GB641250A - Process for the manufacture of di-isopropyl-benzene hydro-peroxides and products resulting therefrom - Google Patents
Process for the manufacture of di-isopropyl-benzene hydro-peroxides and products resulting therefromInfo
- Publication number
- GB641250A GB641250A GB1711847A GB1711847A GB641250A GB 641250 A GB641250 A GB 641250A GB 1711847 A GB1711847 A GB 1711847A GB 1711847 A GB1711847 A GB 1711847A GB 641250 A GB641250 A GB 641250A
- Authority
- GB
- United Kingdom
- Prior art keywords
- hydroperoxides
- benzene
- hydroperoxide
- mono
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
- C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
- C07C409/08—Compounds containing six-membered aromatic rings
- C07C409/12—Compounds containing six-membered aromatic rings with two alpha,alpha-dialkylmethyl hydroperoxy groups bound to carbon atoms of the same six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—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
- C07C45/53—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Di-isopropyl-benzene is emulsified in an aqueous solution and the resulting dispersion brought into intimate contact with molecular oxygen at an elevated temperature, whereby the mono- and di-hydroperoxides are formed. The reaction occurs most readily with p-di-isopropyl-benzene, less easily with the m-isomer and not at all or only very slightly with the o-isomer. The commercially available material (obtained as a by-product in the condensation of propylene and benzene) consists of a mixture of all three isomers, from which the p-form can be separated by fractionation. The p-form may be used to prepare the p-hydroperoxides, and the residual mixture of o- and m-forms to give the m-hydroperoxides. Alternatively, the commercial product may be treated directly, when a mixture of m- and p-hydroperoxides is obtained. It is preferred to hydrogenate the commercial product over Raney nickel to remove unsaturated compounds. The aqueous dispersion is preferably made with the aid of emulsifying agents such as alkali stearates, ricinoleates or lauryl sulphates as in Specification 610,293, and is free from heavy metal compounds or other substances which catalyse the decomposition of peroxides. The pH is preferably between 7.5 and 10.5. The oxygen may be pure, or a mixture rich in oxygen or air may be used. The reaction temperature is preferably between 60 DEG C. and the boiling point of the liquid, preferably 80-95 DEG C., and the pressure may be atmospheric or higher. The introduction of oxygen is continued until the peroxides start to decompose, this point being determined by analysis of the mixture. Absorption of oxygen may be promoted by peroxides previously formed in the liquid or added thereto, or by the addition of benzene diazoacetate or lead tetra-acetate which liberate free radicals at the reaction temperature. The process may be continuous or batch. Two methods are available for the separation of the products: (1) the emulsion is allowed to break and is separated while hot into aqueous and oily layers, the former containing some peroxides and being returned for re-use. The p-di-hydroperoxide crystallizes from the oily layer on cooling and is purified by washing with benzene; residual amounts in the liquid are precipitated by adding benzene. The oily layer may be distilled under reduced pressure (before or after crystallization of the p-di-hydroperoxide) to remove unchanged hydrocarbons, and if the distillation is carried to completion some mono-hydroperoxides are found in the distillate. The residue is cooled or diluted with benzene to precipitate any p-di-hydroperoxide, leaving the mono-hydroperoxides and the m-di-hydroperoxide in the liquid fraction. Method (2) may be applied to the product of method (1) or to the initial emulsion, and depends on the relative solubilities of the peroxides in aqueous sodium hydroxide. The mixture is treated with 10 per cent sodium hydroxide and the aqueous and oily layers separated. The former is brought to a pH around 7 (e.g. 6.5-8), preferably by bubbling in carbon dioxide, and the precipitate filtered off and washed with benzene, giving