The way to obtain ortho-terpenophenols

 

(57) Abstract:

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 fragrances. The method includes ortho-selective alkylation of phenols by camphene as terpenes when heated in the presence of a catalyst - organoaluminium compounds, the alkylation is carried out at 160-190S, as a source of phenol using monatomic or diatomic phenols at a molar ratio of phenol and camphene 1-21-2. Organoaluminium compound selected from phenoxides or alkoxides of aluminum unbalanced (mixed) or symmetric (full) type in the amount of 0.5-1 wt.% aluminum to the mass of the original phenol. Preferably use phenoxide aluminum, non-derivative from the original phenol. The invention allows to increase the conversion rate of camphene to 100% with the content of ortho-terpenophenols about 80 to 98%. 1 C.p. f-crystals, 1 table.

The invention relates to the field of reception of terpenophenols, which are widely used in various industries as antioxidants but also as a source to which the enol [Patent US 2537636, 09.01.1951] condensation of phenol (isomeric Cresols, various xylenols, tri-ALKYLPHENOLS and so on) with camphene in the presence of an acid catalyst (such as a mineral acid, ferric chloride, silica, etc.,) when heated to 70-130C. The use of acid catalysts for the alkylation of phenols is held in ortho-and para-position relative to the hydroxyl group, and thus is formed a mixture of ortho - and para-terpenophenols (data output not shown), which the authors and used as stabilizers for rubber polymers.

There is a method of alkylation of phenols [Patent WO 02055461, 18.07.2002] Diisobutylene, camphene, limonene, a-pinene and other aliphatic olefins series in the presence of a mixture of sulfonic acids and sulfuric acid in a molar ratio of them in the range of 0.3:1 to 3:1. The reaction is carried out at a temperature of 35-75S at atmospheric or increased pressure. The output products of the alkylation of hydroquinone Diisobutylene was 70-75% (product purity of 98.5%). However, the authors in the examples do not give a description of the reaction of hydroquinone with terpene hydrocarbons. It is known that in acidic conditions terpenes undergo various intramolecular rearrangement. Therefore it is impossible to make vyazannykh acid catalysts.

Known most selective way to obtain ortho-terpenophenols [Chemistry and technology of aromatic substances and essential oils, proceedings vol.8, M: Food industry. 1968, S. 142-190], we have chosen for the prototype, when used as a catalyst phenoxide aluminum. According to this method, the molar ratio of phenol:camphene 1.5 to 2.5:1, the amount of aluminum is 1.2 to 3% by weight of phenol, the temperature of the reaction mixture 155-S when the duration of the reaction of 3,5-4 hours. The output of products of alkylation was 53-87%, the yield of ortho-substituted phenols was 45-87%.

The present invention is to increase the selectivity of the process and increasing the yield of ortho-alkylated product.

The present invention allows for the alkylation of one - and diatomic phenols, be used as catalysts organoaluminium connection, and not only derived from the original phenol phenoxide aluminum, in addition, allows to increase the conversion rate of camphene to 75-100% with the release of ortho-terpenophenols 60-98%. This is the technical result of the invention.

In common with the prototype is that the way to obtain ortho-terpenophenols includes alkylation of monohydroxy phenols by camphene in Kay aluminum.

The distinctive feature is that as the initial phenol optionally use the diatomic phenols, the molar ratio of phenol and camphene 1-2:2-1, respectively, organoaluminium compound optionally selected from the group of alkoxides (ethylate, isopropylate, activit-) aluminium asymmetrical (mixed) or symmetric (full) type in the amount of 0.5-1 wt.% aluminum to the mass of the original phenol, with an option to use phenoxide aluminum - non-derivative from the original phenol.

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

The proposed method may alkylation diatomic phenols in the presence of aluminium phenolate, however, this is accompanied by a change in the composition of the catalyst, which is associated with the exchange reaction phenoxide groups. As a consequence, the reaction products contain the corresponding ALKYLPHENOLS (5%) as by-products. Therefore, it is preferable to use alkoxide aluminum katalysatoren with the prototype was able to significantly increase the conversion rate of camphene to 100% and increase yields of ortho-terpenophenols up to 98% (in the prototype 45-87%).

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, heated to 11.0 g of phenol up to 160S. Aluminum shavings (0.1 g) is added in small portions. After complete dissolution of aluminum in the phenol solution is cooled to 40C, then add 14.5 g of camphene (molar ratio of phenol:camphene 1:1). The reaction of lead, keeping the temperature 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 according to the results of GLC analysis contains 90 wt.% ortho-terpenophenols.

Experimental data of examples 2-8 are shown in table.

Example 2. The process is carried out analogously to example 1 at a ratio of phenol:camphene 1:2.

Example 3. Alkylation of phenol by camphene behave analogously to example 1 with 160S, as the catalyst used di-Isobutyraldehyde.

Examples 5 and 6. The process of alkylation of meta - and para-Cresols by camphene behave analogously to example 1 with a ratio of the cresol:camphene 2:1. As catalyst, use appropriate cresolate aluminum. Alkylation of para-cresol is carried out at 190C.

Example 7. Alkylation of para-tert-butylphenol is carried out analogously to example 1, the ratio of p-tert-butylphenol:camphene 2:1 as the catalyst use ISO-propylate aluminum.

Example 8. The process of alkylation of hydroquinone with camphene carried out analogously to example 1, a catalyst for use phenolate.

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 300,3, phase - PEG20, temperature 100-C, heating 6/min, carrier gas - argon. IR spectra were recorded on a Specord M-80 in a thin layer on the plates CVG. The NMR spectra of1H and13With recorded spectrometer “Bruker AM-300” (300 and 75 MHz, respectively), the internal standard chloroform, solvent CDCl3.

1. The way to obtain ortho-terpenophenols, including autstin catalyst - organoaluminium compounds, such as phenoxide aluminum, characterized in that it further as a source of phenol using diatomic phenols, the molar ratio of phenol to camphene 1-21-2, respectively, organoaluminium compound optionally selected from the group of alkoxides of aluminum unbalanced (mixed) or symmetric (full) type in the amount of 0.5-1 wt.% aluminum to the mass of the original phenol.

2. The way to obtain ortho-terpenophenols under item 1, characterized in that the use of aluminium phenolate, not derived from the original phenol.

 

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