DE1056620B - Process for the preparation of 2,2-bisoxyaryl-propanes - Google Patents

Description

Process for the preparation of 2,2-biso-xyaryl-propanes It is already known, 2,2-bisoxyaryl-propanes, such as 2,2-bis- (4-oxyphenyl) -propane, by condensation an oxyaryl compound, such as phenol, with acetone in the presence of an acidic condensing agent, such as sulfuric acid and hydrogen chloride. The result of the reaction However, water has an unfavorable effect on the rate of formation of 2 isoxyaryl propane. Longer reaction times are therefore necessary, if not expensive, for good yields Drainage methods are applied. To avoid these difficulties, recently proposed a saturated dihalide such as 2,2-dichloropropane or an unsaturated monohalide such as 2-chloropropane or a bis (organomercapto) methane, to use instead of acetone as a reactant for the phenol. But also these processes are characterized by disadvantages such as low yields, low yields Quality of the end product, undesirable gumming and formation of by-products, and in some cases long response times and expensive processes for obtaining the 2, isoxyaryl propane.

According to the invention, the process for the preparation of 2,2-bisoxyaryl-propanes is characterized in that propadiene or propyne with a stoichiometric excess of an oxyaryl compound of the general formula wherein R1 and R2 are hydrogen or lower alkyl groups, in the presence of an acidic condensing agent which does not form insoluble complexes with any of the reactants under the reaction conditions, at a temperature of about 30 to 100 ° C.

The reaction proceeds according to the following equation: 2-OR () R1 + C8H4 e R2 CH3 30 to 100 0C 30 to 100 ° C R1O C ~ I P- OR ' RO3-C- Condensation I medium R2 3 113 R2 In these formulas, R1 and R2 stand for hydrogen or lower alkyl groups.

The oxyaryl compounds which can be used for the process according to the invention correspond to the general formula in which R1 and R2 are hydrogen or a lower alkyl group, such as a methyl, ethyl or propyl group, and where R1 and R2 can be the same or different from one another.

The benzene ring should only be alkyl-substituted in the o-position with respect to the oxy group be. An alkyl substitution in the m-position of the benzene ring causes the formation of spirohydride and spirochroman structures with little or no yield to the desired m-alkyl-substituted bisoxyaryl propanes.

Among the oxyaryl compounds that are used to carry out the invention Particularly suitable process are phenol, anisole, o-cresol and o-Mè thylanisoi to call. When using phenol as an oxyaryl compound are particularly good yields of 2,2-bis (4-oxyphenyl) propane were obtained.

Propadiene and Propyne are at the original temperatures and pressures Gases and the reaction mixture are best passed through a suitable gas distributor added below the surface of the reaction mixture. Optionally, the reaction be performed by above the reaction mixture an atmosphere is maintained from the hydrocarbons mentioned.

The method according to the invention has the advantage that mixtures of the two mentioned C3 H4 hydrocarbons can be used without there is a need to separate the individual propadiene or propine fractions before Separate and purify reaction with the oxyaryl compound. The reaction of the Propadiene or propyne or mixtures thereof are rendered more inert by the presence gaseous diluents such as saturated paraffins such as methane, athan and propane, or nitrogen, argon or neon, not hindered. It's not necessary, that such inert compounds may be present from the C8 Hg hydrocarbon removed. In some cases it may be desirable to use such inert diluents to control the reaction temperature and the feed rate of the C3 H4 hydrocarbon to use.

The amounts of reactants used in the process of the invention are not very crucial. In practice, however, it is desirable to have an excess of the oxyaryl compound beyond the stoichiometric amount, and it is preferable an excess of 2 moles of oxyaryl compound per mole of C3H4 hydrocarbon is used. The best yields of 2, 2-bisoxyaryl-prop auen are obtained when about 5 to 7 moles of oxyaryl compound can be used per mole of C3H4 hydrocarbon.

Useful acidic condensing agents include the condensing agents of the Friedel-Crafts type, such as the halides of boron, aluminum, zinc, iron and tin, as well as mineral acids such as sulfuric acid, phenolsulfonic acid and hydrogen fluoride. The Friedel-Crafts condensing agents are preferred for the best yields, and in particular boron trifluoride is used when phenol is the oxyaryl compound employed is.

The acidic condensation mixture should be selected so that it is with complexes that are not insoluble for any of the reactants under the condensation conditions forms. So is z. B. known that phenol in contact with aluminum chloride a forms insoluble complex which inactivates the aluminum chloride so that it the reaction of the C3 H4 compound no longer accelerates. Forms aluminum chloride also with aniline and methyl benzoate complexes. In the method according to the invention however, found that aluminum chloride is a useful condensing agent when it is used with oxyaryl compounds, except phenol and cresol. Possibly Mixtures of two or more acidic condensing agents can be used.

