SU12236A1 - The method of obtaining aralcylamines and their derivatives - Google Patents

Description

The proposed method for the preparation of aralkylaiines and their derivatives consists in the action of halo-metal phthalimide on aromatic hydrocarbons, or their substitution products, with or without solvent and catalyst. The reaction proceeds according to the equation:

SbNs-t-Gal. CH2. MCH Q xSon4

 SbH5. СН2М (§ СБН4 - Н Gal.

The condensation product is converted into salts of aralnyl phthalamine when treated with cold alkalis. acids:

ari. SNG - Maon

.., Mao. WITH ,, .. aryl. "..By f N.

which, when processed with diluted acids, form aralkylamine and phthalic acid:

aryl. CH, ; c§ / QH4 - 2HCI - hH2O aryl. SNG NH. . .HCI + ... ,, / COOH, „H-SsN4 COOH + NaC1

It was also possible, by means of alkali treatment alone, to convert the condensation products obtained from aromatic hydrocarbons, or their substitution products and W halo-methyl phthalimides, into the corresponding aralkylamines and phthalate salts.

Example. 198 parts of chloromethylphthalide imide are boiled with 500 parts of pure benzene and 10 parts of zinc chloride with the refrigerator back in place for many hours, until the release of hydrogen chloride stops. Then benzene is distilled off and the residue is recrystallized from alcohol. 118h The benzyl-phthal-imide thus obtained is placed with 125 parts of a 35% aqueous solution of sodium hydroxide, 500 parts of water and 500 parts of alcohol until completely dissolved. On addition of 280 parts of 25% hydrochloric acid, the alcohol is distilled off and placed in a warm condition until a clear solution is obtained. Upon cooling, phthalic acid is released, after removal of which sodium hydroxide is added, extracted with benzyl amine with ether and purified in a known manner.

Example 2. In 424 parts of 1.3-dimethylbenzene, 195 parts of chloromethyl phthalimide and 10 parts of zinc chloride are added and heated to 90-100 with stirring for several hours until the release of hydrogen chloride stops. Then, unused demethylbenzene is distilled with water vapor and the viscous residue is recrystallized from hot alcohol. At the same time, 2.4-dimethyl-benzyl-phthalimide melting point 110 ° (pseudo-cumyl-phthalimide) is obtained together with small amounts of the body which is not soluble in alcohol. 133 parts of this imide are stirred in the cold from 124 parts of a 35% aqueous solution of sodium hydroxide, 300 parts of water and 300 parts of alcohol - for about 3 hours. After that, 300 h. 25 ° / o-hydrochloric acid is added, the alcohol is distilled off and the mixture is stirred in a water bath for several hours. When cooling, the phthalic acid main box crystallizes out. After its removal, it is possible to crystallize the 2.4-dimethyl-benzyl-amine hydrochloride by melting 210 through evaporation of the neutralized filtrate, or by adding sodium hydroxide to a pure base, boiling at 218-219.

Example 3. 6256-4. 195 parts of chloro-methyl-phthal-imide and 10 parts of zinc chloride are gradually introduced into the molten naphthalene and heated with stirring until the evolution of hydrogen chloride ceases. Then, unused naphthalene is distilled off with steam and, by recrystallization from alcohol, 1-naphthyl-methyl-phthalimide is obtained in the form of white crystals with a melting point of 175 °. 72 parts of this imide are completely dissolved by stirring with 70 parts of a 35% aqueous solution of sodium hydroxide, 200 parts of water and 250 parts of alcohol. Then 180 parts of 25% hydrochloric acid are added, the alcohol is distilled off and the mixture is stirred hot until a clear solution is obtained. After cooling, an excess of a strong solution of sodium hydroxide is added, extracted with ether 1-naphthyl-benzylamine and purified by distillation in vacuo.

Example 4: 155 parts of oxybenzene and 325 parts of chloromethyl phthalimide are dissolved in 2500 parts of water. Upon the addition of 50 parts of zinc chloride, it is gradually heated in a water bath to 70-80 ° until the release of hydrogen chloride stops. The benzene is decanted and distilled. From the residue, a condensation product can be obtained by recrystallization from hot alcohol in the form of pure white crystals. 25 parts of this compound are stirred in the cold for 2 hours from 30 hours to 35 ° / about the solution of sodium hydroxide and 200 parts of water. The solution is then acidified with dilute hydrochloric acid and heated in a water bath to dissolve the separated oil. Phthalic acid is removed by repeated treatment with ether, and then the weakly acidic aqueous solution is evaporated to dryness in vacuo. The residue is extracted with anhydrous alcohol. Upon evaporation of the solution, 4-hydroxy-benzyl-amine-chloro-hydrate is obtained together with a small amount of 2-hydroxy-benzylamine-chloro-hydrate. 4-hydroxy-benzyl-amine melts at 107 °, 2-hydroxy-benzyl-amine- at 129 °.

