It is oxidized to a hydroperoxide, akin to the production of cumene hydroperoxide. A selectivity to phenol as high as 90 percent and higher is attainable in the present process with the major by-product being alphamethylstyrene, which can be recovered and hydrogenated to cumene for recycle in the process. Analysis showed a selectivity to phenol of 86 percent, to alphamethylstyrene of 12 percent and to acetophenone of 2 percent. explosion is high. 9, 343 (1953). Fine Chem. Soc. A 57.3 percent solution of cumene hydroperoxide in cumene was added dropwise into 100 ml. On the other hand, the reaction is too slow with too little catalyst. In using sulfuric acid as the decomposition catalyst, a selectivity to phenol of about 85 to 95 percent is generally obtained. temperature over a shorter time, and simple workup procedures for small A chiral (1S,2S)-cyclohexanediamine backbone salen-zirconium(IV) M. V. Lomonosov Institute of Fine Chemical Technology, Moscow, You can also search for this author in (1) Oxidation process where cumene is oxidized in air to obtain cumene hydroperoxide (CMHP). J. W. Fordham and H. L. Williams, Can. In this process the cumene hydroperoxide instantaneously decomposes to phenol and acetone as it is slowly added in solution with cumene to the mineral acid solution. In the first step, a pair of electrons on the oxygen of the hydroperoxide's “hydroxyl group” is attracted to a proton of the H 3 O + molecule, forming an oxonium ion. R. Spolsky and H. L. Williams, Ind. ;REEL/FRAME:004610/0801, Free format text: Nitroarenes react with anions of tert-butyl and cumyl The order of the reaction was determined with respect to all the reaction components, and the activation energy was calculated for the over-all reaction. Free format text: L. Homer, J. Polymer Sci. (293 ppm.) In all experiments there was greater than 95 percent conversion of the cumene hydroperoxide. 60, 1215 (1938). Migration of the phenyl group to form a carbocation. Analysis of the product showed that 99.9 percent of the cumene hydroperoxide had reacted at a selectivity of 93 percent to phenol. Organ. Since the cleavage reaction is highly exothermic, temperature control of the reaction liquid is generally provided. (384 ppm.) They differ in the catalyst or amount of catalyst which was added to the cumene hydroperoxide at 60° C., the maximum temperature which occurred and the total reaction time. The reaction usually proceeds in high yields and is of Generally, the pressure will range from a pressure moderately below to moderately above atmospheric pressure. Learn more about Institutional subscriptions. Moreover, the selectivity of this phenol catalyzed decomposition of cumene hydroperoxide is very poor, being less than 80 percent selectivity to phenol as determined by a study of the reaction. The non-selective decomposition product particularly as catalyzed by a strong mineral acid includes cumyl alcohol, acetophenone, methylbenzofuran, several organic acids, mono- and dicumylphenol, diacetone alcohol, acetol, mesityl oxide, phorone, alpha-methylstyrene and various oligomers of alpha-methylstyrene which are tar-like substances. Subscription will auto renew annually. The analyses for compounds other than hydroperoxide and boron were accomplished by gas chromatography or by a high performance liquid chromatography. J. M. Kolthoff, and E. J. Meeban, J. Polymer Sci. A new and Within these constraints the concentration of the catalyst can be as low as about 20 parts per million parts of total reaction liquid (ppm.) - Tao, S.-J. The reactor was charged with 22 g. of a 20 percent solution of cumene hydroperoxide (CHP) which heated to 60° C. After the solution had reached a temperature of 60° C., 0.5 ml. Cumene hydroperoxide is treated with dilute HCL to yield phenol and acetone. of the catalyst. The temperature rose to a maximum temperature of 80° C. and after 30 minutes the reaction was substantially complete. Cumene hydroperoxide [Wiki] 1-Methyl-1-phenylet hyl hydroperoxide. This temperature control can be accomplished by controlling the amount of catalyst used or by controlling the rate at which the catalyst is mixed with the cumene hydroperoxide. R. Kino, K. Daikai, T. Kawanami, H. Furuno, J. Inanaga, Org. A maximum temperature of 74° C. was reached. at room temperature, but the potential for an uncontrolled reaction and An I2/CHP-mediated cross-coupling reaction of isocyanides with The degradation of the cumene hydroperoxide proceeds via a carbocation mechanism. After 20 minutes of reaction time, analysis showed a selectivity of 79 percent to phenol, 20 percent to alpha-methylstyrene and one percent to acetophenone. (1,060 ppm.). Step 3. The temperature rose to 85° C. After 40 minutes reaction time, analysis of the products showed a selectivity of 91 percent to phenol and 9 percent to alpha-methylstyrene. A. Chaltykian, in the Collection “Questions of Chemical Kinetics and Reactivity,” (Izd. W. H. Embree, R. Spolsky, and H. L. Williams, Ind. The decomposition product resulting from the Lewis acid catalyzed reactions was light yellow in color and transparent, indicating very slight tar, while the sulfuric acid catalyzed product liquid was black and opaque. The maximum amount of cumene hydroperoxide in the cleavage reaction liquid will suitably be about 20 weight percent, preferably about 10 percent and most preferably about 5 percent. 