PL96221B1 - METHOD OF MAKING NEW AMINOPHENYLETHANOLAMINE - Google Patents

Description

The subject of the invention is a method for preparing new aminophenylethanolamines of the general formula 1, their optically active antipodes and their physiologically acceptable addition salts with inorganic and organic acids. In the above-given general formula 1, Rx represents an atom of hydrogen, fluorine, chlorine, bromine, iodine or gru. ¬ pe nitrile, R2 is a fluorine atom, a straight or branched chain alkyl group with 1-5 carbon atoms, a hydroxyalkyl, aminoalkyl, dialkylaminoalkyl, trifluoromethyl, alkoxy, nitro, nitrile, carboxyl, carbalkoxy or carbamyl, Rs and R4 are the same or different and denote hydrogen atoms, straight-chain or branched alkyl groups with 1-6 carbon atoms, hydroxyalkyl, cycloalkyl, cycloalkylalkyl, alkenyl, alkynyl or optionally substituted ¬ other aralkyl groups. Some compounds with a similar structure are known from British patent descriptions No. 1199,330, 1180,890, German patent descriptions No. 1,543,928, 1193,416 and from Swiss patent description No. 513,113. Moreover, compounds 1 have different pharmacological properties, namely, in addition to the analgesic effect, slowing down uterine contraction and antispasmodic effect on the striated muscles, these compounds have in particular a 32-mimetic and/or Px-blocking effect, and depending on their substitution, they have one or the other action comes to the fore. The pharmacological action of the compounds discussed in the cited patent literature is as follows: The German patent description No. 1,543,928 describes 4-amino-3,5-dibromo- and 4-amino- 3-bromo-5-chloro-phenylethanolamine, which has particularly analgesic properties. The German patent description No. 1,793,416 describes a method for producing 1-(4-amino-3,5-dichlorophenyl)-2-III-butylaminoethanol, which has in particular broncholytic properties. The Swiss patent description No. 513,113 describes further methods for preparing 4-amino-3,5-dihalophenylethanolamines known from the above-mentioned German patent. The obtained compounds are characterized by analgesic, broncholytic, sedative, antipyretic and cough-relieving properties, depending on the substituents present. The general formula given in the British patent description No. 1199,330 also includes, among others, 4-amino -monohalophenyl-ethanolamine, as the closest compound, is only described in example 12 l-(3-amino-4-bromophenyl)-2-cyclopropylaminoethanol. The compounds from this patent have an inhibitory effect on monoamine-oxidase and action on the central nervous system. British patent no. 1,180,890 discusses, among others, 4-amino-3-chloro and 4-amino-3-bromophenyl-ethanolamine, which has a particular analgesic effect. Compounds of general formula 1 have valuable pharmacological properties. In addition to the anesthetic effect, the release of uterine contractions and the antispasmodic effect on the striated muscles, these compounds have a particularly β-mimetic and/or (β-blocking) action, where, depending on the substitution, one comes to the fore or the second action. D(+)-compounds have a particular action on Pi-receptors, and 1(-)-compounds have an outstanding action on |32-receptors. According to the invention, new compounds are prepared by reducing acetophenone of formula 2, wherein Rx - R4 have the meanings given above. The reduction is carried out in particular in a solvent such as methanol, methanol/water, ethanol, isopropanol, ether, tetrahydrofuran or dioxane, preferably with a complex metal hydride such as lithium aluminum hydride or sodium borohydride. sodium, aluminum isopropylate in the presence of a primary or secondary alcohol or with catalytically activated hydrogen, at a temperature from -20° C. to the boiling point of the solvent used. Reductions with complex metal hydrides, however, are preferably carried out with a borohydride. sodium and at room temperature. When using a reactive complex metal hydride, such as aluminum lithium hydride, and possibly high temperature, the nitrile, carboxyl, carbalkoxy or carbamyl groups mentioned in the definition of R2 can be reduced simultaneously. If the reduction is carried out hydrogen in the presence of a catalyst such as Raney nickel, platinum or palladium on bone carbon, then the alkenyl or alkynyl groups mentioned in the definition of R3 and/or R4 can be converted into the corresponding alkyl and/or alkyl groups. or possibly present benzyl groups can be hydrogenolytically cleaved. The obtained compounds of general formula 1 can optionally be separated into their optically active antipodes by cleavage of the racemate or by separation of a mixture of diastereomeric compounds of general formula 3, in which Ri,R2, R3 and R4 have the meanings given above, R6 is a hydrogen atom or an acyl group and R7 is a chiral acyl group followed by cleavage of the groups R7, R6 and R4, where R6 is an acyl group and R4 is an optional substitution. substituted benzyl group. As chiral acyl groups R7, there may be mentioned optically active α-amino acid residues especially protected at the nitrogen atom, e.g. the N-benzyloxycarbonyl-L-alanyl group or optically active terpentoxycarbonyl groups, e.g. The separation of the mixture of diastereomeric compounds of the general formula III into pure diastereomeric compounds is effectively carried out by fractional crystallization and/or by means of column chromatography on an optically active carrier. The subsequent cleavage of the R6 and R7 groups is preferably carried out by hydrolysis or solvolysis in the presence of water or a suitable alcohol, such as methanol, optionally in the presence of an acid or base, at temperatures from 0° to 100°C. The cleavage of the R7 group can also be carried