Hydrolysis with oleum

The hydrolysis with oleum can be performed for diiodinated compounds [57] but the reaction was more difficult. 

Chlorofluoroalkane formation via free-radical or cationic reactions of fluoro-olefins is dealt with on pages 82 and 67 the conversion of the CCU-CFsrCFCl telomers CQs [CFs CFa] a (1 < x < 5) into Q-[CFCl CFsli COzH (with 20% oleum at 140 °C) and HOzC-CFz [CFCFCFzlx-i COzH via reaction with oleum at 200 Cor treatment with AICI3 to give CCls [CFz CFClJai-i CFz-Caa followed by hydrolysis with oleum at 140 °C) is mentioned later (p. 154). ... 

In an alternative method of preparing m/vo-dihydroxyanthraquinonedisulfonic acid by heating the title compound with oleum to effect simultaneous hydrolysis, denitration and sulfonation of the nucleus, there is the possibility of formation of methyl nitrate from the scission fragments. 

Aminopyridine has been prepared by heating nicotinamide in an alkaline potassium hypobromite solution at 70° by hydrolysis of 8-pyridylurethan with oleum by heating 3-amino-pyridine-2-carboxylic acid at 250° by reduction of 3-nitro-pyridine with zinc and hydrochloric acid and by heating 3-bromopyridine with ammonia and copper sulfate in a sealed tube. ... 

Following initial studies in 1974 the preparation of TPPTS was carried out via the sulfonation of TPP with oleum (i.e., concentrated sulfuric acid containing 20% by weight of S03) at 40 °C in one day. After hydrolysis and neutralization by NaOH, an aqueous solution of sodium sulfate and a mixture of different P compounds - consisting mainly of TPPTS and the corresponding P-oxide ( TPPOTS ) as key chemical species - were obtained (Scheme 1) [20],... 

Because of the chemical inertness of perchloroarene nuclei, hydrolyses in perchloro-organic chemistry are frequently and most conveniently effected with oleum. If the stability of the intermediate carbenium ion is very high (for example because of charge delocalization), then its formation becomes quite apparent by its deep colour, and the hydrolysis takes place in the subsequent aqueous treatment. However, if its stability is comparatively low, a carbenium ion sulphate is the stable species that subsequently undergoes hydrolysis. In the treatment of [26] with oleum, a deep-blue solution of the carbenium ion [27] is formed initially, and is gradually converted into an almost colourless suspension of chlorosulphonate [28]... 

Because of steric shielding, the hydrolysis of aromatic chlorinated esters and amides cannot be carried out under normal conditions, not even with the Hammett-Newman method, i.e. treatment with concentrated sulphuric acid and then with water. For comparison, the hydrolysis of highly hindered esters, such as ethyl mesitoate, can readily be performed in concentrated sulphuric acid (Treffers and Hammett, 1937 Newman et al., 1945). Hydrolysis of the perchlorinated esters can be effected with oleum in excellent yields. (To perform that of perchloroamides, hot (160°C) oleum is required (Ballester et al., 1978b).) It is assumed that the mechanism of hydrolysis for perchloroesters with oleum is analogous to that proposed by Newman, i.e. 

Treatment of / -methoxyheptachlorostyrene with oleum affords / -hydroxy-heptachlorostyrene. The hydrolysis of a,/ -dimethoxyhexachlorostyrene by means of concentrated sulphuric acid gives a//-/ -ethoxyhexachloroaceto-phenone (Ballester et al., 1980e) total hydrolysis can be accomplished with oleum. It is noteworthy that hydrolytic oxidation results from the direct treatment of dimethoxyhexachlorostyrene with oleum, 4-methoxytetra-chlorobenzoic acid being the product (79). 

The first step consists of the air oxidation of cyclohexane to a mixture of cyclohexanol and cyclohexanone as described in section 10.2.2(a). The mixture is passed over a zinc oxide catalyst at about 400°C, when most of the cyclohexanol is dehydrogenated to cyclohexanone. The cyclohexanone is separated by distillation and is then treated with aqueous hydroxylamine sulphate at about 100°C to form the oxime. The reaction mixture is neutralized with aqueous ammonia or sodium hydroxide and the crude oxime separated as an oily layer. This is stirred with oleum (sulphur trioxide in sulphuric acid) at 120°C and the oxime undergoes the Beckmann rearrangement to give caprolactam. In one process, the solution containing the lactam is continuously withdrawn from the reactor and rapidly cooled to below l C to minimize hydrolysis. The solution is then further cooled and neutralized with aqueous ammonia. Crude caprolactam separates as an oil and is purified by distillation under reduced pressure or by recrystallization. 

