Method of producing 2,6-diisobornyl-4-methylphenol

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 2,6-diisobornyl-4-methylphenol, which is of interest as an antioxidant and stabiliser of polymer materials. The method involves alkylation of p-cresol with camphene as a terpene while heating in the presence of a catalyst selected from a group of aluminium-containing compounds. The reaction mixture is diluted with an organic solvent selected from saturated hydrocarbons (octane, heptane, hexane), petroleum ether, aromatic hydrocarbons, chloroform, dichloromethane, methyl-tert-butyl ether, diethyl ether; aluminium oxide (neutral) and activated carbon are added in ratio of 1-100-0.1-1 in amount of 1-20 wt % to the reaction mixture; after mixing and settling, the sorbents are filtered, washed with an organic solvent and the solvent is evaporated at low pressure.

EFFECT: invention increases technological effectiveness of the process by avoiding formation of large amount of flush water.

9 ex

 

The invention relates to the field of reception of terpenophenols that are of interest as antioxidants and stabilizers of polymeric materials and can be used in various industries, as well as pharmacologically active substances a wide spectrum of action.

A known method of producing terpenophenols [RF Patent №2233262, publ. 27.07.04.], which includes ortho-selective alkylation of phenols by camphene as terpenes when heated in the presence of a catalyst organoaluminium compounds. This alkylation is carried out at 160-190°C, as the source of the phenol used monatomic or diatomic phenols at a molar ratio of phenol and camphene 1-2:1-2. The disadvantage of this method is that the output dialkylamino product 2,6-Diisobutyl-4-METHYLPHENOL not exceed 10%.

There is a method of interaction monoisobutyl-para-cresol with formaldehyde [Thomas H. Newby, Middlebury, Conn., Compositions of matter stabilized with isobornyl derivatives, US patent office, 17, 1953, No. 2628953] at a molar ratio of 2:1 in the presence of epirate boron TRIFLUORIDE at 100°C. the Disadvantage of this invention is the formation of 2,6-Diisobutyl-4-methyl-phenol as a by-product in minimum quantities.

A method of obtaining dialkylamino phenol [Leland J. Kitchen, Akron, Ohio, Rearrangement of terpenyl aryl ethers, US patent office, 9, 191,, No. 2537647] boiling phenylisobornyl ether in benzene solution using as catalyst epirate boron TRIFLUORIDE within 7 hours the Yield of 2,6-Diisobutyl-4-methyl-phenol is 44%. The disadvantage is that the synthesis takes place in two stages. First get phenylisobornyl ester in 11 days, and then spend it exchanged.

A method of obtaining 2,6-Diisobutyl-4-methyl-phenol [Kheifets L.A., Solow L.M., Belov VN, GOH, 1962, T. 32, No. 5, s-1476]by alkylation of p-cresol with camphene in the presence of a 35%aqueous solution BF3in acetic acid at a molar ratio of p-cresol:camphene 1:2. The reaction is carried out at a temperature of 95-100°C at atmospheric pressure. Output dialkylamino product - 2,6-Diisobutyl-4-METHYLPHENOL was 55%.

There is a method of alkylation of p-cresol with camphene in the presence of cresolate aluminum in a molar ratio of p-cresol:camphene 1-2:1 [Youtubehave, Avicodin // Russian journal of chemistry, 2004, vol XLVIII, No. 3, p.31-37]. The reaction is carried out at a temperature of 160-220°C at atmospheric pressure. The disadvantage of this method is low output dialkylamino p-cresol, which amounted to 4.5-20%. The above output is total without specifying the exact ratio dialkylamines p-Cresols with isobornylic, isocamphylic and isovanillin structure of the patient, the new Deputy. The formation of terpenophenols with different structure of terpene fragment inevitably, as the temperature of the reaction medium reaches 220°C.

A method of obtaining 2,6-Diisobutyl-4-METHYLPHENOL, which is the alkylation of p-cresol by camphene when heated in the presence of a catalyst. The alkylation is carried out at a temperature of 20-180°C and a molar ratio of p-cresol:camphene 1:2, and the catalyst used aluminium-containing compounds in amounts of 0.5 to 100 wt.% aluminum to the mass of the original phenol [RF Patent №2394807. 20.07.2010. Bull. No. 20]. This method allows you to get dialkylamino phenols with the release of 80-95% and chosen for the prototype. The disadvantage of this method is the processing of the reaction mixture, which includes the use of mineral acids to decompose the catalyst and, consequently, a large amount of wash water.

The present invention is to improve the technological process. This is the technical result.

