DD292904A5 - PROCESS FOR THE PREPARATION OF P-ALKYLCALIX 4 ARENES - Google Patents

Abstract

The invention relates to a process for the preparation of p-alkylcalix & 4! Arenen. The aim is a simple and economical preparation of p-Alkylcalix & 4! Arenen of the general formula I with n4. The compounds are prepared from a precondensate prepared from p-alkylphenol and formaldehyde, or from p-tertiary alkylcalixes or from a mixture of p-alkylphenol and paraformaldehyde, in each case in the presence of alkali metal hydroxides as catalyst, in a mixture of straight-chain hydrocarbons the chain length C11 to C20 at 217 to 257C. The p-alkylcalix & 4! Arenes are isolated in well-crystallized form directly from the reaction mixture. Particularly suitable is the process for the preparation of p-tert-butylcalix & 4! Arene {p-alkylcalix & 4! Arene; Paraffin, straight chain; Mixture; Kettenlaenge; precondensate; alkyl phenol; Formaldehyde; Paraformaldehyde; ! P-Alkylcalix & 8 arenes; Catalyst; alkali}

Description

in the R has the same meaning as in formula I, and formaldehyde in the form of an aqueous solution, preferably with 30 to 40 parts by mass in% formaldehyde,

- or from a p-Alkylcalix [8] arene of the general formula I with R as in formula I and η = 8

- or from a mixture of the p-alkylphenol of the general formula II in which R has the same meaning as in formula I, and paraformaldehyde

by a reaction catalyzed with alkali metal hydroxide in an organic solvent as the reaction medium, characterized in that the organic solvent used is a mixture of straight-chain hydrocarbons of chain length Cn to C ₂ o and boiling range 250 ^° C. to 260 ^° C. under atmospheric pressure, into which the respective starting material and the alkali metal hydroxide, 1 to 10 hours at 217 ° C to 257 ° C with exclusion of oxygen stirred while distilling off the water of reaction, then unreacted solid at 100 ° C to 160 ⁰ C separated from the reaction mixture, the solids-free reaction solution to 17 ° C to 42 ⁰ C and the precipitated, well crystalline p-alkylcalix [4] arene isolated in a conventional manner, washed with a hydrocarbon mixture of chain length C ₅ to C ₇ and dried in vacuo at 0.5 to 1, OkPa ,

2. The method according to claim 1, characterized in that as a mixture of straight-chain hydrocarbons of chain length C ₁₁ to C ₂ o an isolated by Molsiebextraktion from a Erdölmitteleldestillatschnitt n-paraffin mixture of the composition 2.5 to 10 mass fractions in% η-paraffins C ₁₁ to C ₁₂ , 80 to 90 parts by weight in% η-paraffins C ₁₃ to C ₁₇ and 0.5 to 10 parts by weight in% n paraffins C ₁₈ to C _{20 is} used.

3. The method according to claim 1, characterized in that as alkali metal hydroxide sodium or potassium hydroxide, preferably in the form of an aqueous solution in a ratio of 2 to 10 substance proportions in%, based on the phenolic unit used, is used.

Field of application of the invention

The invention relates to a process for the preparation of p-alkyl calix [4] arenes, which are useful as stabilizers for polymers or for the production of ion-sensitive electrodes or as macrocyclic synthesis building blocks.

Characteristic of the known state of the art

p-Alkylcalix [4] arenes have gained increasing interest in recent years due to their special structure. (Top Curr.Chem 123 (1984) 1)

For practical use of p-alkylcalix [4] arenes, it is necessary to develop technologically simple and economical production processes for these compounds. According to literature (J. Org. Chem. 51 [1986] 742) is used for the production

the p-alkylcalix [4] arene was used as the reaction medium by base-catalyzed reaction of the polar diphenyl ethers. The disadvantage of this method is that in addition to a significant odor nuisance by the diphenyl ether, this is toxic as a toxic compound toxic. In addition, a complex stage for the isolation of the p-alkylcalix [4] arenes is necessary in this process. Furthermore, p-alkylcalix [4] arenes can be prepared by base-catalyzed reaction of p-alkylphenols and paraformaldehyde in tetralin. (J. Org. Chem. 43 [1978] 4280) The tetralin as a reaction medium has the disadvantage that it is toxic as an aromatic compound and that it forms due to its easy auto-oxidizing period, which by their spontaneous decomposition at higher temperatures to significant hazards to lead. In addition, potassium tert-butylate is used as the catalyst in this process, which is obtained only in a complicated process from potassium and tert-butanol and is too expensive for industrial application.

Object of the invention

The aim of the invention is to develop a technologically simple and economical process for the preparation of p-Alkylcalix [4] arenes.

Explanation of the essence of the invention

The object of the invention is to prepare p-alkylcalix [4] arenes using a non-toxic and odor-free reaction medium in the presence of readily available basic catalysts.

This object is achieved by a process for the preparation of p-alkylcalix [4] arenes of the general formula I.

solved, in which

R = n-alkyl C, to C ₄ ; iso-alkyl C ₃ to C ₅ ; tert.-alkyl C ₄ and C ₆ , cyclohexyl and

mean, from a precondensate prepared from the corresponding alkylphenol of general formula II

II.

in which R has the same meaning as in formula I, and formaldehyde in the form of an aqueous solution with preferably 30 to 40 parts by mass in% formaldehyde, or from a p-alkylcalix [8] arene of the general formula I with R = as in formula I. and

or from a mixture of the p-alkylphenol of the general formula II with R as in formula I.