the p-di-hydroperoxide. The benzene is distilled from the washings to give the m-di-hydroperoxide. The oily layer insoluble in 10 per cent sodium hydroxide is treated with 40-50 per cent sodium hydroxide, when the sodium salt of the p-mono-hydroperoxide is precipitated; this can be hydrolysed to the free peroxide by warming with water. The solution from the 40-50 per cent alkali is separated into aqueous and oily layers, the former being rejected. The latter is distilled in vacuo to remove hydrocarbons leaving the m-mono-hydroperoxide. Examples are given. Phenols are obtained by treating the hydroperoxides with mineral acids. Thus the p-mono-hydroperoxide gives p-isopropyl-phenol, and the di-hydroperoxides yield resorcinol and hydroquinone respectively. Ketones result from the treatment of the hydroperoxides with aqueous ferrous sulphate, the mono-hydroperoxides giving isopropylacetophenones and the di-hydroperoxides diacetyl benzenes. Acetone is a by-product in the conversion into phenols as above. Carbinols which are mono- and di-(b -hydroxyisopropyl)-benzenes are obtained by reduction of the hydroperoxides with aqueous sodium sulphite. On dehydration with alkali bisulphates they yield (a -methyl-vinyl)-benzenes. Specification 626,095 also is referred to.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE498321D BE498321A (en) | 1947-06-28 | ||
GB1711847A GB641250A (en) | 1947-06-28 | 1947-06-28 | Process for the manufacture of di-isopropyl-benzene hydro-peroxides and products resulting therefrom |
FR968209D FR968209A (en) | 1947-06-28 | 1948-06-25 | Peroxide compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1711847A GB641250A (en) | 1947-06-28 | 1947-06-28 | Process for the manufacture of di-isopropyl-benzene hydro-peroxides and products resulting therefrom |
Publications (1)
Publication Number | Publication Date |
---|---|
GB641250A true GB641250A (en) | 1950-08-09 |
Family
ID=10089580
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB1711847A Expired GB641250A (en) | 1947-06-28 | 1947-06-28 | Process for the manufacture of di-isopropyl-benzene hydro-peroxides and products resulting therefrom |
Country Status (3)
Country | Link |
---|---|
BE (1) | BE498321A (en) |
FR (1) | FR968209A (en) |
GB (1) | GB641250A (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2785205A (en) * | 1954-07-01 | 1957-03-12 | Hercules Powder Co Ltd | Recovery of phenols |
US2820832A (en) * | 1954-06-18 | 1958-01-21 | Ici Ltd | Production of hydroperoxides |
DE969266C (en) * | 1951-04-28 | 1958-05-14 | Rhone Poulenc Sa | Process for the production of cumene hydroperoxide by the catalytic oxidation of cumene |
US2862857A (en) * | 1954-07-01 | 1958-12-02 | Hercules Powder Co Ltd | Azeotropic distillation of monohydric and dihydric phenols |
US2911391A (en) * | 1952-12-31 | 1959-11-03 | Hercules Powder Co Ltd | Polymer hydroperoxides |
US2915557A (en) * | 1956-06-05 | 1959-12-01 | Shell Dev | Process for recovering di-isopropylbenzene-di-hydroperoxide from di-isopropylbenzene oxidation products |
US2950320A (en) * | 1953-05-27 | 1960-08-23 | Hercules Powder Co Ltd | 5-benzoyl pentanol-1 |
DE1247313B (en) * | 1959-06-24 | 1967-08-17 | Hibernia Ag | Process for the production of diisopropylbenzene dihydroperoxides |
US3993696A (en) * | 1973-05-02 | 1976-11-23 | Sumitomo Chemical Company, Limited | Method for recovering hydroperoxide |
EP0084417A1 (en) * | 1982-01-07 | 1983-07-27 | Sumitomo Chemical Company, Limited | Production of aromatic carbonyl compounds including novel acetophenones |
EP0012613B1 (en) * | 1978-12-14 | 1984-08-08 | Mobil Oil Corporation | A process for producing 3-alkylphenols and 1,3-dihydroxybenzene |
US4929771A (en) * | 1987-12-09 | 1990-05-29 | Ciba-Geigy Corporation | Process for the preparation of alkyl-substituted phenols or naphthols |
EP0796833A2 (en) * | 1996-03-20 | 1997-09-24 | Rütgers Kureha Solvents GmbH | Process for the preparation of hydroxyaromatics |
CN113135819A (en) * | 2021-04-29 | 2021-07-20 | 北京工业大学 | Method for improving yield of resorcinol prepared by m-diisopropylbenzene oxidation |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE947309C (en) * | 1952-06-19 | 1956-08-16 | Rhone Poulenc Sa | Process for the production of hydroquinone |
