DE1768444B - Process for the preparation of bromine derivatives of bis (hydroxyphenyl) dialkylmetha nen - Google Patents

Description

3 ⁴

phenyO-dialkylmethane, in particular 2,2-bis- (4-hy- from 10 to 50 ⁰ C, after completion of droxyphenyl) propane, converted into bromine derivatives, the addition of the reaction mixture for a short time the more than 3 bromine atoms as substituents carry the aromatic parts of the molecule to be heated to temperatures of 80 to 100 ° C. Particularly and with continued stirring for some time, this temperature can advantageously be maintained after the 5 according to the invention. The mostly finely crystalline special 2,2-bis- (4-hydroxyphenyl) propane formed primarily in the bis (hydroxyphenyl) dialkylmethane process ins- reaction mixture, with bromine precipitate of the desired bromine derivative of the corresponding tetrabromo derivatives, bis exemplified - (Hydroxyphenyl) -dialkylmethane dissolves 2.2 - bis - (3.5 - dibromo - 4 - hydroxyphenyl) - at least largely again. In the case of propane and hydrogen bromide convert. The bis io subsequent cooling of the reaction mixture (hydroxyphenyl) -dialkylmethane can after the in falls the desired bromine derivative as a coarsely crystalline the USA Chemical reaction mixture is to be separated. The washed and then dried bromine process described with Wasser Gesellschaft, 25 (1892), p. 344, by reacting ketones with phenols derivative, can be obtained in an outstanding manner with this procedure. Purity and completely colorless, leaving it without further

The reaction medium is intended to be used industrially in the purification of the invention

according to the procedure for the first use from 99.5 can be. The filtrate can be used immediately as a reaction

up to 80 percent by weight, preferably 98 to 90 percent of the medium can be used for a new application,

percent by weight, of the organic solvents mentioned 20 in the procedure according to the invention

solvents and 0.5 to 20 percent by weight, preliminary yields of bromine derivatives of 95 to 97 ° / "the

preferably 2 to 10 percent by weight, water. Theory received. In addition, 95 to 100%

For the second and the following approach, gaseous hydrogen bromide is obtained as the theory.

Reaction medium uses the filtrate, the organic The yields are thus higher than in the process

niche phase thus on the 25 of the German Auslegeschrift 1 266 309 to be produced in each case, although the

Bromine derivative of bis (hydroxyphenyl) dialkylmethane Working up the reaction mixture considerably reduces

and the aqueous phase of which is sown in hydrogen bromide.

is done. In the method according to the invention, the following is the method according to the invention

the organic solvents, including benzene, explained using examples,

not brominated under the reaction conditions. 3 °

To carry out the inventive example 1
driving you can in this reaction medium the

Introduce the total amount of bromine required. In an agitator tank with a capacity of 900 l

The amount of bromine should be at least 3 moles per mole of that from 650 kg of dibromoethane and 200 kg of 50% strength

bis (hydroxyphenyl) dialkyl methane to be brominated 35 aqueous hydrogen bromide solution to be ordered

and must be dimensioned in such a way that each tion medium and 720 kg of bromine are submitted. In this

Gram atom of the hydrogen to be substituted in the reaction mixture will be released within 10 hours

1 mole of bromine introduced into the reaction mixture, 250 kg of 2,2-bis (hydro \ yphenyl) propane and

will. In this mixture is to be brominated tigern the stirring at temperatures of 10 to 20 ^0C

Bis (hydroxyphenyl) dialkyl methane slowly metered in. The gas escaping during the reaction

gen. The addition can be continuous or in portions, hydrogen bromide is collected. To

respectively. A technically particularly favorable work termination of the addition of the 2,2-bis (hydroxyphenyl) -

wise results when the reaction medium before propane, the reaction mixture is slow

Beginning of the reaction, the total amount of 90'C is not heated and then cooled and

required bromine is added, but only 45 filtered. After drying, 566 kg - 95%

part of it, preferably 30 to 1% of the total theory of pure, white 2,2-bis (3,5-dibro.n-

crowd. The remaining bromine is then obtained in the course of 4-hydroxyphenyl) propane, which is a bromine

the bromination simultaneously with the bis (hydroxyl content of 58.5 to 58.8 percent by weight and one

phenyD-dialkylmethane at two locally from each other has a melting point of 179 C,

separate places den-. Reaction mixture fed. In addition, 50 kg will 341-96 ° / ₀ of theory of

