused no tissue reaction, a satisfactory substitute for bone was unavailable. In the search for an inert metal, Burch (1938) obtained tantalum* and, for the first time, used it in surgery. 1 Burch and Carney's observations on the inertia of tanta lum in tissues were reported in 194~. 3 Burke (1940) reported that no reaction was produced by tantalum wire in soft tissue. 2 The adaptability of tanta lum to neurosurgery was demonstrated by Pudenz (194~) 6,7. He proved that brain substance and meninges of cats tolerated the metal extremely well and that the skull plate replacements were efficient. Fulcher (1943) 4 reported a case in which he repaired a frontal skull defect with tanta lum sheet metal. Neither Craig nor Spurling have reported their considerable experiences with tantalum in several applications in the field of neurosurgery, t Some information regarding tanta lum will explain its suitability for use in surgery, and particularly in cranioplasty. I t is an element; a heavy metal with a density of 16.6 (about twice tha t of steel). I t reacts only to strong alkalies, hydrofluoric acid, and concentrated or fuming sulfuric acid at ordinary temperatures. I t is virtually non-magnetic and is very high in the E M F Series ~. These attributes obviate the storage-battery effect frequently found in alloys when placed in tissues. Its chemical inertia obviates reactions to body fluids. Tanta lum is workable when cold but cannot be cast. Strength and thermal conductivity are approximately tha t of steel. The coefficient of expansion of tantalum is 50 per cent that of steel, 40 per cent that of copper and 30 per cent that of silver :,. Its workability makes it adaptable to the situation in contrast to stock or specially cast metal replacements. In the range of body temperature, changes in size of the metal are insignificant.

The Absorption of Gasoline Vapor in Natural Gas by Fuming Sulfuric Acid.

The Absorption of Gasoline Vapor in Natural Gas by Fuming Sulfuric Acid.