out with a complex metal hydride, such as lithium aluminum hydride, in a suitable solvent, for example ether, tetrahydrofuran or dioxane, effectively at a temperature of -20° to 20°C. If R2 in the compound of general formula 3 represents a nitrile group, it can be reduced at the same time. Depending on the type of substituents R6 and R7, their cleavage may occur gradually or in one stage. If R4 is an optionally substituted benzyl group, then its cleavage takes place in compounds in which R6 does not represent a nitro group, by hydrogenolysis in the presence of a suitable catalyst, such as palladium on carbon or barium sulfate, in a suitable solvent, e.g. an alcohol such as methanol or acetic acid, optionally with the addition of a mineral acid such as hydrochloric acid and optionally under elevated hydrogen pressure, especially at temperatures from 20 to 50°C. If R2 in the compound of general formula 3 is a nitrile group, it can be reduced at the same time. Cleavage of R4 may occur before or after cleavage of R6 and R7. If a compound of the general formula 1 is obtained, in which R2 is a nitrile group, it can be converted into the corresponding carbamyl compound. If R2 is a carbamyl or carbalkoxy group, these groups can be converted into the corresponding carboxyl groups in the compound of the general formula 1 by hydrolysis. The obtained compounds of the general formula 1 are optionally converted with inorganic or organic acids in their physiologically acceptable addition salts using 1, 2 or 3 equivalents of the appropriate acid. Suitable acids include, for example, hydrochloric, hydrobromic, sulfuric, phosphoric, lactic, citric, tartaric, maleic or fumaric acid. The compounds of general formula 2 used as starting products are obtained by methods known from the literature, e.g. appropriate 2-haloacetophenones with appropriate amines. The starting compound of formula 2 used in the process according to the invention does not have to be obtained in its pure state in all cases, it can also be used as a raw product. As already mentioned above, the new compounds of the general formula 1 exhibit valuable pharmacological properties, in particular 32-mi- 40 45 50 18 eo96 2 metic and/or 3-blocking activity, and depending on their substitution, primarily one occurs or second action. D(+)-compounds have a particularly selective effect on (^-receptors, and 1(—)-compounds have a particular action on (J2-receptors. For example, the following substances were tested for their action on |32-receptors : A = 1-(amino^-bromo^-fluoro-phenyl/-2-tert-butylaminoethanol hydrochloride, B = 1-(4'-amino-3'-chloro-5'-fluorophenyl) hydrochloride /-2-cyclopropylaminoethanol, C = 1-(4'-amino-3'-chloro-5'-fluorophenyl/-2-tert-butylaminoethanol hydrochloride, 15 D = 1-/4'-amino- 3'-fluorophenyl/-2-tert-butylaminoethanol, E = 1-(4'-amino-3'-trifluoromethylphenyl/-2-tert-pentylaminoethanol hydrobromide, F = 1-/4-hydrochloride '-amino-3'-chloro-5'-triflu- 2° oromethyl-phenyl/-2-tert.butylaminoethanol, G = 1-(4'-amino-3'-chloro-5'-hydrochloride) triyl-(oromethyl-phenyl)-2-cyclobutylaminoethanol, H = 1-(4,-amino-3'-chloro-5)-cyanophenyl/-2-III-25-butylaminoethanol, I = W4'-amino-hydrochloride 3'-bromo-5'-cyanophenyl/-2-tert-butylaminoethanol, K = 1-(4'-amino-3'-bromo-5'-fluorophenyl/-2-cyclobutylaminoethanol hydrochloride, 30 L = 1-(4'-amino-3'-fluoro-5'-iodophenyl)-2-cyclopopropylaminoethanol hydrochloride, M = 1-(4'-amino-3'-fluoro-5'-cyanophenyl) hydrochloride /-2-isopropylaminoethanol, N = 1-(4'-amino-3'-cyanophenyl/-2-35-cyclobutylaminoethanol hydrobromide, O = 1-(4'-amino-3'-cyanophenyl/-2-tertium) .- -pentylamino-ethanol, P = 1-(4'-amino-3'-chloro-5'-cyanophenyl/-2-propylaminoethanol hydrochloride, 40 Q = 1-(4'-amino-3'-) hydrochloride chloro-5'-cyanophenyl/-2-II-butylaminoethanol, . R = 1-(4'-amino-3'-chloro-5'-cyanophenyl)-2(hydroxy-tert-butylamino)-ethanol hydrochloride, *5 S = 1-(4'-amino hydrochloride) -3'-Chloro-5'-cyanophenyl/-2-III-pentylaminoethanol, T = 1-(4'-amino-3'-chloro-5'-cyanophenyl/-2-cyclopentylaminoethanol hydrochloride, U = 1-(4'-amino-3'-chloro-5'-cyanophenyl/-2-[l-(3,4-methylenedioxyphenyl)-2-propylaminoJ-ethanol hydrochloride, V = 1- /4'-amino-3'-bromo-5'-cyanophenyl/-2-cyclobutylaminoethanol, W = 1-(4'-amino-'3',5'-dicyanophenyl/-2-III) hydrochloride -p. butylaminoethanol, 5'-nitrophenyl(-2-III-butylamino-ethanol). The blocking action was tested as an antagonist against tachycardia induced by a standard dose of 1.0 µl/kg of intravenously administered N-isopropyl-radrenaline sulfate in 6 anesthetized cats. The ED50 was determined by graphical operation from the percentage attenuation of the increase in heart rate caused by N-isopropylradrenaline sulfate obtained with the different doses (Tables II and III). The 32-agonist effect was tested as an antagonist to bronchoconstriction induced by an intravenous dose of 20 µg/kg of acetylcholine in guinea pigs tested using the Konzett-R6ssler method. The percentage of bronchoconstriction reduction achieved with different doses was determined. by graphical extrapolation of ED50 (Table I). The 32-blocking effect was tested as an antagonist to the broncholytic effect induced by 5 µg/kg of intravenously administered N-isopropylnoradrenaline sulfate in anesthetized guinea pigs, using the Konzett-R6ssler method, when bronchospasm was induced in them with a standard amount of 20 µl/kg of intravenously administered acetylcholine (Table III). The acute toxicity of the substance was determined in groups consisting of 10 mice each. The LD50 was calculated on the basis of the doses intravenously, in which 50% of the animals died within 14 days. The experiments were carried out using the Litchfield and Wilcoxon method (Tables II and III). T a 151 i c a I Substance A B 1 C D E G tf I K L M N O P Q R ' S T U V L W Y | 1 Action |32-mimetic ni - 9 6 11 6 6 4 6 - 5 6 | n2 4 4 3 4 4 3 4 3 3 4 3 3 3 3 4 4 3 3 3 . | ED50 y/kg intravenously 8.3 24.0 19.0 18.0 19.5 6.8 0.2 4.8 58.0 0.08 0.32 6.9 3.6 27.0 .7 , 0 1.9 9.8 2.7 .5 11.3 31.5 | Operating time in minutes 150 50 120 80 130 125 95 40 50 40 40 40 v 65 50 80 65 40 50 65 50 65 80 | nj = number of animals/dose, n2 = number of doses taken into account when determining EDso.96 221 Table II Substance 1 A B C E F G H I K L M Action on f^-receptors * ni 2 3 4 4 4 3 6 6 n2 3 3 4 | ED50 y/kg intravenously 4 18-.5 14.0 8.0 13.5 .0 11.5 0.74 1.3 0.27 0.022 | LD50 mg/kg, intravenously | 34.5 57.0 .1 . 