Ammonium fluorosulfate is produced from ammonium fluoride by reaction with sulfur trioxide, oleum, or potassium pyrosulfate, 1 2820 (48). Solutions of ammonium fluorosulfate show Htfle evidence of hydrolysis and the salt may be recrystallized from hot water. Ammonium fluorosulfate absorbs anhydrous ammonia to form a series of Hquid amines that contain 2.5—6 moles of ammonia per mole of salt (77). 

Davies and Reider (1996) have given some details of the HIV protease inhibitor CRDCIVAN (INDINAVIR) for which (lS,2R)-c -amino indanol is required. Indene is epoxidized enantioselectively, using the lacobsen strategy (SS-salen Mn catalyst, aqueous NaOH and PiNO), to (lS,2/ )-indene oxide in a two-phase system, in which the OH concentration is controlled. Indene oxide was subjected to the Ritter reaction with MeCN, in the presence of oleum, and subsequent hydrolysis and crystallization in the presence of tartaric acid gives the desired amino indanol. 

H acid (4.2) is possibly the most important single naphthalene-based intermediate. The preparation of this intermediate starts with a high-temperature sulphonation of naphthalene using 65% oleum (anhydrous sulphuric acid in which 65% by mass of sulphur trioxide has been dissolved) to give mainly naphthalene-1,3,6-trisulphonic acid, the nitration product from which is purified by selective isolation. Reduction of the nitro group followed by hydrolysis of the 1-sulphonic acid substituent by heating with sodium hydroxide solution at 180 °C completes the process (Scheme 4.27). 

The HjC-O-Te bonds are remarkably stable no cis-trans isomerization was observed when the hydroxy methoxy tellurium tetrafluorides were kept at temperatures below 130°. The bonds are not cleaved by 65% oleum or chlorosulfonic acid at room temperature, instead, the sulfate esters HjCO-TeF tO-SOjH) were formed. These sulfate esters were transformed to HO-TeFiCO-SOjH) upon heating to 100°. Cesium chloride dissolved in an excess of cis- or /run.s-hydroxy methoxy tellurium tetrafluoride liberated hydrogen chloride with the formation of very hygroscopic cesium methoxo(oxo)letrafluorotellurates(VI). Trunj-hydroxy methoxy tellurium tetrafluoride reacts instantaneously with water with loss of fluoride. The cu-compound is stable toward hydrolysis at room temperature. ... 

Methylaminoanthraquinone has been prepared from 1-chloro-, 1-bromo-, and 1-nitroanthraquinone by treatment with alcoholic methylamine under pressure from 1-methoxy- and 1-phenoxyanthraquinone with methylamine in pyridine solution at 150° from potassium anthraquinone-1-sulfonate with aqueous methylamine at 150-160° from 1-aminoanthraquinone by treatment with formaldehyde, or methyl alcohol in sulfuric acid or oleum and by hydrolysis of />-toluenesulfonyl-methylaminoanthraquinone with sulfuric acid. ... 

A polymerisation variant is to use as catalyst oleum (a 30-60% solution of SOs in sulfuric acid), or better, in order to accelerate the reaction, a catalytic mixture of oleum-perchloric acid (or a perchlorate, such as magnesium perchlorate) [12,16,25,28]. Similar structures with sulfate ester units (structure 7.7) are obtained. By the hydrolysis of the resulting structure the desired PTHF with terminal hydroxyl groups is obtained [13, 25, 28]. 

ACETIC ACID, ZINC SALT (557-34-6 5970-45-6, dihydrate) Zn(CjH302)2 Zn(C2H302)2 2H20 Noncombustible solid. Moisture may cause hydrolysis or deconq)osition. Aqueous solution is a base. Incompatible with strong oxidizers, acids, oleum, strong bases. Thermal decomposition above 1472°F/800°C releases oxides of zinc and carbon and acetic acid fumes. 

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