Hydrogen peroxide from propane

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

Chlorine dioxide Copper Fluorine Hydrazine Hydrocarbons (benzene, butane, propane, gasoline, turpentine, etc) Hydrocyanic acid Hydrofluoric acid, anhydrous (hydrogen fluoride) Hydrogen peroxide Ammonia, methane, phosphine or hydrogen sulphide Acetylene, hydrogen peroxide Isolate from everything Hydrogen peroxide, nitric acid, or any other oxidant Fluorine, chlorine, bromine, chromic acid, peroxide Nitric acid, alkalis Ammonia, aqueous or anhydrous Copper, chromium, iron, most metals or their salts, any flammable liquid, combustible materials, aniline, nitromethane... 

This trimeric propylidene peroxide , formed from propanal and hydrogen peroxide, is an extremely explosive and friction-sensitive oil. 

It is possible to obtain anti-Markovnikov products when HBr is added to alkenes in the presence of free radical initiators, e.g. hydrogen peroxide (HOOH) or alkyl peroxide (ROOR). The free radical initiators change the mechanism of addition from an electrophilic addition to a free radical addition. This change of mechanism gives rise to the anh-Markovnikov regiochemistry. For example, 2-methyl propene reacts with HBr in the presence of peroxide (ROOR) to form 1-bromo-2-methyl propane, which is an anh-Markovnikov product. Radical additions do not proceed with HCl or HI. 

The experimental results obtained with these reactors are summarized in Table I. Both reaction temperature and the molar ratio of propane to oxygen in the feed were kept constant at 430°C. and 3, respectively, while residence time was varied from 5 to 15 sec. Each experimental run was continued for about 4 hours. The hydrogen peroxide concentration in the liquid product sample was frequently checked by titration during the run. After the constant analytical value was attained, the products were subjected to the analytical procedure described before for obtaining the data given in the table. 

The main products were hydrogen peroxide, methanol, formaldehyde, acetaldehyde, and water. The change in mole ratio of propane and oxygen in feed from 2 to 8 had almost no influence upon the hydrogen peroxide formation. The yields of methanol, formaldehyde, and acetaldehyde increased and that of water decreased with decreasing mole ratio... 

Fig. 15. The influence of the pic d arret on product forrhation during the oxidation of propane. Initial temperature = 430 °C initial pressure of propane = 90 torr initial pressure of oxygen = 210 torr volume of reaction vessel = 30 cm , (b) Left ordinate +, methyl alcohol. Right ordinate x, isopropyl alcohol , ethyl alcohol o, n-propyl alcohol 1, allyl alcohol, (c) Left ordinate +, hydrogen peroxide , formaldehyde. Right ordinate x, total aldehydes, (d) +, propene i, methane , ethylene x ethane. (From ref. 147.)...

However, there is another way in which the overall conversion from propene to propan-l-ol may be accomplished. This proceeds by the indirect route of hydroboration, using diborane, followed by the oxidation of the resultant trialkylboron with alkaline hydrogen peroxide. For the present purposes, we are only concerned with the reaction between diborane and the alkene. Diborane is generated in situ, but reacts as if it were the monomer BH3, which is a Lewis acid. Write down the... 

Figure 9.5-2 The excess Gibbs energy for several mixtures. Curve 1 Trimethyl methane (1) and benzene at 0°C. [Data from V. Mathot and A. Desmyter, J. Chem. Phys. 21, 782 (1953).] Curve 2 Trimethyl methane (1) and carbon tetrachloride at 0°C. [Data from ibid.] Curve 3 Methane (1) and propane at 100 K. [Data from A. J. B. Cutler and J. A. Morrison, Trans. Farad. Soc., 61, 429 (1965).] Curve 4 Water (1) and hydrogen peroxide at 75°C. [From the smoothed data of G. Scatchard, G. M, Kavanagh, and L. B. Ticknor, J. Am. Chem. Soc., 74, 3715 (1952).]...

Still other approaches to methods for cost reduction have been patented for the formation of hydrogen peroxide by direct oxidation of hydrogen and of hydrocarbons, such as propane, n-butane, and isobutane and for its recovery from the aqueous solutions thus formed. 

Spin-traps DMPO (5,5-dimethyl-l- pyrroline-N-oxide), MNP (2-methyl-2-nitroso-propane, dimer), dG (2 -deoxyguanosine monophosphate), 8-HOdG standard (8-hydroxy-2 -deoxyguanosine) and deferoxamine mesylate were purchased from Sigma phosphate buffer (pH 7.4), hydrogen peroxide (H2O2) (30%), were purchased from Merck. All other chemicals used were of analytical quality. 

Hydroboration of tra s-2-(l-propenyl)furan and tra s-2-(l-propenyl) thiophene with BMS, 9-BBN, ChXjBH, and SiajBH proceeds smoothly, and the or-ganoborane thus obtained on oxidation with alkaline hydrogen peroxide yields the main product l-(2-furanyl)-propan-l-ol, in about 90% yield arising from... 

DFP is stable and in the absence of moisture can be stored for considerable periods without decomposition. Hydrolysis in neutral aqueous solution occurs slowly. The reaction is catalyzed by both acid and base. At pH>7, hydrolysis is proportional to the hydroxide ion concentration and at high pH is extremely rapid. The product is always diisopropyl phosphoric acid (equation 38), except under more forcing conditions which eventually produce phosphate (and propan-2-ol). The hydrolysis is strongly catalyzed by the addition of a-effect nucleophiles such as hypochlorite, peroxide, hydroxylamine, hydroxamic acid and their substituted derivatives . Under basic conditions, such nucleophiles (HOX) are present as the anion and are responsible for the rapid initial displacement of fluoride ion from DFP to give intermediate 36 shown in equation 39. Displacement of OX by hydroxide ion regenerates the catalytic OX anion. The reaction with hydrogen... 

---