and paraformaldehyde by an alkali metal hydroxide catalyzed reaction in an organic solvent as the reaction medium by the invention as the organic solvent, a mixture of straight-chain hydrocarbons of chain length Cn to C ₂ o and the boiling range 250 ⁰ C to 260 ⁰ C is used at atmospheric pressure, in which the respective starting material and the alkali metal hydroxide, 1 to 10 hours at 217 ° C to 257 ° C stirred with exclusion of oxygen, distilling off the water of reaction formed, then unreacted solid at 100 ⁰ C to 160 ⁰ C separated from the reaction mixture, the solids-free reaction solution to 17 Cooled to 42 ° C and the precipitated, well crystalline pA! Kylcalix [4] arene isolated in a conventional manner, washed with a hydrocarbon mixture of chain length C ₅ to C ₇ and dried in vacuo at 0.5 to 1, OkPa , As a mixture of straight-chain hydrocarbons of chain length Cn to C ₂₀ , an n-paraffin mixture of the composition 2.5 to 10 mass fractions in% η-paraffins Cn to Ci ₂ , 80 to 90 mass fractions in% η-paraffins Ci _{3 is} isolated by molecular sieve extraction from a petroleum middle distillate cut used to Ci ₇ and 0.5 to 10 parts by weight in% η-paraffins Ci ₈ to C ₂₀ . The alkali metal hydroxide used is preferably potassium hydroxide or sodium hydroxide in a ratio of from 2 to 10 molar proportions in%, based on the phenolic unit used. The use is preferably in the form of an aqueous solution.

The process of the invention surprisingly yields p-alkylcalix [4] arenes in a well crystallized form using an almost odorless, non-toxic reaction medium. Compounds, preferably by

This process according to the invention are prepared, the p-tert-butyl calix [4] arene (formula I, η = 4, R = t.-C ₄ H ₉ ) and p-tert-amylcalix [4] arene (formula I , η = 4, R = t.-C ₅ Hn). The p-alkylcalix [4] arenes prepared by the process according to the invention can be used for metal ion extraction or for ion-sensitive electrodes, as stabilizers of polymeric materials and as synthesis starting material for calix [4] arene derivatives.

embodiments example 1

50 g of p-tert-butylphenol, 70 m ³ 30% aqueous formaldehyde solution and 0.6 g of sodium hydroxide are exposed in an open flask for one hour 100 ⁰ C to 110 ⁰ C. The resulting high-viscosity mass is allowed to cool to room temperature and crushed it after solidification in small pieces. These are suspended in a stirred vessel with a water separator in 400 cm ^{3 of} a mixture of straight-chain paraffins C _n to C ₂ o and heated with stirring and exclusion of oxygen. At 110 ⁰ C, the distilling off of the reaction water begins.

The temperature is further increased, above 152 ° C, a white solid precipitates first. The mixture is then heated at 217 ° C to 252 ° C for about 5 hours to boiling. The majority of the solid goes back into solution. After the 5 hours of reaction time allowed to settle denver permanent Feststoffsich and pulls at 100 ⁰ C to 160 ° C the hot solution from the settled solids from. When the solution is cooled to room temperature, crystals of p-tert-butylcalix [4] arene precipitate, which are isolated by filtration and washed with a mixture of paraffins C _s to C ₇ . It is then dried in vacuo at 0.5 to 1.0 kPa

Yield: 32 g (60% based on phenol); Mp 34O ⁰ C to 345 ⁰ C

Example 2

50 g of p-tert-butylcalix [8] arene (formula I, η = 8, R = tert-butyl) and 0.6 g of sodium hydroxide in 2 ml of water are dissolved in a stirred vessel with water separator in 400 cm ^{3 of} a mixture of straight-chain paraffins of the preferred chain length C ₁₃ to C ₁₇ and suspended under exclusion of oxygen for 6 hours at 217 ° C to 252 ° C stirred. The majority of the solid goes into solution. After the 6 hours, unreacted p-tert-butylcalix [8] arene is allowed to settle and the hot liquid phase is removed from the solid. When the liquid phase is cooled to room temperature, crystals are precipitated, which are isolated by filtration and washed with a low-boiling hydrocarbon mixture C ₅ to C ₇ . The drying is then carried out in vacuo at 0.5 to 1, OkPa

Yield: 35 g (70% based on t.-butylcalix [8] arene); Mp 341 ⁰ C to 346 ° C

Example 3

In a stirred vessel with a water separator 50 g of p-tert-butylphenol, 20 g of paraformaldehyde and 0.8 cm ³ 10n aqueous potassium hydroxide in 500cm ^{3 of} a mixture of straight-chain paraffins with exclusion of oxygen for two hours at 120 ⁰ C and then boiled for four hours at 247 ° C to boiling heated.

The unreacted solid is allowed to settle and separates the hot reaction solution from the solid. On cooling to 17 to 27 ° C, p-tert-butylcalix [4] arene crystallizes, which is isolated and washed with a mixture of paraffins C ₅ to C ₇ . It is then dried in vacuo at 0.5 to 1, OkPa.

Yield: 17g (33% based on phenol); Mp 340 ° C to 345 ° C

Example 4

As described in Example 1, a precondensate is prepared from 50 g of tert-amylphenol, 70 cm ^{3 of} a 30% aqueous formaldehyde solution and 0.6 g of sodium hydroxide. This is likewise suspended, as described in Example 1, in a stirred vessel in 400 cm ^{3 of} a mixture of straight-chain paraffins and further processed. Yield: 22 g (50% based on the phenol used); Mp. 308 ° C to 310 ⁰ C.

Claims (1)

claims: 1. A process for the preparation of p-Alkylcalix [4] arenes of the general formula OH in which R = n-alkyl C ₁ to C ₄ ; iso-alkyl C ₃ to C ₅ ; tert.-alkyl C ₄ and C ₅ or cyclohexyl and n = 4 mean, - From a precondensate, prepared from the corresponding p-alkylphenol of the general formula