69.2 36.5 36.3 60.0 67.0 45.2 66.4 58.4 1 1 1 N O P Q R S T U V W X 1 Y 1 2 1 5 6 6 6 6 6 6 6 8 1 3 . 6 1 4 4 4 4 4 4 4 | c. 4 0.070 0.086 0.76 0.32 0.76 0.45 0.70 1.4 0.078 0.92 2.8 4.5 d. IT board 1 5 1 1 61.8 62.0 53.4 40.4 81.8 33.7 39.1 13.5 38.5 166.0 .8 42.4 n! = number of animals/dose n2 = number of doses Substance 1 A — d(+) C — d(+) D — d(+) F — d(+) ni 2 7 6 8 8 Table III Blocking effect on Pi-receptors n2 3 4 4 3 4 ED50 /kg intravenously 4 8.4 6.2 1.5 12.5 ni 4 Blocking effect on |32-n2 receptors 6 1 1 1 1 ED50 /kg intravenously 7 2000 2000 2000 2000 LD50 mg/kg intravenously 8 37.2 34.2 33.2 [ nj = number of animals n2 = number . doses tested on individual animals. The new compounds of the general formula I can optionally be converted into commonly used pharmaceutical forms in combination with other active substances. The unit dose is 1-100 y9, but especially 5-50 y. The following examples explain the invention in more detail, without limiting its scope. Example I. 1-(4-amino-3-bromo-5-fluorophenyl)-2-diethylaminoethanol 3.4 g of 4'-amino-3'-bromo-2-ethyl-amino-5'-fluoroacetophenone hydrochloride are dissolved in 20 ml of methanol and, while stirring, a solution of 570 mg of sodium borohydride in 5 ml of water is slowly added at room temperature , the pH value is adjusted to 3-6 by the simultaneous addition of 3N hydrochloric acid. After completing the addition of the sodium borohydride solution, the mixture is stirred for another 30 minutes at room temperature. Then 3n is added. hydrochloric acid until the pH value is 1. The hydrochloric acid solution is extracted twice with chloroform and the chloroform extracts are discarded. The aqueous solution is made basic with ammonia and extracted. exactly with chloroform. The chloroform extracts were combined, dried over sodium sulfate and concentrated in a vacuum until dry. A colorless oil remains, which is dissolved in ethyl acetate. After adding an ethereal solution of hydrochloric acid, a colorless precipitate forms, which is filtered off and dissolved in water. The aqueous solution is made basic with sodium hydroxide solution and extracted with chloroform. The chloroform extract is washed with water, dried over sodium sulfate and evaporated in vacuo. A colorless oil remains. The structure of the compound is confirmed by the nuclear resonance spectrum (NMR/CDC1S): 0.85 - 1.2 ppm triplet [6 protons, N/CH2 - CH8/2], 2.4 - 2.9 ppm multiplet [ 6 protons, N/CHg—/s], 4.15 ppm singlet (2 protons, NH2), 4.4—4.7 ppm multiplet (1 proton, CH), 4.85 ppm singlet (1 proton, OH) , 6.9—7.4 ppm multiplet (2 aromatic protons). Example II. 1-(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-2-tert-butylaminoethanol hydrochloride 80 g 4'-amino-3'-chloro-5'-trifluoromethylacetophenone hydrochloride ( decomposition 223-231°) is dissolved in 500 ml of methanol and cooled to - 15°C. While stirring, 9.5 g of sodium borohydride are added in portions within 1 hour, maintaining the temperature from -1 to -15°C. After another hour, while maintaining the temperature at -15°C, it is acidified with 2N hydrochloric acid and the methanol is removed in vacuo. The remaining aqueous solution is made basic with ammonia and extracted with acetic acid ester. The organic phase is washed with water, dried and treated with 50 ml of 4.5 N hydrochloric acid in isopropanol. The precipitated hydrochloride of the above-mentioned compound at 60 nm is filtered off and washed with acetic acid ester and ether. Melting point 205-207°C (decomposition). By concentrating the mother liquors, even further substances can be obtained. 5 Example III. 1-(4'-amino-3'-bromo-5'-cyanophenyl)-2-dimethylaminoethanol hydrochloride. 2 g of 4'-amino-3'-bromo-5'-cyano-2-dimethylaminoacetophenone are dissolved in 300 ml of methanol and a solution of 10 g of sodium borohydride in 100 ml of water is added dropwise at room temperature. It is left overnight, the sodium borohydride still present is decomposed by acidification with hydrochloric acid, the methanol is evaporated in a vacuum, the residue is dissolved in water, extracted three times with approximately 1500 ml of chloroform, the chloroform solution is washed with a small amount of water, dried over sodium sulfate and concentrated to dryness. The residue is dissolved in ethanol and acidified with an alcoholic hydrochloric acid solution, and 1-(4-amino-3-bromo-5-cyanophenyl)-2-dimethylaminoethanol hydrochloride crystallizes. which is recrystallized from ethanol. Melting point 187-190°C. Example IV. 1-(4'-amino-3'-fluorophenyl)-2'-25-tertiary-butylaminoethanol Prepared from 4'-amino-2'-III-tertiary-butylamino-3'-fluoroacetophenone hydrochloride and boron sodium oxide, similarly to example I. Melting point of hydrochloride 196-197°C 30 (decomposition). Example V. 1-(4'-amino-3'bromo-5'fluorophenyl/-2-tert.butylaminoethanol. Prepared from 4'amino-3'-bromo-2'-tert. hydrochloride .butylamino-5'-fluoroacetophenone and 35. sodium borohydride, analogously to Example I. Melting point of the hydrochloride 207-208°C (decomposition). Example VI. 1-(4'-amino-3'-chloro-5'-trifluoromethyl-phenyl)-2-cyclobutylaminoethanol Prepared from 4'-amino-3'-chloro-2-cyclobutylamino-5-trifluoromethylacetophene hydrochloride nu and sodium borane, similarly to Example II. Melting point of the hydrochloride 177-178°C. Example VII. 2'-ethylamino-1(4'-amino-3'-chloro-5'-fluorophenyl)ethanol Prepared from 2-ethylamino-4'amino-3'-chloro-5'-fluoro-a-ethylaminoacetophenone and sodium borohydride, analogously to Example I. Melting point of the hydrochloride 186-188°C (decomposition). Example VIII. 1-/4'-amino-3'-chloro-5'-fluorophenyl/-2-isopropylaminoethanol Prepared from 4'-amino-3'-chloro-5'-fluoro-2-isopropylaminoacetophenone hydrochloride and sodium borohydride, analogously to Example I. Melting point of the hydrochloride 152-154°C (decomposition). Example IX. 1-(4'-amino-3'-chloro-5'-fluoro-«phenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino^3'-chloro-5'-fluoro-a-cyclopropylaminoacetophenone and borohydride sodium, similarly to example I. Melting point of hydrochloride 175-^177°C (decomposition). <& 40 45 50 Example preferably butylamino-3'-chloro-5'-fluQroacetophenone and sodium borohydride, analogously to Example I. Melting point of the hydrochloride 206-208°C (decomposition). Example XI. 1-(4'-amino-3'-chloro-5'-fluorophenyl)-2-tertpentylaminoethanol Prepared from 4'-amino-3'-chloro-5'-fluoro-2 hydrochloride -III-pentylaminoacetophenone and sodium borohydride, analogously to Example I. Melting point of the hydrochloride 187-188°C (decomposition). Example XII. 1-(4'-amino-3'-chloro-5'-fluorophenyl)-2-[l-(3,4-methylenedioxyphenyl)-2-propylamino]-ethanol Prepared from 4'-amino- 3'-chloro-5'-fluoro-2-[l-(3,4-methylenedioxyphenyl)-2-propylamino]-acetophenone and sodium borohydride, analogously to Example I. Melting point of the hydrochloride 119-121 °C (decomposition). Example XIII. 1-^-amino^-chloro^-fluorophenyl/-2-dimethylaminoethanol. It is prepared from 4'-amino-3'-chloro-2-dimethylamino-5'-fluoroacetophenone hydrochloride and sodium borohydride, analogously to in example I. Melting point of the hydrochloride 208-210°C (decomposition). Example XIV. 1-(4'-amino-3'-chloro-5'-fluorophenyl)-2-diethylaminoethanol Prepared from 4'-amino-3'-chloro-2-diethylamino-5'-fluoroacetophenone hydrochloride and boron sodium chloride, similarly to example I. Temperature 39-41°C. Example XV. 2-ethylamino-1-(4'-amino-3'-bromo-5'-fluorophenyl)-ethanol Prepared from 2-ethylamino-4'-amino-3'-bromo-5'-fluoroacetophenone hydrochloride and borane sodium, analogously to Example I. Melting point of the hydrochloride 167-169°C (decomposition). Example XVI. 1-^-amino-S^bromo-S^fluorophenyl/-2-isopropylaminoethanol. Prepared from 4'-amino-3'-bromo-5'-fluoro-2-isopropylaminoacetophenone hydrochloride and sodium borohydride, similarly to example I. Melting point of hydrochloride 171-173°C (decomposition). Example XVII. 1-(4'-amino-3'-bromo-5'-fluorophenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino-3'-bromo-2-cyclopropylamino-5'-fluoroacetophenone and sodium borohydride , similarly to Example I. Melting point of the hydrochloride 185-187°C (decomposition). Example XVIII. 1-(4'-amino-3'-bromo-5'-fluorophenyl)-2-(hydroxy-tert.butylamino)-ethanol Prepared from 4'-amino-3'-bromo- hydrochloride 5'-fluoro-2-(hydroxy-tert.butylamino)-acetophenpne and sodium borohydride, analogously to Example I. Melting point 122-125°C. Example XIX. 1-(4'-amino-3'-bromo-5'-fluorophenyl) : Prepared from 4'-amino-3'-bromo-5^fluoro-2- chloride III-pentylaminoacetophenone and bo-MISI 11 11 sodium hydride, analogously to example I. Melting point of the hydrochloride 185-187°C (decomposition). Example XX. 1-(4'-amino-3'-bromo-5'-fluorophenyl)-2-[l-(3,4-methylene dioxyphenyl)-2-propyl-5 amino]-ethanol Preparated from 4'-amino -3'-bromo-5'-fluoro-2-[l- (3,4-methylene dioxyphenyl)-2-propylamino]-acetophenone and sodium borohydride, analogously to Example I. Melting point 126-128°C . *° Example XXI. 1-(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-2-isopropylaminoethanol Prepared from 4'-amino-3'-chloro-2-isopropylamino-5'-trifluoromethylacetophenone hydrochloride and sodium borohydride, similarly to Example II. Melting point 104-106°C. Example XXII. 1-(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino-3'-chloro-2-cyclopropylamino-5'-trifluoromethyl-acetophenone and boron-*) sodium dodecate, similarly to example II. Melting point 138-139°C. Example XXIII. 1-(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-2-(hydroxy-tert.butylamino)-ethanol 16 Prepared from 4'-amino-3'-chloro hydrochloride - ro-2-(hydroxy-tertiary-butylamino)-5'-trifluoromethylacetophenone and sodium borohydride, similarly to Example II. Melting point of the hydrochloride219-220°C. » Example XXIV. 1-(4'-amino-3'-chloro-5'-tri-fluoromethyl-phenyl)-2-tertiary-pehtylaminoethanol Prepared from 4'-amino-3'-chloro-2-ni- hydrochloride mainly pentylamine-5'-trifluoromethyl-acetophenone and sodium borohydride, similarly to Example II. Melting point of hydrochloride 176-178°C (decomposition). Example XXV. 1-/4'-amino-3'-chloro-5'-tri-fluoromethyl-phenyl/-2-[2-methylO-4-hydroxybutyl/- -/2/-amino]-ethanol * Prepared from 4' -amino-3'-chloro-2-[2-methyl-4-hydroxybutyl-(2)-ammo]-5'-trifluoromethyl-acetophenone and sodium borohydride, analogously to Example II. Melting point of hydrochloride 148-150°C (decomposition). « Example XXVI. 2-[3-ethynyl-pentyl-(3)-amino]-1-(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-ethanol Prepared from 2-[3-ethynylpen- hydrochloride tyl-(3)-amino]-4'-amino-3'-chloro-5'-trifluoromethylacetophenone and sodium borohydride, analogous to Example II. Melting point of the hydrochloride 185-187°C (decomposition). - Example XXVII. 