Hydrogen peroxide Hydrolysis

Organoperoxysulfonic acids and their salts have been prepared by the reaction of arenesulfonyl chlorides with calcium, silver, or sodium peroxide treatment of metal salts of organosulfonic acids with hydrogen peroxide hydrolysis of di(organosulfonyl) peroxides, RS(0)2—OO—S(02)R, with hydrogen peroxide and sulfoxidation of saturated, non aromatic hydrocarbons, eg, cyclohexane (44,181). 

CH3CH2OHCH3. B.p. 82 C. Manufactured by hydrolysis of propene. Used in the production of acetone (propanone) by oxidation, for the preparation of esters (e.g. the ethanoate used as a solvent), amines (diisopropylamines, etc.), glycerol, hydrogen peroxide. The alcohol is used as an important solvent for many resins, aerosols, anti-freezes. U.S. production 1978 775 000 tonnes. 

B). Many nitriles when treated with hydrogen peroxide in warm alkaline solution undergo hydrolysis to amides which can thus be readily obtained in high yield. Insoluble liquid nitriles can be treated directly in the aqueous suspension, but for insoluble solid nitriles the addition of a suitable organic solvent to give a complete solution may be desirable, although the completion of the hydrolysis may not then be so readily detected. 

In this preparation, phenyi-2-nitropropene is reduced to phenyl-2-nitropropane with sodium borohydride in methanol, followed by hydrolysis of the nitro group with hydrogen peroxide and potassium carbonate, a variety of the Nef reaction. The preparation is a one-pot synthesis, without isolation of the intermediate. 

Aldehydes are easily oxidized to carboxylic acids under conditions of ozonide hydroly SIS When one wishes to isolate the aldehyde itself a reducing agent such as zinc is included during the hydrolysis step Zinc reduces the ozonide and reacts with any oxi dants present (excess ozone and hydrogen peroxide) to prevent them from oxidizing any aldehyde formed An alternative more modem technique follows ozone treatment of the alkene m methanol with reduction by dimethyl sulfide (CH3SCH3)... 

A fixed-bed reactor for this hydrolysis that uses feed-forward control has been described (11) the reaction, which is first order ia both reactants, has also been studied kiaeticaHy (12—14). Hydrogen peroxide interacts with acetyl chloride to yield both peroxyacetic acid [79-21-0] and acetyl peroxide... 

Hydrolysis of Peroxycarboxylic Systems. Peroxyacetic acid [79-21-0] is produced commercially by the controlled autoxidation of acetaldehyde (qv). Under hydrolytic conditions, it forms an equiHbrium mixture with acetic acid and hydrogen peroxide. The hydrogen peroxide can be recovered from the mixture by extractive distillation (89) or by precipitating as the calcium salt followed by carbonating with carbon dioxide. These methods are not practiced on a commercial scale. Alternatively, the peroxycarboxyHc acid and alcohols can be treated with an estetifying catalyst to form H2O2 and the corresponding ester (90,91) (see Peroxides and peroxy compounds). 

The electrolytic processes for commercial production of hydrogen peroxide are based on (/) the oxidation of sulfuric acid or sulfates to peroxydisulfuric acid [13445-49-3] (peroxydisulfates) with the formation of hydrogen and (2) the double hydrolysis of the peroxydisulfuric acid (peroxydisulfates) to Caro s acid and then hydrogen peroxide. To avoid electrolysis of water, smooth platinum electrodes are used because of the high oxygen overvoltage. The overall reaction is... 

Rea.ctlons, When free (R-R, R -tartaric acid (4) is heated above its melting point, amorphous anhydrides are formed which, on boiling with water, regenerate the acid. Further heating causes simultaneous formation of pymvic acid, CH COCOOH pyrotartaric acid, HOOCCH2CH(CH2)COOH and, finally, a black, charred residue. In the presence of a ferrous salt and hydrogen peroxide, dihydroxymaleic acid [526-84-1] (7) is formed. Nitrating the acid yields a dinitro ester which, on hydrolysis, is converted to dihydroxytartaric acid [617 8-1] (8), which upon further oxidation yields tartronic acid [80-69-3] (9). 