The acidic condensing agents are preferably used in amounts of 1 to 5 parts per 100 parts by weight of oxyaryl compound are used, but can also slightly larger or smaller amounts can be used. Preferably they should be acidic Condensation agent and the reactants are practically free of water, since the presence of water reduces the rate of formation of the desired 2,2-bisoxyaryl propane reduced. Since water is not formed in this reaction, practically anhydrous Reaction conditions are maintained by the reactants and the condensing agent must be dried before use. However, it is not a crucial requirement of the process according to the invention that anhydrous conditions be maintained as the presence is lower Amounts of water in the acidic condensing agent or the respondents can be allowed. So acts z. B. boron trifluoride monohydrate (13 F3 1120) as a condensing agent, but results in lower reaction rates, than when using anhydrous boron trifluoride.

The reaction between the oxyaryl compound and the C3 H4 hydrocarbon runs at moderate temperatures, namely at around 30 to 1000 C. Will be normal solid oxyaryl compounds, such as phenol and o-cresol, are used, temperatures above 400 C or at least temperatures at which a reaction occurs in the liquid phase guaranteed is preferred. Temperatures above 1000 C are not so suitable as side reactions can occur and the end product can decompose.

When carrying out the process in batches, each according to the selected temperature and the feed rate of the C3 H4 compound the implementation time take 15 minutes to 5 hours or a little more. With continuous or semi-continuous process, the actual response time can be much shorter be. Both decreased and increased pressures can be used, however atmospheric pressures are most comfortable.

The 2,2-bisoxyarylpropane produced according to the invention can be obtained from the Reaction mixture can be obtained in a conventional manner, such as by distillation, crystallization and extraction. Preferably, however, after removal of the acidic condensing agent the reaction mixture is distilled under reduced pressure and the end product as Distillation residue obtained. It can also be proceeded in such a way that the acidic Condensing agent by diluting the reaction mixture with a mixture of cold water and ice or a mixture of ice and dilute hydrochloric acid and then the organic products are obtained.

If phenol is used as a reactant, the 2,2-bis (4-oxyphenyl) propane is used from the reaction mixture easily by crystallization of one of phenol and the 2,2-bis- (4-oxyphenyl) -propane at a temperature below 900 C formed complex removed. The crystalline complex can easily be filtered off from the reaction mixture and by the action of heat as in a distillation to distill off the unreacted phenol or by washing the crystalline material with hot Water, which washes out the phenol, will be destroyed.

The former method is more advantageous as the water treatment results in a wet phenol which must be dried before reuse.

In addition, due to its low solubility in water, something can 2,2-bis- (4-oxyphenyl) -propane are lost The thermal decomposition of the crystalline Complex is reduced by heating the crystalline complex at a Pressure of 25 to 70 mm Hg to a temperature of 100 to 1250 C and then Brief heating to 200 to 2200 C to remove the last traces of phenol carried out. The 2,2-bis (4-oxyphenyl) propane thus obtained is usually more as 95 to 97% pure.

The recovery of 2,2-13 isoxyaryl propanes using of boron trifluoride as an acidic condensing agent can also by neutralizing the boron trifluoride by adding an excess of calcium oxide and water through be guided. After filtering off the inorganic Materials can use the solution to recover the unreacted phenol and remove it to be distilled from water. The 2,2-bis (4-oxyphenyl) propane is then made obtained from the distillation residue.

The residue can optionally be used for further purification of the product washed with chloroform or recrystallized from dilute acetic acid.

Other 2,2-bisoxyaryl propanes made by the process of the invention are preferably made by removing the acidic condensation mixture by pouring the reaction mixture on ice or ice and dilute hydrochloric acid and then Distillation of the organic portion of the washed reaction mixture recovered. There Most used acidic condensing agents in ice water, or cold water cold dilute hydrochloric acid are soluble, while the oxyaryl compounds (except Phenol) and the reaction products are not, so becomes the organic part of the reaction mixture separated from the cold aqueous mixture and distilled, the formed 2,2-Bisoxyaryl-propane is obtained as the distillation residue.

The invention is described in more detail by the following examples.

Example 1 To 281.2 g (3 moles) of anhydrous phenol were added at 50 to 550 C 7.3 g (0.17 mol) of boron trifluoride were added by passing the boron trifluoride through the Molten phenol was passed through until the desired weight of catalyst had been recorded, which was measured by occasionally weighing the reaction vessel became. The air was then purged from the reaction vessel by adding nitrogen for 2 minutes was passed through. Then 20.0 g (0.5 mol) of gaseous propadiene were added slowly introduced below the liquid level of the mixture of phenol and catalyst. The reaction mixture was passed during the 32 minutes that the propadiene was introduced was maintained at a temperature of 50 to 55 ° C.