1-(4'-amino-3'-chloro-5'-tri-fluoromethylphenyl)-2-[1-(3,4-methylenedioxyphenyl-*yl)-2-pylamino]-ethanol Prepared from 4'- hydrochloride amino-3'-chloro-2-[l-(3,4-methylene dioxyphenyl)-2-propylamino]-5'-trifluoromethylacetophenone and sodium borohydride, analogously to Example II. Melting point of hydrochloride 206-207°C (decomposition). Example XXVIII. 1-(4'-amino-3'-chloro-5'-trifluoromethyl-phenyl)-2-dimethylaminoethanol Prepared from 4'-amino-3'-chloro-2-dimethylamino-5'-trifluoromethylacetophene hydrochloride *nu and sodium borohydride, similarly to Example II. Melting point of the hydrochloride 162-164°C. Example XXIX. 1-(4'-amino-3'-chloro-5'-fluoromethylphenyl)-2-(N-methylethylamino)-ethanol Prepared from 4'-amino-3'-chloro-2-(N) hydrochloride -methyl-ethylamino/5'-trifluoromethylacetophenone and sodium borohydride, analogously to Example II. Melting point 48-49°C. Example XXX. 1-(4'-amino-3'-chloro-5'-tri-fluoromethyl-phenyl)-2-diethylaminoethanol Prepared from 4'-amino-3'-chloro-2-diethylamino-5'-trifluoromethylacetophenone hydrochloride and sodium borohydride, similarly to Example II. Melting point of the hydrochloride 149--151°C. / Example XXXI. 1-(4-amino-3-chloro-5-tri-fluoromethyl-phenyl)-2-(N-benzyl-N-III-ter-butyl)-aminoethanol Prepared from 2'-amino-2-/ N-benzyl-N-III-butyl(-amino-3'-chloro-5'-trifluoromethyl-acetophenone and sodium borohydride, analogously to Example II. Oil, uniform in thin-layer chromatogram (Si02, chloroform: methanol = = 15:1, Rf: ~0.75). Example XXXII. 1-(4'-amino-3'-bromo-5'-trifluoromethylphenyl)-2-isopropylaminoethanol Prepared from 4'-amino-3'-bromo-2-isopropylamino-5'-trifluoromethylacetophenone hydrochloride and sodium borohydride, similarly to Example II. Melting point 102-103°C. Melting point of the hydrochloride: 177-179°C (decomposition). Example XXXIII. 1-(4'-amino-3'-bromo-5'-trifluoromethylphenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino-3'-bromo-2-cyclopropylamino-5'-trifluoromethylacetophenone hydrochloride and sodium borohydride, similarly to Example II. Melting point 141.5-142.5°C. Melting point of hydrochloride 195-195.5°C (decomposition). j Example XXXIV. 1-(4'-amino-3'-bromo-5'-trifluoromethylphenyl)-2-tertiary-butylaminoethanol Prepared from 4'-amino-3'-2-tert-butylamino- hydrochloride 5'-trifluoromethylacetophenone and sodium borohydride, similarly to Example II. Melting point 85-87°C. Melting point of the hydrochloride: 205-206°C (decomposition). Example XXXV. 1-(4'-amino-3'-bromo-5'-trifluoromethyl-phenyl)-2-cyclobutylaminoethanol Prepared from 4'-amino-3'-bromo-2-cyclobutylamino-5'-trifluoromethylacetophene hydrochloride nonium and sodium borohydride, similarly to Example II. Melting point of hydrochloride 189-191°C (decomposition). Example XXXVI. 1-(4'-amino-3'-bromo-5'-trifluoromethylphenyl)-2-tert pentylaminoethanol Preparated from 4'-amino-3'-bromo-2-tert hydrochloride pentylamino-5'-trifluoromethylacetophenone and sodium borohydride, similarly to Example II. Melting point of the hydrochloride salt: 166.5-168.5°C (decomposition). The said compound is filtered off and washed with acetic acid ester and ether. Melting point 205-207°C (decomposition). By concentrating the mother liquors, even further substances can be obtained. Example III. 1-(4'-amino-3'-bromo-5'-cyanophenyl)-2-dimethylaminoethanol hydrochloride. 2 g of 4'-amino-3'-bromo-5'-cyano-2-dimethylaminoacetophenone are dissolved in 300 ml of methanol and a solution of 10 g of sodium borohydride in 100 ml of water is added dropwise at room temperature. It is left overnight, the sodium borohydride still present is decomposed by acidification with hydrochloric acid, the methanol is evaporated in a vacuum, the residue is dissolved in water, extracted three times with about 1500 ml of chloroform, washed with a small amount of water and dried. ad sodium sulfate and concentrate until dry. The residue is dissolved in ethanol and acidified with alcohol. hydrochloric acid solution, whereby 1-(4-amino-3-bromo-5-cyanophenyl)-2-dimethylaminoethanol hydrochloride crystallizes and is recrystallized from ethanol. Melting point 187-190°C. Example - IV. 1-(4'-amino-3'-fluorophenyl)-2'-tertiary-butylaminoethanol Prepared from 4'-amino-2'-tertiary-butylamino-3'-fluoroacetophenone hydrochloride and borohydride sodium, similarly to example I. Melting point of hydrochloride 196-197°C (decomposition). Example V. 1-(4'-amino-3'bromo-5'fluorophenyl)-2-tert.butylaminoethanol Prepared from 4'amino-3'-bromo-2'-tert. hydrochloride butylamind-5'-fluoroacetophenone and sodium borohydride, similarly to Example I. Melting point of the hydrochloride: 207-208°C (decomposition). Example VI. 1-(4'-amino-3'-chloro-5'-trifluoromethyl-phenyl)-2-cyclobutylaminoethanol Prepared from 4'-amino-3'-chloro-2-cyclobutylamino-5-trifluoromethylacetophene hydrochloride nu and sodium borane, similarly to Example II. Melting point of the hydrochloride 177-178°C. Example VII. 2'-ethylamino-1(4'-amino-3'-chloro-5'-fluorophenyl)ethanol Prepared from 2-ethylamino-4,amino-3'-chloro-5'-fluoro-a-ethylaminoacetophenone and sodium borohydride, analogously to Example I. Melting point of the hydrochloride 186-188°C (decomposition). Example VIII. 1-(4'-amino-3'-chloro-5'-fluoro-phenyl)-2-isopropylaminoethanol Prepared from 4'-amino-3'-chloro-5'-fluoro-2-isopropylaminoacetophenone hydrochloride and boro ¬ sodium hydride, similarly to example I. Melting point of hydrochloride 152-154°C (decomposition). Example IX. 1-(4'-amino-3'-chloro-5'-fluoro-phenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino-3'-chloro-5'-fluoro-a-cyclopropylaminoacetophenone and sodium borohydride , similarly to Example I. Melting point of the hydrochloride 175-177°C (decomposition). Example 3'-chloro-5'-fluoroacetophenone