Method of producing isocamphylphenols

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing isocamphylphenols which are widely used in different industries as antioxidants and stabilisers. The method involves alkylation of monohydric phenols with camphene as terpene while heating to temperature not lower than 100°C. The catalyst of the process is montmorillonite KSF which is taken in amount of 50-200% of the weight of the initial phenol. The molar ratio of phenol to camphene is equal to 1:1-2.

EFFECT: method increases selectivity of the process and increases output of isocamphylphenols.

1 tbl, 4 ex

 

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.

There is a method of interaction of benzene with camphene in a molar ratio of 1:1 [Titov TF, Fomenko CENTURIES, D.V. Korchagina, Salakhutdinov NF, Jonah KG, Barkhash VA, the Journal of organic chemistry, 1997, v.33, no .5, s-741]. The alkylation is carried out at room temperature for 1 hour in the presence of a catalyst zeolite Hβ (calcined). The result is 2,2,3-Exo-trimethyl-5-Exo-Panevezio[2.2.1]heptane with a yield of 56%.

There is a method of interaction camphene with guaiacol [US patent No. 5,874,648, publ. 23.02.1999] in the presence of an acid catalyst (such as bromine TRIFLUORIDE and acetic acid). However, the authors of the patent does not give a description of the reaction conditions and the quantitative composition of the products of alkylation.

A known method of producing monoisobutyrate [Fomenko CENTURIES, D.V. Korchagina, Salakhutdinov NF, Bagryanskaya YOU, Gatilov J.V., Jonah KG, Barkhash VA, the Journal of organic chemistry, 2000, T.36, No.. 4, s-576] by alkylation of o-cresol, 2,3-dimethylphenol, 2,6-dimethylphenol and 3.5-dimethylphenol with camphene in the presence of methylene chloride at room temperature for 5 h, 8 h, 5 h, 10 h is respectively. The disadvantage of this invention is the formation of monoisocyanates as by-products in minimum quantities (3-10%).

A method of obtaining monoalkylated phenols [Kheifets L.A., aulchenko I.S. Chemistry and technology of aromatic substances and essential oils. M., 1968, p.142-185], we have chosen for the prototype, boiling phenol and camphene (molar ratio 2:1) in the presence of a 35%solution of boron TRIFLUORIDE in acetic acid for 4 h at 100°C. the Total yield of terpenophenols with isocamphylic structure of terpene Deputy - 54%, the yield of 2-isoamylene and 4-isoamylene is 32% and 22%, respectively. When boiling para-cresol with camphene (molar ratio 2:1) in the presence of a 35%solution of boron TRIFLUORIDE in acetic acid for 4 h at 100°C output 2-isoamylene is 28%, respectively.

The present invention is to increase the selectivity of the process and increasing the yield of itemfilename.

The present invention allows for the alkylation of phenols, using as catalyst montmorillonite KSF, in addition, allows to increase the conversion of phenol to 98-100% with the release of itemfilename 70-95%. This is the technical result.

The technical result is achieved in that a method of obtaining itemfilename, including alkilirovanie monohydroxy phenols by camphene as terpenes when heated to a temperature of not lower than 100°C, according to the invention as catalyst choose montmorillonite KSF in the amount of 50-200 wt.% to the mass of the original phenol, the molar ratio of phenol to camphene 1÷1-2, respectively.

The method is as follows.

The method of producing terpenophenols includes alkylation of monohydroxy phenols by camphene as terpenes when heated. The molar ratio of phenol and camphene 1:1 and 1:2. Montmorillonite KSF choose the number of 50-200 wt.% to the mass of the original phenol and camphene. The alkylation of phenols by camphene are in the presence of montmorillonite KSF at the temperature of the reaction medium at 100°C, which avoids the formation of by-products and to increase the output of itemfilename 70-100% (in the prototype, 54%).

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 n-cresol and 1.26 g of camphene (molar ratio of n-cresol:camphene 1:1). The reaction of lead, maintaining a temperature of 100°C, until complete conversion of phenol (control according to GC). Upon completion of the reaction, the reaction mixture was cooled, diluted with diethyl ether, filtered off from the catalyst and evaporated the solvent. The thus treated reaction mixture contains 100 wt.% monoalkylated phenols.

Experimental data of examples 2-4 are shown in the table.

the example 2. The process is carried out analogously to example 1 at a ratio of n-cresol:camphene 1:2.

Example 3. Alkylation of phenol by camphene behave analogously to example 1 at a ratio of phenol:camphene 1:1.

Example 4. Alkylation of ortho-cresol behave analogously to example 1 at a ratio of initial components is 1:1.

Monitoring the progress of reactions and the identity of the substances was performed using TLC on Sorbfil plates UV-254 (eluent - hexane:diethyl ether 3:1), and by GLC using chromatograph "Crystal 2000", capillary column HP-5MS, 60 m, 0.251 mm, temperature range 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 and13C were recorded on a spectrometer Bruker AM-300" (300 and 75 MHz, respectively), the internal standard chloroform, solvent CDCl3.

The method of producing itemfilename, including alkylation of monohydroxy phenols by camphene as terpenes when heated to a temperature of not lower than 100°C., wherein the catalyst is chosen montmorillonite KSF in the amount of 50-200% of the weight of the original phenol, the molar ratio of phenol and camphene 1÷1-2, respectively.



 

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