The technical result is that the method of obtaining 2,6-Diisobutyl-4-METHYLPHENOL includes alkylation of p-cresol by camphene as terpenes when heated in the presence of a catalyst selected from the group of aluminium-containing compounds according to the invention the reaction mixture is diluted with organic dissolved the LEM, selected from saturated hydrocarbons (octane, heptane, hexane), petroleum ether, aromatic hydrocarbons, chloroform, dichloromethane, methyl tert-butyl ether, diethyl ether, adding aluminum oxide (neutral) and activated carbon in a ratio of 1-100÷0.1-1 in an amount of 1-20 wt.% to the reaction mixture, after stirring and settling sorbents filtered, washed with an organic solvent, the solvent is evaporated under reduced pressure.

The method is as follows.

In addition distinctive features of the prototype is that removal of the catalyst the reaction mixture is diluted with an organic solvent selected from saturated hydrocarbons (octane, heptane, hexane), petroleum ether, aromatic hydrocarbons, chloroform, dichloromethane, methyl tert-butyl ether, diethyl ether, add aluminum oxide (neutral) and activated carbon in a ratio of 1-100-0.1-1 in an amount of 1-20 wt.% to the reaction mixture, after stirring and settling sorbents filtered, washed with an organic solvent, the solvent is evaporated under reduced pressure. The thus treated reaction mixture contains 95 wt.% dialkylamines phenols. The obtained semi-crystalline mass is filled with ethyl alcohol and filtered drop down a white precipitate, the output is basically what about the product 2,6-Diisobutyl-4-METHYLPHENOL was 87%.

The method is illustrated by the following examples.

Example 1. In a two-neck flask of 100 ml equipped with a thermometer and reflux condenser, heat 1.0 g of p-cresol to 180°C. Aluminum shavings (0.1 g) added in small portions. After complete dissolution of aluminum in the phenol solution is cooled to 40°C, then add 2.5 g of camphene (molar ratio of p-cresol:camphene 1:2), the reaction of lead, keeping the temperature to 180°C (control according to GC). Upon completion of the reaction, the reaction mixture was cooled, diluted with an organic solvent (methyl tert-butyl ether), add aluminum oxide (neutral) and activated carbon (in the ratio 10:1) in an amount of 0.11 g, the mixture is stirred for 30 min and defend. Sorbents filtered, washed with an organic solvent. The solvent is evaporated under reduced pressure. The obtained semi-crystalline mass is filled with ethyl alcohol and filtered drop down a white precipitate. The thus treated reaction mixture contains 95 wt.% dialkylamines phenols, the output of the main product 2,6-Diisobutyl-4-METHYLPHENOL is 87%.

Example 2. The process is carried out analogously to example 1, a catalyst for use isopropyl aluminum. The output of the main product 2,6-Diisobutyl-4-METHYLPHENOL is 52%.

Example 3. Alkylation of para-cresol by camphene are similarly note the ru 1 at 140°C, as catalyst, use aluminum hydride. The output of the main product 2,6-Diisobutyl-4-METHYLPHENOL is 4%.

Example 4. The alkylation process is conducted analogously to example 1, except that the solvent used petroleum ether. The output of the main product 2,6-Diisobutyl-4-METHYLPHENOL is 40-50%.

Example 5. The alkylation process is conducted analogously to example 1, except that the solvent used chloroform. The output of the main product 2,6-Diisobutyl-4-METHYLPHENOL is 65%.

Example 6. The alkylation process is conducted analogously to example 1, except that the solvent used CH2Cl2. The output of the main product 2,6-Diisobutyl-4-METHYLPHENOL reaches about 60%.

Example 7. The alkylation process is conducted analogously to example 1, except that the solvent used benzene. The output of the main product 2,6-Diisobutyl-4-METHYLPHENOL is 25%.

Example 8. The alkylation process is conducted analogously to example 1, except that the solvent used hexane. The output of the main product 2,6-Diisobutyl-4-METHYLPHENOL reaches about 40%.

Example 9. The alkylation process is conducted analogously to example 1, except that the solvent used diethyl-the new ether. The output of the main product 2,6-Diisobutyl-4-METHYLPHENOL is 80%.

The method of obtaining 2,6-Diisobutyl-4-METHYLPHENOL, including the alkylation of p-cresol by camphene as terpenes when heated in the presence of a catalyst selected from the group containing aluminum compounds, wherein the reaction mixture is diluted with an organic solvent selected from saturated hydrocarbons (octane, heptane, hexane), petroleum ether, aromatic hydrocarbons, chloroform, dichloromethane, methyl tert-butyl ether, diethyl ether, add aluminum oxide (neutral) and activated carbon in a ratio of 1-100÷0,1-1 in an amount of 1-20 wt.% to the reaction mixture, after stirring and settling sorbents filtered, washed with an organic solvent, the solvent is evaporated under reduced pressure.



 

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