and sodium borohydride, analogously to Example I. Melting point of the hydrochloride 206-208°C (decomposition). Example XI. 1-(4'-amino-3'-chloro-5'-fluorophenyl)-2-tertpentylaminoethanol Prepared from 4'-amino-3'-chloro-5'-fluoro-2 hydrochloride -III-pentylaminoacetophenone and sodium borohydride, analogously to Example I. Melting point of the hydrochloride 187-188°C (decomposition). Example XII. 1-(4'-amino-3'-chloro-5'-fluorophenyl)-2-[l-(3,4-methylenedioxyphenyl)-2-propylamino]-ethanol Prepared from 4'-amino- 3'-chloro-5'-fluoro-2-[l-(3,4-methylenedioxyphenyl)-2-propylamino]-ace-M tophenone and sodium borohydride, analogously to Example I. Melting point of the hydrochloride 119- 121°C (decomposition). Example XIII. 1-(4'-amino-3'-chloro-5'-fluorophenyl)-2-dimethylaminoethanol. "Prepared from 4'-amino-3'-chloro-2-dimethylamino-5'-fluoroacetophenone hydrochloride and sodium borohydride, analogously to Example I. Melting point of the hydrochloride: 208-210°C (decomposition). Example XIV. 1-(4'-amino-3'-chloro-5'-fluorophenyl)-2-diethylaminoethanol Prepared from 4'-amino-3'-chloro-2-diethylamino-5,-fluoroacetophenone hydrochloride and boron ¬ sodium chloride, similarly to example I. Temperature 39°C. Example XV. 2-ethylamino-1-(4'-amino-3'-bromo-5'-fluorophenyl)ethanol Prepared from 2-ethylamino-4'-amino-3'-bromo-5'-fluoroacetophenone hydrochloride and borane - 40 towards sodium, analogously to Example I. Melting point of the hydrochloride 167-169°C (decomposition). Example XVI. 1-(4,-amino-3'-bromo-5'-fluorophenyl)-2-isopropylaminoethanol 45 Prepared from 4'-amino-3'-bromo-5'-fluoro-2-isopropylaminoacetophenone hydrochloride and sodium borohydride analogously to Example I. Melting point of the hydrochloride 171-173°C (decomposition). 50 Example XVII. 1-^-amino^-bromo-S^fluorophenyl/-2-cyclopropylaminoethanol Prepared from 4'-amino-3'-bromo-2-cyclopropylamino-5'-fluoroacetophenone and sodium borohydride, analogously to the example I. Melting point of the hydrochloride 185-187°C (decomposition). Example XVIII. 1-(4'-amino-3'-bromo-5'-fluorophenyl)-2-(hydroxy-tert.butylamino)-ethaneQ1 Prepared from 4'-amino-3'-bromo- hydrochloride 5,-fluoro-2-(hydroxy-III-butylamino)-ace- in tophenone and sodium borohydride, analogously to Example I. Melting point 122-125°C. Example XIX, 1-(4'-araine- 3'-bromo-5'-fluorophenyl/-2-tert.pentylaminoethanol Prepared from 4'-amino-3'-bromo-*-5'-fluoro-2-tert.pentylaminoacetophenorph chloride and because -11 96 221 12 sodium hydride, analogously to example I. Melting point of the hydrochloride 185-187°C (decomposition). Example XX. 1-(4'-amino-3'-bromo-5'-fluorophenyl)-2-[l-(3,4-methylenedioxyphenyl)-2-propylamino]-ethanol Prepared from 4'-amino- 3'-bromo-5'-fluoro-2-[l-(3,4-methylenedioxyphenyl)-2-propylamino]-acetophenone and sodium borohydride, similarly to Example I. Melting point 126-128°C. Example XXI. 1-(4'-amino-3'-chloro-5Vtri-fluoromethylphenyl)-2-isopropylaminoethanol _ Prepared from 4'-amino-3'-chloro-2-isopropylamino-5'-trifluoromethylacetophenone hydrochloride and borohydride sodium, similarly to Example II. Melting point 104-106°C. Example XXII. 1-(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino-3'-chloro-2-cyclopropylamino-5'-trifluoromethyl-acetophenone and sodium borohydride, analogously to example II. Melting point 138-139°C. Example XXIII. 1-(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-2-(hydroxy-tert.butylamino)-ethanol Prepared from 4'-amino-3'-chloro- hydrochloride ro-2-(hydroxy-III-butylamino)-5'-trifluoromethylacetophenone and sodium borohydride, similarly to Example II. Melting point of the hydrochloride 219-220°C. Example XXIV. 1-(4'-amino-3'-chloro-5'-tri-fluoromethyl-phenyl)-2-III-pentylaminoethanol Prepared from 4'-amino-3'-chloro-2-III- hydrochloride mainly pentylamino-5'-trifluoromethyl-acetophenone and sodium borohydride, similarly to Example II. Melting point of hydrochloride 176-178°C (decomposition). Example XXV. 1-(4'-amino-3'-chloro-5'-tri-fluoromethyl-phenyl/-2-[2-methyl-4-hydroxybutyl/- -/2/-amino]-ethanol Prepared from 4'- amino-3'-chloro-2-[2-methyl-4-hydroxybutyl-(2)-amino]-5'-trifluoromethyl-acetophenone and sodium borohydride, analogously to Example II. Melting point of hydrochloride 148-150°C (decomposition). Example XXVI. 2-[3-ethynyl-pientyl-(3)-aminol-1-M^amino-S^chlor.o-S^trifluoromethylphenyl]-ethanol Prepared from 2-[3-ethynyl-pentyl-ZSZ-amino^^ hydrochloride -amino-S^chloro-S^trifluoromethylacetophenone and sodium borohydride, analogous to Example II. Melting point of the hydrochloride: 185-187°C (decomposition). Example XXVII. 1-(4'-amino-3'-chloro-5'-trifluoromethylferiyl)-2- [1-(3,4-methylene dioxyphenyl)-propylaminol-ethanol Preparated from 4'-amino-3 hydrochloride '-chloro-2-[l-(3,4-methylenedioxyphenyl)-2-propylamino]-5'-trifluoromethylacetophenone and sodium borohydride, analogously to Example II. Melting point of the hydrochloride: 206-207°C (decomposition). "Example XXVIII. 1-(4-amino-3'-chloro-5'-trifluoromethyl-phenyl)-2-dimethylaminoethanol. Prepared from 4'-amino-3'-chloro-2-dimethylamino-5' hydrochloride -trifluoromethylacetophenone and sodium borohydride, analogously to Example 2. Melting point of the hydrochloride 162-164°C. Example XXIX 1-(4'-ammo-3'-chlqro-5'-fluomethylphenyl)- 2-(N-methylethylamino)-ethanol. Prepared from 4'-amino-3'-chloro-3-ZN-methyl-ethylamino/S-trifluoromethylacetophenone hydrochloride and sodium borohydride, analogously to Example 2. Melting point 48 -49°C. io Example XXX. 1-^-amino^-chloro^-tri-fluoromethyl-phenyl]-2-diethylaminoethanol Prepared from 4'-amino-3'-chloro-2-diethylamino-5' hydrochloride -trifluoromethylacetophenone and sodium borohydride, analogously to example II. Melting point of the hydrochloride 149--151°C. Example XXXI. 1-(4-amino-3-chloro-5-tri-fluoromethyl-phenyl/-2-/N "-benzyl-N-III-part-butyl/-aminoethanol Prepared from 2'-amino-2-(N-benzyl-N-III-part.