After completion of the reaction, the product was obtained by adding 50% ccm of cold water and 11.1 g (0.2 mol) of calcium oxide were added to the reaction mixture and the mixture at a temperature of 50 to 550 C to remove the organic Components was filtered. That. Water and the unreacted phenol were from the washed reaction mixture by distillation at a pressure of 10 up to 15 mm Hg away. The residue consisted of almost pure 2,2-bis- (4-oxyphenyl) propane with a melting point of 1580 C. The yield was 85.9% 2,2-bis (4-oxyphenyl) propane, based on the added propadiene.

Example 2 To 324 g (3.0 moles) of anisole kept at 390 ° C was added 13.5 g (0.10 mol) of anhydrous aluminum chloride were added with stirring and the system Purged with nitrogen for 2 minutes. In this mixture were 19.9 g (0.50 mol) gaseous propadiene slowly for 100 minutes while maintaining a Temperature of 39 to 470 C initiated below the surface of the liquid. To After completing the addition of the propadiene, the reaction mixture became a mixture poured from ice and 10% hydrochloric acid.

A yellow layer forming on top of the ice cream mixture was removed and diluted with 100 cc of diethyl ether to facilitate separation of the phases. tern. The organic layer was added one after the other with portions of 100 ccm each of 10% hydrochloric acid, water, 50% sodium hydroxide solution and twice more washed with water. Unreacted anisole became from the washed material removed by distillation at a pressure of 10 mm Hg and with a reduction in the Pressure in the distillation column to 3 mm Hg of colorless 2,2-bis- (4-methoxyphenyl) propane obtained as a distillate.

The yield of 2,2-bis (4-methoxyphenyl) propane was 43% by weight on Propadien. It had the following properties: Kp.3 = 183 to 1890C. n2D0 = 1.5692.

The physical constants of the described in the literature Connection are: bp = 190 ° C. n 3 ° = 1.5696.

The elemental analysis resulted in the following values: Found ....................... C 80.1%, H 8.2%; calculated ............. C 79.7 0 / o., 11 7.90 / o.

The infrared absorption spectrum showed predominantly p-substitution in the aromatic core. Another confirmation of the constitution of this product was obtained by converting the methyl ether to the well-known 2,2-bis (4-oxyphenyl) propane was split. A mixed melting point with an authentic sample gave no degradation.

Example 3 To 141 g (1.5 moles) of anhydrous phenol became anhydrous Boron trifluoride was added by passing this through the molten phenol until 1.4 g (0.02 mole) had been absorbed, such as by intermittent weighing of the reaction vessel was detected. Then 8 g (0.20 mol) became gaseous Propyne was added by stirring this below the surface for 32 minutes the liquid mixture was introduced. The reaction temperature was thereby on Maintained 50.0 C and after the addition of the propyne the reaction mixture stirred for another 45 minutes, cooling to a temperature below 400 C, thus the complex of phenol and 2,2-bis- (4-oxyphenyl) propane from the reaction mixture crystallized out. The crystals were filtered off at a temperature of 410.degree and washed with 53.5 g of freshly melted dry phenol. The crystalline Complex was decomposed by heating under a reduced pressure of 20 mm Hg was used to remove the phenol from the complex and 24.5 g of pure 2,2-bis- (4-oxyphenyl) propane were obtained obtained from the distillation residue. F. = 1580 C. The yield was 54 bis 55% of 2,2-bis (4-oxyphenyl) propane, based on propyne.

Example 4 To 649 g (5 mol) of distilled cresol were added to a Temperature of 350 ° C. 9.8 g (0.14 mol) boron trifluoride were added with stirring by adding this was introduced into the molten cresol until the desired amount of Catalyst was added, and then the system was flushed with nitrogen. - Then 43.7 g (1.09 mol) of gaseous propadiene were added slowly with stirring for 5 hours introduced below the surface of the mixture of cresol and the catalyst, with the mixture on a Maintain temperature of 49 to 550 C. became.

The reaction mixture became 30 minutes after the addition of the propadiene touched.

The product was obtained by decomposing the catalyst with 15 cc of water and 10 g (0.18 mole) calcium oxide recovered. After standing for 2 days, the inorganic The precipitate was filtered off and a further 10 g of calcium oxide were added. The not implemented o-Cresol was made by distillation at a pressure of 20 mm Hg and a temperature away from 1820 C.

The distillation residue was fractionated at a pressure of 1 mm Hg distilled and at a temperature of 187 to 1940 C 151 g of crude 2,2-bis (4-oxy-3-methylphenyl) propane collected. This corresponds to a yield of 540/0. Pure crystallized 2,2-bis- (4-oxy-3-methylpheny1 propane was converted from a benzene-n-hexane solution after a long period of time Stand at 20 C. The compound had a melting point of 99-1050 C. The elemental analysis gave the following values: C11 H20 O2 Found C 79.49 O / o, H 8.03 O / o, phenolic OH 12.66 0 / o; calculated C 79.65%, H 7.87%, phenolic OH 13.27 O / o.