DE947308C (en) * | 1952-06-19 | 1956-08-16 | Rhone Poulenc Sa | Process for the production of hydroquinone |
DE961168C (en) * | 1952-08-23 | 1957-04-04 | Distillers Co Yeast Ltd | Process for the preparation of m- and p-diisopropylbenzene dihydroperoxides |
US2736753A (en) * | 1952-09-10 | 1956-02-28 | Hercules Powder Co Ltd | Recovery of phenols |
US2790010A (en) * | 1952-12-18 | 1957-04-23 | Hooker Electrochemical Co | Synthesis of meta-substituted phenols |
US2784238A (en) * | 1953-02-21 | 1957-03-05 | Hercules Powder Co Ltd | Catalyst reactivation in process for production of resorcinols |
DE1084731B (en) * | 1953-06-13 | 1960-07-07 | Distillers Co Yeast Ltd | Process for the production of resorcinol |
US2820064A (en) * | 1953-06-24 | 1958-01-14 | Eastman Kodak Co | Autoxidation of hydrocarbons |
US2856432A (en) * | 1953-09-04 | 1958-10-14 | Hercules Powder Co Ltd | Aromatic dihydroperoxide production |
US2856433A (en) * | 1953-09-05 | 1958-10-14 | Hercules Powder Co Ltd | Separation of organic compounds |
DE961708C (en) * | 1953-09-05 | 1957-04-11 | Distillers Co Yeast Ltd | Process for the production of dihydroperoxides from the mixtures obtained in the oxidation of substituted aromatic hydrocarbons |
US2812357A (en) * | 1954-01-12 | 1957-11-05 | Hercules Powder Co Ltd | Removal of hydroperoxide carbinols from aromatic hydroperoxides |
US2805258A (en) * | 1955-05-23 | 1957-09-03 | Koppers Co Inc | Process for the preparation of hydroperoxides from diisopropylbenzenes |
DE1643971C3 (en) * | 1967-07-13 | 1975-04-10 | Bayer Ag, 5090 Leverkusen | m- and p-isopropenylphenyl-dimethylcarbinol and processes for their preparation |
-
0
- BE BE498321D patent/BE498321A/xx unknown
-
1947
- 1947-06-28 GB GB1711847A patent/GB641250A/en not_active Expired
-
1948
- 1948-06-25 FR FR968209D patent/FR968209A/en not_active Expired
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE969266C (en) * | 1951-04-28 | 1958-05-14 | Rhone Poulenc Sa | Process for the production of cumene hydroperoxide by the catalytic oxidation of cumene |
US2911391A (en) * | 1952-12-31 | 1959-11-03 | Hercules Powder Co Ltd | Polymer hydroperoxides |
US2950320A (en) * | 1953-05-27 | 1960-08-23 | Hercules Powder Co Ltd | 5-benzoyl pentanol-1 |
US2820832A (en) * | 1954-06-18 | 1958-01-21 | Ici Ltd | Production of hydroperoxides |
US2785205A (en) * | 1954-07-01 | 1957-03-12 | Hercules Powder Co Ltd | Recovery of phenols |
US2862857A (en) * | 1954-07-01 | 1958-12-02 | Hercules Powder Co Ltd | Azeotropic distillation of monohydric and dihydric phenols |
US2915557A (en) * | 1956-06-05 | 1959-12-01 | Shell Dev | Process for recovering di-isopropylbenzene-di-hydroperoxide from di-isopropylbenzene oxidation products |
DE1247313B (en) * | 1959-06-24 | 1967-08-17 | Hibernia Ag | Process for the production of diisopropylbenzene dihydroperoxides |
US3993696A (en) * | 1973-05-02 | 1976-11-23 | Sumitomo Chemical Company, Limited | Method for recovering hydroperoxide |
EP0012613B1 (en) * | 1978-12-14 | 1984-08-08 | Mobil Oil Corporation | A process for producing 3-alkylphenols and 1,3-dihydroxybenzene |
EP0084417A1 (en) * | 1982-01-07 | 1983-07-27 | Sumitomo Chemical Company, Limited | Production of aromatic carbonyl compounds including novel acetophenones |
US4929771A (en) * | 1987-12-09 | 1990-05-29 | Ciba-Geigy Corporation | Process for the preparation of alkyl-substituted phenols or naphthols |
EP0796833A2 (en) * | 1996-03-20 | 1997-09-24 | Rütgers Kureha Solvents GmbH | Process for the preparation of hydroxyaromatics |
EP0796833A3 (en) * | 1996-03-20 | 1998-04-01 | Rütgers Kureha Solvents GmbH | Process for the preparation of hydroxyaromatics |
US6107527A (en) * | 1996-03-20 | 2000-08-22 | Rutgers Kureha Solvents Gmbh | Process for the production of hydroxy-aromatic substances |
CN113135819A (en) * | 2021-04-29 | 2021-07-20 | 北京工业大学 | Method for improving yield of resorcinol prepared by m-diisopropylbenzene oxidation |
Also Published As
Publication number | Publication date |
---|---|
BE498321A (en) | |
FR968209A (en) | 1950-11-22 |
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