-butyl)-amino-3'-chloro-5' -trifluoromethyl-acetophenone and sodium borohydride, similarly to Example II. Oil, uniform in thin-layer chromatogram (Si02, chloroform: methanol = » = 15:1, Rf: ~ 0.75). Example XXXII. 1-(4'-amino-3'-bromo-5'-trifluoromethylphenyl)-2-isopropylaminoethanol Prepared from 4'-amino-3'-bromo-2-isopropylamino-5'-trifluoromethylacetophene-50 hydrochloride nu and sodium borohydride, similarly to Example II. Melting point 102-103°C. Melting point of the hydrochloride: 177-179°C (decomposition). Example XXXIII. 1-(4'-amino-3'-bromo-5'-trifluoromethylphenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino-3'-bromo-2-cyclopropylamino-5'-trifluoromethylacetophenone hydrochloride and sodium borohydride, similarly to Example II. Melting point 141.5-142.5°C. 40 Melting point of hydrochloride 195-195.5°C (decomposition). Example XXXIV. 1-(4'-amino-3'-bromo-5'-trifluoromethylphenyl)-2-tert.butylaminoethanol - 45 Prepared from 4'-amino-3'-2-tert. hydrochloride. butylamino-5'-trifluoromethylacetophenone. and sodium borohydride, similarly to Example II. Melting point 85-87°C. Melting point of the hydrochloride: 205-206°C (decomposition). Example XXXV. 1-(4'-amino-3'-bromo-5'-trifluoromethyl-phenyl)-2-cyclobutylaminoethanol Prepared from 4'-amino-3'-bromo-2-cyclobutylamino-5'-trifluoromethylacetophene hydrochloride in nonium and sodium borohydride, similarly to Example II. Melting point of hydrochloride 189-191°C (decomposition). Example XXXVI. 1-(4'-amino-3'-bromo-5'-trifluoromethylphenyl)-2-phyll-pentylamihoeta-«o nol Prepared from 4'-amino-3'-bromo-2-III hydrochloride -pentylamino-5'-trifluoromethylacetophenone and sodium borohydride, similarly to Example II. Melting point of hydrogen chloride 166.5-168.5°C (decomposition).96 221 13 14 Example XXXVII. 2-[3-ethynylpentyl-(3)-amino]-1-(4'^mino-3'-bromo-5'-trifluoromethylphenyl)-ethanol Prepared from 4'-amino-3'-bro hydrochloride - mo-5'-trifluoromethyl-a-[3-ethynylentyl-(3)-amino]-acetophenone and sodium borohydride analogously to Example II. Melting point of hydrochloride 189-190°C (decomposition). Example XXXVIII, 1-(4'-amino-3'-bromo-5'-trifluoromethylphenyl)-2-dimethylaminoethanol 10 Prepared from 4'-amino-3'-bromo-2-dimethylamino-5/- hydrochloride trifluDromethylacetophenone and sodium borohydride, similarly to Example II. Melting point of the hydrochloride 149-151°C. 15 Example XXXIX. 1-(4-amino-3'-bromo-5'-trifluoromethylphenyl)-2-(N-methylethylamino)-ethanol Prepared from 4'-amino-3'-bromo-2-/N- hydrochloride methyl-ethylamino-5'-trifluoromethylacetophenone and sodium borohydride, analogously to Example II. Melting point 52.5-53.5°C. Example XL. 1-(4'-amino-3'-bromo-5'-tri-fluoromethyl-phenyl)-2-diethylaminoethanol Prepared from 4,-amino-3,-bromo-2-diethylamino-5'- hydrochloride trifluoromethylacetophenone and sodium borohydride, similarly to Example II. Melting point of the hydrochloride 159-160°C. Example XLI. 1-(4'-amino-3'-methylphenyl)-30 -2-tert-butylaminoethanol Prepared from 4'-amino-3'-methyl-2-tert-butylaminoacetophenone and sodium borohydride, anal ¬ logically as in example III. Melting point of the hydrochloride salt 108°C (decomposition): 35 Example XLII. 1-(4'-amino-3'-chloro-5'-methylphenyl)-2-methylaminoethanol Prepared from 4'-amino-3'-chloro-5'-methyl-2-methylaminoacetophenone and sodium borohydride, similarly to example III. Melting point 95-96°C. Example XLIII. 2-ethylamino-1-(4'-amino-3'-chloro-5'-methylphenyl)-ethanol Prepared from 2-ethylamino-4'-amino-3'-chloro-5'-methylacetophenone and sodium borohydride , similarly to example III. Melting point 107-108.5°C. Example XLIV. 1-(4'-amino-3'-chloro-5'-methylphenyl)-2-dimethylaminoethanol Prepared from 4,-amino-3,-chloro 50-2-dimethylamino-5'-methylacetophenone hydrochloride and boron sodium hydride, analogously to Example I. Melting point of the hydrochloride 120-125°C (decomposition). Example XLV. 1-(4'-amino-3'-chloro-5'-methyl-55)-2-(N-methylethylamino)-ethanol Prepared from 4'-amino-3'-chloro-5,-methyl hydrochloride -2-(N-methylethylamino)-acetophenone and sodium borohydride, similarly to Example I. Melting point of the hydrochloride: 93-96°C. 60 Example XLVI. 1-(4'-amino-3'-chloro-5'-methylphenyl)-2-diethylaminoethanol Prepared from 4'-amino-3'-chloro-2-diethylamino-5'-methylacetophenone hydrochloride and boron sodium hydride, analogously to Example I. Melting point of hydrochloride 118-122°C (decomposition). Example XLVII. 1-(4'-amino-3'-chloro-5'-methylphenyl)-2-(N-benzyl-N-III-ter.butyl)-amino-ethanol Prepared from 4'-amino-2- (N-benzyl-N-III-butyl)-amino-3'-chloro-5'-methylacetophenone and sodium borohydride, similarly to Example III. Melting point of the hydrochloride: 200-201°C. Example XLVIII , 1-(4'-amino-3'-bromo-5'-methylphenyl)-2-dimethylaminoethanol Prepared from 4'amino-3'-bromo-2-dimethylamino-5'-methylacetophenone and borohydride sodium, similarly to example III. Melting point of hydrochloride 123-125°C (decomposition). Example XLIX. 1-(4'-amino-3'-bromo-5'-methylphenyl)-2-diethylaminoethanol Prepared from 4'-amino-3'-bromo-2-diethyl-amino-5'-methylacetophenone and sodium borohydride , similarly to example III. Melting point 48-50°C. Example composed of 4'affin-3'-bromo-2-(n-benzyl-N-III-butyl)-amino-5'-methylacetophene and sodium borohydride, analogously to Example III. The product is pure according to thin layer chromatography (= SiOs, chloroform: methanol = = 9:1, Rf value: ~ 0.9). Example LI. 1-(3'-ethyl-4'-amino-5'-chlorophenyl)-2-diethylaminoethanol Prepared from 3'-ethyl-4'-amino-5'-chloro-2-diethylaminoacetophenone and sodium