The melting points of 2,2-bis- (4-oxy-3-methylphenyl) propane described so far do not match and vary from 96.5 to 1400 C.

Example 5 To 280.0 g (2.59 moles) of anisole was added 11.7 g with stirring g (0.089 mol) of anhydrous aluminum chloride were added and the system with nitrogen rinsed out. 8.3 g (0.458 mol) of gaseous propyne were slowly added to this mixture initiated for 50 minutes below the liquid surface, the reaction temperature was maintained between 33 and 460 C. After completion of the propyne addition the reaction mixture was stirred for a further 1/2 hour, whereby to room temperature has been cooled.

The reaction mixture was worked up in the usual manner by the catalyst is decomposed with cold water and each time with 100 ccm of 100% hydrochloric acid, Water and diluted alkali. The unreacted anisole was removed and the 2,2-bis (4-methoxyphenyl) propane isolated by distillation. A 30% yield was obtained. The product boiled at a pressure of 2 mm Hg at 176 to 1780 C.

Example 6 To 141 g (1.5 moles) of anhydrous phenol was added 1.5 g of boron trifluoride added with stirring and the system flushed with nitrogen for 2 minutes. then 10 g (0.25 mole) of propadiene was slowly submerged over 14 minutes the mixture of phenol and the catalyst introduced and the temperature to 50 held up to 550 C. The reaction mixture was allowed to cool to room temperature, whereupon abundant crystallization occurred.

The reaction mixture was heated to a temperature of 41 to 420 ° C heated and filtered at this temperature, both the solid crystalline Material as well as the filtrate, which unreacted phenol and part of the Catalyst contained, were recovered. The solid complex from the phenol and the Bis-phenol was washed with freshly melted phenol to remove the last residue of the adhering boron Remove trifluoride catalyst. The crystalline material was distilled at a reduced pressure of 20 mm Hg, with the overhead Remainder of the unreacted phenol was drawn off. Remained as the distillation residue 2,2-bis (4-oxyphenyl) propane in a 61% yield (based on the propadiene). F. = 1560 C.

The filtrate containing the phenol and the catalyst and the Phenol used to wash the crystalline complex were combined and others Phenol was added so that again about 1.5 moles of phenol and the catalyst were present again was 1 0 / o of the weight of the phenol. To this mixture of phenol and Catalyst were slow at a temperature of 50-550 for 42 minutes C 10 g of propadiene (0.25 mol) were added.

The final product was obtained as described above, and the yield of 2,2-bis (4-oxyphenyl) propane was 76 in this second batch 0 / o, based on the propadiene. F. = 1500 C.

This example shows that the process can be continuous or semi-continuous using recovered phenol and catalyst can.

Example 7 1.4 g (10 / o) boron trifluoride were added to 141 g (1.5 mol) of phenol slowly admitted. The mixture was kept at a temperature of 50 to 55 "C, being a gaseous mixture of propyne (33.7 mole percent) and propadiene (65.1 Mole percent) slowly under the surface of the liquid mixture for 80 minutes was initiated from phenol and the catalyst. After the reaction was finished the product, as described in Example 6, isolated. It had good color and a melting point of 1530 C.

Example 8 To 62.9 g (0.51 mol) of o-methyl anisole was added 6.8 g (0.051 mole) Mol) anhydrous aluminum chloride was added. The mixture was brought to a temperature kept from 50 to 550 C and gaseous propyne slowly below the surface initiated the liquid reaction mixture. The aluminum chloride was accordingly Example 2 removed and the remaining mixture through at a pressure of 50 mm Hg Purified distillation to recover unreacted o-methyl anisole. It was a 540% yield of 2,2-bis (4-methoxy-3-methylphenyl) propane was obtained. The product was very viscous and shows the following elemental analysis: Found C 80.24e / 0, H 8.52%, 0 11.240 / o (from difference); calculated C 80.3 ° / o, H 8.510 / o, 0.11.19 ° / o (from difference).

Claims (3)

PATENTANS-PRtJCHE: i Process for the preparation of 2,2-bisoxyaryl-propanes, characterized in that propadiene or propyne with a stoichiometric excess of an oxyaryl compound of the general formula wherein R1 and R2 represent water or a lower alkyl group, is reacted at a temperature of about 30 to 1000 C in the presence of an acidic condensing agent which does not form insoluble complexes with any of the reactants under the reaction conditions. 2. The method according to claim 1, characterized in that in the event Phenol is used as the oxyaryl compound, boron trifluoride as the acidic condensing agent is used. 3. The method according to claim i and 2, characterized in that the acidic condensing agents in an amount of 1 to 5 parts by weight per 100 parts by weight Oxyaryl compound is used. ~~~~~~~ Publications Considered: British Patent specification Kr. 710 479.