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 widely used in different industries as an antioxidant, as well as an initial component in synthesis of surfactants and fragrance compounds. The method involves alkylation of p-cresol with camphene while heating in the presence of a catalyst. Alkylation is carried out while heating to 20-180°C and with molar ratio of p-cresol to camphene equal to 1:2. The catalyst used is an aluminium-containing compound taken in amount of 0.5-100 wt % aluminium to the mass of the initial phenol.

EFFECT: method enables to obtain an end product with high selectivity and output.

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The invention relates to the field of reception of terpenophenols, which are widely used in various industries as antioxidants but also as the source components in the synthesis of surfactants and aromatic substances, as well as the physiologically active substance is 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 mono-isobornyl-para-cresol with formaldehyde [Thomas H. Newby, Middlebury, Conn., Compositions of matter stabilized with isobornyl derivatives, US patent office, 17, 1953, No. 2,628,953] at a molar ratio of 2:1. The alkylation is carried out at 100°C in the presence of epirate boron TRIFLUORIDE. 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 [Leiand J. Kitche, Akron, Ohio, Rearrangement of terpenyl aryl ethers, US patent office, 9, 1951, No. 2,537,647] 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 dialkylamino phenol [Fomenko CENTURIES, D.V. Korchagina, Salakhutdinov NF, Bagryanskaya YOU, Gatilov J.V., Jonah KG, Barkhash VA, the Journal of organic chemistry, issue 4, 2000, s-576] in the presence of methylene chloride. According to this method, the molar ratio of 2,3-dimethylphenol:camphene 1:5 at room temperature the reaction mixture and the duration of reaction 8 o'clock the Output of products of alkylation was 51%, the output disubstituted phenols was 5%. The disadvantage of this method is the formation of dialkylamines phenols with 1,4,7-anticreativity[2.2.1]heptylene structure Deputy.

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 F3in 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 and other Natural synthetic terpenophenols. Russian chemical journal, 2004, vol XLVIII, No. 3, p.31-37], we have chosen for the prototype. 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 terpenic Deputy. The formation of terpenophenols with different structure of terpene fragment inevitably, as the temperature of the reaction medium reaches 220°C.

The present invention is to increase the selectivity of the process and increasing the yield of 2,6-Diisobutyl-4-METHYLPHENOL.

The present invention allows for the alkylation of phenols using as catalysts organoaluminium compounds, mineral acids, zeolites, cation exchange resin, clay, in addition, allows to increase the conversion of p-cresol to 75-100% with the release of dialkylamines phenols 80-95%. This is the technical result is subramania.

The technical result is achieved in that a method of obtaining 2,6-Diisobutyl-4-METHYLPHENOL, including the alkylation of p-cresol by camphene as terpenes when heated, as a catalyst choose aluminium-containing compounds in amounts of 0.5 to 100 wt.% aluminum to the mass of the original phenol, according to the invention, the alkylation is carried out by heating to 20-180°C, the molar ratio of p-cresol:camphene 1:2, as organoaluminium connections use phenoxide and alkoxides of aluminum unbalanced (mixed) or symmetric (full) type. In addition, as a catalyst used phenoxide aluminum when heated to 180°C; isopropyl aluminum when heated to 180°C; the hydride of aluminum when heated to 140°C; montmorillonite-KSF in the amount of 100 wt.% when heated to 20-100°C.

The method is as follows.

Phenoxide aluminium receive in situ by heating aluminum in a solution of the corresponding phenol. Using the interaction of phenol with aluminum-alkoxide and alyuminiiorganicheskikh compounds or aluminum hydride (alkyl radical from C2to C20) in situ get mixed or full phenoxide. Use the hydrides of aluminium full or mixed type (containing the alkyl radical from C4to C8).

In addition distinctive features of the prototype is alkilirovanie of p-cresol with camphene in the presence of zeolite TS-10 and montmorillonite KSF. As a consequence, the reaction products contain the monosubstituted esters and para-Cresols with different structure of terpene Deputy. Therefore, it is preferable to use alkoxide aluminum catalysts, which avoids the formation of by-products and to increase the output dialkylamino phenol up to 80-95% (in the prototype, 55%).

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 g of p-cresol to 180°C. Aluminum shavings (0.1 g) is 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 the lead, maintaining the temperature of 180°C, until complete conversion of the camphene (control according to GC). Upon completion of the reaction, the reaction mixture was cooled, diluted with diethyl ether, mineral acid is added to decompose the catalyst, and then washed with an alkaline solution to remove excess phenol, water until neutral. The organic layer is dried over anhydrous Na2SO4and evaporated the solvent. The thus treated reaction mixture contains 95 wt.% dialkylamines phenols.

Experimental data of examples 2-9 are shown in the table.

Example 2. The process is carried out analogously to example , as the catalyst used isopropylate aluminum.

Example 3. Alkylation of para-cresol by camphene behave analogously to example 1 at 140°C as the catalyst use aluminum hydride.

Example 4-6. The process of alkylation of para-cresol are similar to example 1 at 20°C, 40°C and 100°C as the catalyst used zeolite TS-10.

Example 7-9. The process of alkylation of para-cresol by camphene behave analogously to example 1. As the catalyst used KSF-montmorillonite. Alkylation of para-cresol is carried out at 40°C, 70°C and 100°C.

Monitoring the progress of reactions and the identity of the substances was carried out by TLC on Silufol UV-254 plates (eluent - hexane:diethyl ether 3:1), and by GLC using chromatograph "Crystal 2000", capillary column HP-5MS, 60m, 0.251mm, temperature 100-240°C, heating 6°/min, carrier gas - argon. IR spectra were recorded on a Specord M-80 in a thin layer on KBr plates. The NMR spectra of1H and13With recorded spectrometer "Bruker AM-300" (300 and 75 MHz, respectively), the internal standard chloroform, solvent CDCl3.

Table
No. AveSource p-cresolThe molar ratio of p-cresol:camphene The catalyst, wt.% Al by weight of phenolTemperature, °CConversion, %Content dialkylamines phenols, %The content of 2,6-Diisobutyl phenol, %
1p-cresol1:2(ArO)3Al
1,0
180958474
2p-cresol1:2(i-PrO)3A1
1,0
180827052
3p-cresol1:2AlH3
1,0
1409054
4p-cresol1:2zeolites2042--
5 p-cresol1:2zeolites409211
6p-cresol1:2zeolites1009526
7p-cresol1:2KSF20991
8p-cresol1:2KSF7098205
9p-cresol1:2KSF10095338

1. The method of obtaining 2,6-Diisobutyl-4-METHYLPHENOL, including the alkylation of p-cresol by camphene when heated in the presence of a catalyst, Otley is audica fact, the alkylation is carried out by heating to 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.

2. The method according to claim 1, characterized in that the alkylation is carried out at 180°C, and the catalyst used phenoxide aluminum.

3. The method according to claim 1, characterized in that the catalyst used isopropylate aluminum when heated to 180°C.

4. The method according to claim 1, characterized in that the catalyst used hydride aluminum when heated to 140°C.

5. The method according to claim 1, characterized in that the catalyst used montmorillonite - KSP in the amount of 100 wt.% when heated to 20 to 100°C.



 

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