130, 8134-8135. In this oxidation reaction the maximum concentration of cumene hydroperoxide that can conveniently be produced is about 30 percent. R. J. Ohrr and H. L. Williams, Disc. Cumene hydroperoxide is decomposed to phenol and acetone using a Lewis acid catalyst of the group tungsten hexafluoride, silicon tetrafluoride, stannous chloride, stannic fluoride, antimony pentachloride, sulfur monochloride and sulfur tetrafluoride. B. Lamb and A. G. Jacques, J. The solvent used in this process can be the cumene associated with the cumene hydroperoxide as described above. cumene hydroperoxide, Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds, Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition, Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides, CHEVRON RESEARCH COMPANY, SAN FRANCISCO, CA. Cumene Hydroperoxide (CMHP, CHP) Cumene hydroperoxide is a relatively stable organic peroxide. Soc. Cumene can be readily oxidized with air to form cumene hydroperoxide and the hydroperoxide can then be decomposed to form equal molar amounts of phenol and acetone. Phys. Protonation of cumene hydroperoxide. The activity of iron salts depends on the experimental conditions and its variation is probably to be explained by the hydrolysis of these salts. Lett., Wang, Y.-Q. It was shown that the amine is able to reduce ferric salts, both in acid and in alkaline media. Ji, Org. PubMed Google Scholar, Razumovskii, S.D., Medvedev, S.S. Kinetics of the reaction between cumene hydroperoxide and triethylenetetramine in presence of iron salts in aqueous solutions. It was shown that the amine is able to reduce ferric salts, both in acid and in alkaline media. under mild conditions. A total of 35.2 g. of the cumene hydroperoxide was added over 60 minutes. When operating under the general conditions described herein, particularly within a temperature range between about 60° and 80° C., the decomposition reaction to substantial completion, as a batch or as a continuous process, will take place in about two minutes to about two hours, and preferably will take place in about five to about 45 minutes. It was determined that the selectivity to phenol was 91 percent, to alpha-methylstyrene 8 percent and to acetophenone one percent. MECHANISM. 2017, 19, 448-451. In this reaction 0.02 g. (910 ppm.) Am. of a two percent solution of sulfuric acid in acetone in a 300 ml. 16, 113 (1951). ;ASSIGNOR:GULF RESEARCH AND DEVELOPMENT COMPANY, A CORP. OF DE. and about 0.5 weight percent of the catalyst. Cumene hydroperoxide-induced calcium release from mitochondria has been studied. Decomposition of cumene hydroperoxide using a Lewis acid catalyst, Application filed by Gulf Research and Development Co. A COR, Free format text: ;ASSIGNOR:GULF RESEARCH AND DEVELOPMENT COMPANY, A CORP. OF DE. However, since phenol and acetone are the desired reaction product, a phenol-acetone solvent is generally desirable in order to simplify product separation. complex as the catalyst enables a highly enantioselective α-hydroxylation of developed for the epoxidation of α,β-unsaturated ketones, thus providing A 0.2 M solution in benzene has a half-life of 29 hours at 145°C. When the reaction product is distilled, these by-products remain in the residue which is collectively called "tar" or "tars". After the cumene hydroperoxide reached 60° C., 0.002 g. (91 ppm.) A 0.5 ml. The cumene hydroperoxide can desirably be prepared by oxidation of cumene with air in the conventional manner. Other usable solvents include aromatic solvents such as benzene, toluene, and the like; ethers such as diethyl ether and tetrahydrofuran, or any other solvent which is compatible with the reactant and catalyst and can be conveniently separated. This production method is made up of the following processes. Soc. The following reactions were carried out in a glass reactor equipped with a magnetic stirrer and operated at a pressure within the reactor slightly above atmospheric pressure. The desired decomposition of cumene hydroperoxide is a cleavage to equal mols of phenol and acetone, that is, about 62 weight percent phenol and 38 weight percent acetone. Am. The reactor was cooled by a cold finger in the liquid. The catalyst of this invention is a Lewis acid selected from the group tungsten hexafluoride, silicon tetrafluoride, stannous chloride, stannic fluoride, antimony pentachloride, sulfur monochloride and sulfur tetrafluoride. β-keto esters using cumene hydroperoxide (CHP) as the oxidant to provide chiral 18, 438 (1955). It has been reported that the main products in this "tar" are cumylphenol and dicumylphenol, the polymers of alpha-methylstyrene, acetophenone and diacetone alcohol.