Example 5. In 324 parts of met-hydroxybenzene, 195 parts of chloromethyl phthalimide are dissolved, 10 parts of zinc chloride are added and heated to 120. When the release of hydrogen chloride is removed, the excess meth-hydroxybenzene is distilled off with steam and the residue is treated with cold alcohol, whereby the 4-meth-hydroxybenzyl-phthalimide formed is obtained in a quantity almost equal to the theoretically calculated, in the form of crystals of melting point 104 °. 50 hours of this compound are stirred in the cold for 2 hours with 50 hours of alcohol, 100 hours of a 35% aqueous solution of sodium hydroxide and 200 hours. water. The solution is then acidified with dilute hydrochloric acid, the alcohol is distilled off, and the separated oil is dissolved by adding water. After phthalic acid is removed by agitation with ether, the hydrochloric acid solution is evaporated in vacuo, the residue is extracted with alcohol, and 4-meth-hydroxy-1-benzyl-amine hydrochloride is thus obtained. From the concentrated aqueous solution of the salt, the free base is obtained by adding

hydrate of sodium oxide and treatment with ether.

Example b. According to the indications given in Example 5, it is possible even without the use of a catalyst to condense 63 parts of gua cola and 32 parts of chloromethyl phthalimide into 4-hydroxy-3-meth-hydroxy-benzyl-phthal; imica having a melting point of 154 By cleavage by the described method, vanillylamine is obtained.

Example 7. In 411 parts of 2-nitro-1-methyl-benzene, 195 parts of chloromethyl phthalimide were dissolved. After the addition of 10 parts, zinc chloride is heated to 120-130 with stirring, until the evolution of hydrogen chloride stops. Excess nitromethyl benzene is distilled off with steam, the residue is recrystallized from alcohol. 100 . the condensation product is stirred in the cold with 80 parts of a 35% sodium hydroxide solution, 300 parts of water and 300 hours. alcohol before dissolution. Then 150 parts of 25% hydrochloric acid are added, the alcohol is distilled off and the mixture is stirred in a water bath until everything is dissolved. Upon cooling, the phthalic acid which is separated out is filtered off, the filtrate is stirred with an excess of ammonia and extracted with 3-nitro-4-methyl-benzyl-amine ether, which can be purified by distillation in vacuo.

Example 8. 26.5 hours. 2.4 - dimethylbenzyl-phthalimide (cf. example 2) is dissolved in 130 parts of nitrobenzene and heated with 19.5 parts of chloromethyl-phthalimide and 3 parts of zinc chloride to 80-100. After the release of chloride hydrogen crystallizes the reaction product; 2.4-dimethyl-1-5-di-ooftalimidomethyl-benzene as white crystals; temp. 274 After the distillation of nitrobenzene, it is possible to obtain some more of the same compound from the residue. 37 parts of it are stirred from 150 parts of alcohol, 150 parts of water and 20 hours of 35 / about-th solution of sodium hydroxide in a hot state until complete dissolution. Then, 90 parts of hydrochloric acid 12 ° Be are added in the cold and stirring while heating and at the same time distilling off the alcohol to obtain a clear solution. Phthalic acid crystallizes out of solution upon cooling. The filtrate mixed with excess sodium hydroxide is treated with ether. From the ethereal solution, 2.4-dimethyl-1.5-di-Syu-amino-methyl) benzene is obtained in the form of white crystals, melting at 125 °.

Example 9. 27.4 parts of 1-naphtho-methylphthalimide are dissolved in 500 parts of nitrobenzene and heated to 100-120 ° C with 78 parts of chloromethyl phthalimide and 10 parts of zinc chloride. At the end of the evolution of hydrogen chloride, water nitrobenzene is distilled off with steam. 1.4-8-tri- (shaminomethyl) -naphthalene forms triphthalimide, which is obtained in the form of crystals, very difficult to dissolve in alcohol. 107h This phthalimide is dissolved in 509 parts of alcohol, 430 parts of water and 70 parts of a 35 ° / aqueous solution of sodium hydroxide, and then split with 200 parts of hydrochloric acid 12 Ve. Phthalic acid is separated and the retarder, to which excess sodium hydroxide is added, is shaken with chloroform. After evaporation of chloroform 1.4.8-tri- (a) -amino-methyl) -naphthalene remains as a water-soluble oil, boiling at a pressure of 15 mm at a temperature of 240-245

Example 10 89 parts of anthracene are dissolved with 195 parts of chloromethyl phthalimide and 10 parts of zinc chloride in nitrobenzene. The solution is heated to 85-100. 146 parts of the product obtained are dissolved in 1000 parts of alcohol, 400 parts of water and 83 parts of a solution of sodium hydroxide 35 Ve in a hot form and. 200 parts of hydrochloric acid 12 ° Be are cleaved. Phthalic acid is separated, the solution is mixed with excess sodium hydroxide, and 9.10-di- (α) -aminomethyl) anthracene is recovered by stirring with benzene. It forms crystals, which are difficultly soluble in water and decompose at a temperature between 250 and 270 °.

Example 11. 240 parts of the benzyl phthalimide prepared according to the method described in Example 1 are heated in a water bath with 550 parts of potassium hydroxide and 1700 parts of water, dissolving to form phthalamic acid. Distill the solution at

150-220 °, 1000 parts of water are added to the dry residue and all the liquid is again distilled. In the distillates there is an amount almost equal to the theoretically calculated benzyl amine, which, when the calculated amount of hydrochloric acid is added, is obtained by evaporation in the form of pure hydrochloride.

The subject of the patent. The method of producing aralkylamines and their derivatives, characterized in that the aromatic hydrocarbons or their derivatives, in the presence or absence of solvents and catalysts, are acted with sh-halo-methyl-phthal-imide and the resulting condensation product is treated with acids or alkalis in order to split it.