It can also be advantageous to add gaseous hydrogen bromide to the reaction medium and, for example, the filtrate

obtained before the start of the reaction only 15 to 1% of the total 840 kg of the reaction medium, which after

add amount of bromine and in the course of the addition of 12 to 25 kg of ethylene bromide directly for

Bromination 70 to 95% of the amount of bromine can be used at the same time the next batch,

with the bis (hydroxyphenyl) dialkylmethane at two 55 ...

spatially separated places the reaction example

to feed mixture. The remaining amount of bromine is put in an 800 liter agitator tank, the

in this procedure, after the addition is complete, with two locally separated as far as possible from one another

of bis (hydroxyphenyl) * dialkylmethane added. lying adding devices is provided

The simultaneous introduction of bromine and bis-60 that of 650 kg of dibromoethane and 220 kg of 50% strength

(hydroxyphenyl) dialkylmethane in the reaction aqueous hydrogen bromide solution existing react

medium takes place continuously or initially in proportions of tion medium. To this reaction medium

Locally as far apart as possible from one another. 45 kg of bromine are first given. Subsequently

During the addition of the reaction part or parts are continuous within 4 to 6 hours

The reaction mixture is moved vigorously, 65 and a total of 250 kg of 2,2-bis (hydroxyphenyl) propane

with temperatures of 10 to 10O ⁰ C upright- 665 kg of bromine through one of the addition devices

can be obtained. Here it is advantageous to add during lines. Here, the reaction mixture

represents Zueabe the reactants stirred temperatures and at temperatures of 18 to 25 ^0C

held. The gaseous escaping during the reaction Hydrogen bromide is collected.

After the addition of the reactants has ended, the mixture is kept at the specified temperature for some time and finally heated to 90 ° C. for a short time and then cooled and filtered. After drying, 578 kg = 97% of theory of pure, white 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane are obtained, which has a bromine content of 58.5 to 58.8 percent by weight and a Melting point of 179 ⁰ C has.

In addition, 341kg = 96% of theory gaseous hydrogen bromide and obtained as a filtrate 855 kg of the reaction medium, which after addition 1.5 to 3.0 parts by weight of dibromoethane can be used directly for the next batch.

Example 3

The reaction mixture consisting of 650 kg of dibromoethane and 220 kg of about 50% aqueous hydrogen bromide solution is placed in an 8001-capacity agitator tank, which is provided with two locally separated addition devices as far as possible. 50 kg of bromine are introduced into this reaction mixture. 250 kg of 2,2-bis- (hydroxyphenyl) -S propane and 625 kg of bromine are then added continuously through one of the adding devices over the course _{of 4 1/2} hours, with stirring and while maintaining a temperature of 15 to 25 ° C. After this addition has ended, another 35 kg of bromine are metered in over the course of 30 minutes. The gaseous hydrogen bromide escaping during the reaction

ίο is collected. After completion of addition of the reactants the mixture is kept for some time at the indicated temperature and heated at the end for a short time to 90 ^c C, then cooled and filtered.

After drying, 583 kg = 98% of theory of pure, white 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane obtained, which has a bromine content of 58.5 to 58.8 percent by weight and a Has a melting point of 179 ° C.

In addition, 344 kg = 97% ^of theory of gaseous hydrogen bromide and 840 kg of the reaction medium as a filtrate, which can be used directly for the next use after adding 1.5 to 3.0 parts by weight of dibromoethane.

Claims (3)