Acid-cataly2ed hydroxylation of naphthalene with 90% hydrogen peroxide gives either 1-naphthol or 2-naphthiol at a 98% yield, depending on the acidity of the system and the solvent used. In anhydrous hydrogen fluoride or 70% HF—30% pyridine solution at — 10 to + 20°C, 1-naphthol is the product formed in > 98% selectivity. In contrast, 2-naphthol is obtained in hydroxylation in super acid (HF—BF, HF—SbF, HF—TaF, FSO H—SbF ) solution at — 60 to — 78°C in > 98% selectivity (57). Of the three commercial methods of manufacture, the pressure hydrolysis of 1-naphthaleneamine with aqueous sulfuric acid at 180°C has been abandoned, at least in the United States. The caustic fusion of sodium 1-naphthalenesulfonate with 50 wt % aqueous sodium hydroxide at ca 290°C followed by the neutralization gives 1-naphthalenol in a ca 90% yield. 

Peroxomonophosphoric acid can be prepared by the hydrolysis of peroxodiphosphates ia aqueous acid and by the reaction of hydrogen peroxide with phosphorus pentoxide (45). It is not produced or used commercially and the salts that have been prepared are unstable and impure. 

Acidic hydrolysis of these hydroxyaLkyl hydroperoxides yields carboxyUc acids, whereas basic hydrolysis regenerates the parent aldehyde, hydrogen peroxide, and often other products. When derived from either aldehydes or cycHc ketones, peroxides (1, X = OH, = H, R, = alkylene or... 

Acid hydrolysis of peroxides (4) and (5) generates carbonyl compounds (parent ketones or aldehydes) and hydrogen peroxide. Basic hydrolysis of cycHc diperoxides with a-hydrogen (those from aldehydes) yields carboxyHc acids (44) ... 

Petoxycatboxyhc acids have been obtained from the hydrolysis of stable o2onides with catboxyhc acids, pethydtolysis of acyhinida2ohdes, reaction of ketenes with hydrogen peroxide, electrochemical oxidation of alcohols and catboxyhc acids, and oxidation of catboxyhc acids with oxygen in the presence of o2one (181). 

The direct conversion of aniline into aminophenols may be achieved by hydrogen peroxide hydroxylation in SbE —HE at —20 to —40° C. The reaction yields all possible aminophenols via the action of H20" 2 on the anilinium ions the major product is 3-aminophenol (64% yield) (70,71). This isomer may also be made by the hydrolysis of 3-aminoaniline [108-45-2] in dilute acid at 190°C (72). Another method of limited importance, but useful in the synthesis of derivatives, is the dehydrogenation of aminocyclohexenones (73). 

The action of hydrogen peroxide on freshly precipitated hydrated Ti(IV) oxide or the hydrolysis of a peroxide compound such as K2[Ti(02)(S0 2] yields, after drying, a yellow soHd, stable below 0°C, of composition TiO 2H2O. There is one peroxo group per titanium, but the precise stmcture is not known. The yellow soHd loses oxygen and water when heated and Hberates chlorine from hydrochloric acid. When freshly prepared, it is stable in acid or alkah, giving peroxy salts. 

Methylstibonic acid, the only aLkylstibonic acid known with certainty, was not reported until 1990 (144). Previous attempts to obtain aLkylstibonic acids were unsuccessful (144). The methyl compound was prepared by two methods, the hydrolysis of a tetraaLkoxymethylantimony compound or the oxidation of dimethoxymethylstibine [54553-25-2], C3H202Sb, with hydrogen peroxide ... 

Peracid Analysis. Peracid concentrations can be measured in a product or in the bath by use of a standard iodide / thiosulfate titration (60). With preformed peracids or peracids formed via perhydrolysis care must be exercised to minimize the interference of hydrogen peroxide, present intentionally as a component of the perhydrolysis reaction or as a result of the hydrolysis of the peracid (87,88) as shown in equation 18. 

Other Cellulosics. Rayon is bleached similarly to cotton but under milder conditions since the fibers are more easily damaged and since there is less colored material to bleach. Cellulose acetate and triacetate are not usually bleached. They can be bleached like rayon, except a slightly lower pH is used to prevent hydrolysis. The above fibers are most commonly bleached with hydrogen peroxide. Linen, dax, and jute requite more bleaching and mil der conditions than cotton, so multiple steps are usually used. Commonly an acidic or neutral hypochlorite solution is followed by alkaline hypochlorite, peroxide, chlorite, or permanganate, or a chlorite step is done between two peroxide steps. A one-step process with sodium chlorite and hydrogen peroxide is also used. 

The final solution should be checked for absence of free cyanide. The hypochlorite or CI2 + NaOH method is by far the most widely used commercially (45). However, other methods are oxidation to cyanate using hydrogen peroxide, o2one, permanganate, or chlorite electrolysis to CO2, NH, and cyanate hydrolysis at elevated temperatures to NH and salts of formic acid air or steam stripping at low pH biological decomposition to CO2 and N2 chromium... 

---