of bis- (hydroxyphenyl) -dialkylmethane and destil- Patent claims: Aqueous hydrogen bromide is released from the aqueous layer of the mother liquor. 1. Process for the preparation of bromine derivatives To carry out this process, the bis (hydroxyphenyl) dialkylmethane with more than 5 aqueous organic solvents is first added to the bis (hydroxyphenyl) dialkylmethane, which brominates to more than 3 bromine atoms per molecule, during the reaction resulting bromine water- borne. The resulting mixture is then added long fuel by reacting bis (hydroxyphenyl) - sam and with constant stirring, the bromine, dialkylmethanes with about 1 mole of bromine per gram Proven to be advantageous, the filtrate, the hydrous benzene, methyl bromide or water is obtained after bromination has taken place in the separation of chlorinated or brominated aliphatic bromine derivative containing bromine, not, as in the table hydrocarbons with 2 to 4 carbon atoms German interpretation 1266309 described by work up or mixtures thereof at temperatures of 10 distillation, but to use directly for the up to 100 ⁰ C, characterized in that 15 next Bromierungsansatz, ttei this is that the mixture of 99.5 to 80 wt operation with the second and with each percent of the organic solvent and 0.5 lowing approach already at the beginning the bromination up to 20 percent by weight of water, firstly a mixture of bromine, which mixes a saturated aqueous bromine and then contains the bis (hydroxy hydrogen solution). In the course of the reaction of phenyl) dialkylmethane for bromination slowly, in this case all hydrogen bromide can be introduced in gaseous form and obtained after the bromination has ended. The organic phase used and the cooling of the reaction mixture, the bromine, is filtered off on the bromine derivative of the bis derivative to be produced and the filtrate is immediately saturated with the (hydroxyphenyl) dialkylmethane and fed to the next operation. so that greater yields in the individual approaches 2. traversing ^r · mch claim 1, marked thereby be achieved 25th It has been shown, however, that the mixture of organic in this way of working a blue coloration of the reaction solvent and water can initially only occur to medium. Sometimes the discoloration is 1 percent by weight of the total amount of bromine too strong that the separated bromine derivative also mixes and then the bis-to be brominated is discolored, which makes this (hydroxyphenyl) dialkylmethane and the remaining bromine derivative, for example as a flame retardant composite bromine, usable at the same time to two locally from each other nente for plastics, is impaired. If the separation leads to a filtrate in the reaction mixture after the bromine derivative has been separated off and reacts. according to the information in the German interpretative document 3. The method according to claim 1, characterized in 1 266 309 in an aqueous and an organic phase draws that the mixture of organic 35 is separated, the organic phase before the re-solvent and water first 15 to 1 use distilled and weight percent with fresh water is mixed with the entire amount of bromine, this discoloration does not occur. It is and then the bis to be brominated (hy- therefore technically more advantageous, the filtrate directly to one droxyphenyl) dialkylmethane and 70 to 95 °, “the new approach to feed. Brommenge simultaneously at two local 40 It was therefore looked for possibilities that discoloration of the reaction medium and thus also discoloration of the reaction medium at separate points in the reaction mixture introduces and implements and after adding the amount of the end product to be avoided and anyway complete bis (hydroxyphenyl) dialkylmethane that is the best way of working for direct recyclables Adds bromine and converts it. Turning the filtrate as a reaction medium for a 45 new approach. A process for the production of bromine derivatives of bis (hydroxyphenyl) dialkyl methanes with more than 3 chromium atoms per molecule with recovery of the bromine formed during the conversion of the German Auslegeschrift 1266 309, 50 hydrogen by converting bis (hydroxyphenyl) was already a process for the production of bromodialkyl methanes with about 1 mol of bromine per Cirammtferivatcn of bis - (hydroxyphenyl) -dialkylmethane atom of the hydrogen to be substituted in water with more than 3 bromine atoms per molecule containing benzene, methyl bromide or water-containing finning of the bromochlorinated or brominated aliphatic hydrocarbon formed during the reaction by conversion of bis ( hydroxy 55 hydrogens with 2 to 4 carbon atoms or their phenyl) dialkyl methanes with bromine in an aqueous mixture at temperatures of 10 to 100 ⁰ C, rigen, organic solvent described. Found there. This process is characterized by the fact that the bromination is carried out in one of the following ways: the mixture of 99.5 to 80 weight percent benzene or methyl bromide, percent of the organic solvent and 0.5 to ethyl bromide, propyl bromide, butyl bromide, ethylene 60 20 weight percent water first admixes bromide bromide or ethylene chloride or their mixtures and then slowly introduces the bis (hydroxyphenyl) dialkyl and at least 10 weight percent water methane for bromination and after the mixture at a temperature of 10 ends the bromination and cooling des up to 100 ⁰ C with more than 3 moles of bromine per mole of bis-Rfionsgemisches the bromine derivative is filtered off and (hydroxyphenyl) dialkylmethane through, each 65 the filtrate directly to the next operation gram-atom of the hydrogen to be substituted. about 1 mole of bromine is used, and filtered off by the method according to the invention the cooled reaction mixture, the bromine derivative all bis (hydroxy-