borohydride, similarly to example III. Melting point of the hydrochloride 121-124°C. Example LII. 1-(3'-ethyl-4'-amino-5'-bromo-phenyl)-2-diethylaminoethanol Prepared from 3'-ethyl-4'-amino-5'-bromo-2-diethylamino-acetophenone and borohydride sodium, similarly to example III. Melting point of the hydrochloride 132-134°C. Example LIII. 1-(4'-amino-3'-tert.butyl--5'-chlorophenyl/-2-tert.butylaminoethanol Prepared from 4'-amino-3'-tert.butyl-2- III-butylamino-5'-chloroacetophenone and sodium borohydride, analogously to Example I. Melting point of the hydrochloride from 218°C (decomposition). Example LIV. 1-(4'-amino-3'-hydroxymethylphenyl)-2-dimethylaminoethanol. It is prepared from 4'-amino-2-dimethylamino-3'-hydroxymethylacetophenone and sodium borohydride, analogously to Example I. Confirms the structure the spectrum in the ultraviolet and infrared. UV/Ethanol/: maximum at 250 nm (E = = 0.5), inflection at 275-305 nm (E = 0.11), IR(CH2C12): OH at 3600 cm-1, NH2 at 3380 and 3450 cm -1, N(CH3)2 at 2780 and 2830 cm"1. Example LV. 1-(4'-amino-3'-hydroxymethyl-phenyl)-2-diethylaminoethanol. Prepared from 4'-amino-2-diethylamino- 2'-hydrofylmethylacetophenone and sodium borohydride, analogously to Example I. Melting point of the dihydrochloride from 125°C (decomposition).96 221 16 Example LVI. 1-(4'-amino-3'-chloro-5'- cyanophenyl/-2-isopropylaminoethanol. Prepared from 4'-amino-3'-chloro-5'-cyano-2-isopropylaminoacetophenone and sodium borohydride, analogously to Example 3. Melting point of the hydrochloride 185-188°C. Example LVII: 1-(4'-amino-3'-chloro-5'-cyanophenyl)-2-tert-butylaminoethanol Prepared from 4'-amino-3'-chloro-5'-cyano-2 - tertiary butylaminoacetophenone and sodium borohydride, similarly to Example 3. Melting point 125-133°C. Example LVIII 1-(4'-amino-3'-chloro-5'-cyanophenyl) /-2-dimethylaminoethanol. It is prepared from 4'-amino-3'-chloro-5'-cyano-2-15-dimethylaminoacetophenone and sodium borohydride, analogously to Example III. Melting point of the hydrochloride 187-189°C. Example LIX. 1-(4'-amino-3'-chloro-5'-cyanophenyl)-2-diethylaminoethanol 20 f Prepared from 4'-amino-3'-chloro-5'-cyano-2-diethylaminoacetophenone and borohydride sodium, similarly to example III. Melting point 69-71°C. Example LX. 1-(4'-amino-3'-bromo-5'-cyano-phenyl)-2-isopropylaminoethanol Prepared from 4'-amino-3'-bromo-5'-cyano-2-isopropylaminoacetophenone and sodium borohydride , similarly to example III. Melting point of the hydrochloride 186-189°C. 30 Example LXI. 1-(4'-amino-3'-bromo-5'-cyanophenyl)-2-tert-butylaminoethanol Prepared from 4'-amino-3'-bromo-2-tert-butylamino -5'-cyanoacetophenone and sodium borohydride, similarly to Example III. Melting point of the hydrochloride 213-215°C. Example LXII. l-/4'-amino-3'-bromo-5'-cyanophenyl/-2-diethylaminoethanol Prepared from 4'-amino-3'-bromo-5'-cyano-2-diethylaminoacetophenone and sodium borohydride, 40 similarly to example III. Melting point 72-74°C. Example LXIII. 1-(4'-amino-3'-bromo-5'-carboxyphenyl)-2-tert.butylaminoethanol Prepared from 4'-amino-3'-bromo-2-tert.bu- 45 tylamino-5'-carboxyacetophenone and sodium borohydride, similarly to Example III. Melting point from 218°C (decomposition). Example LXIV. 1-(4'-amino-3'-chloro-5'-methoxyphenyl/-2-tert.-butylaminoethanol 50 Prepared from 4'-amino-2-tert.-butylamino-3'- hydrochloride chloro-5'-methoxyacetophenone and sodium borohydride, analogously to Example I. Melting point of the hydrochloride 175-178°C (decomposition). 55 Example LXV. W4'-amino-5'-bromo-3'-hydroxymethylphenyl/-2-dimethylaminoethanol. Prepared by bromination of 1-(4-amino-3-hydroxymethyl-phenyl)-2-dimethylaminoethanol, analogously to Example VI. Melting point 60°C 87-92°C. Example LXVI. l-/4'-amino-3'-bromo-5'-cyanophenyl/-2-cyclopropylaminoethanol -** 7.5 g 4'-amino-3'-bromo-5'-cyano-2-cyclopropyl- laminoacetophenone dissolved in 200 ml of quart-65 hydrogenofuran and 100 ml of water, 3 g of sodium borohydride are added at room temperature and stirred for 1 hour, then the excess sodium borohydride is decomposed with the addition of acetone. The insoluble substances are filtered off and the solvent is distilled off. in a vacuum. The residue is dissolved in hot isopropanol and by adding an isopropanol hydrochloric acid solution, 1-(4-amino-3-bromo-5-cyanophenyl)-2-cyclopropylaminoethanol hydrochloride is obtained, which is recrystallized from isopropanol. Melting point 190-193°C (decomposition). Example LXVII. 1-(4'-amino-3'-bromo-5'-fluorophenyl)-2-cyclobutylaminoethanol a) 20 g of 4'-amino-3'-bromo-5'-fluoroacetophenone are dissolved in 300 ml of chloroform. After heating to boiling, a solution of 4.3 ml of bromine in 20 ml of chloroform is slowly added dropwise while stirring, then stirred for another 5 minutes at boiling point and cooled to room temperature. To the crude solution of 4'-aminQ-3', While stirring and cooling with ice, a mixture of 15 g of cyclobutylamine and 14 ml of triethylamine was added dropwise to 2-dibromo-5'-fluoroacetophenpne. After the addition is complete, it is heated to reflux temperature for 2 hours. After cooling, the organic phase and the concentration are washed in vacuo until boiling. The residue consists of crude 4'-amino-3'-bromo-2-cyclobutylamino-5'-fluoroacetophenone. b) The crude ketone obtained under a) is dissolved in 30 ml of tetrahydrofuran. The solution is mixed with 5 ml of water and then 4.5 g of sodium borohydride are added in portions while stirring and cooling with ice. The solution is stirred and cooled for 3 hours and then left at room temperature overnight. Then the excess sodium borohydride is decomposed with acetone and the solution is concentrated in vacuo to dryness. The residue is treated with water and chloroform, the organic phase is extracted with 3 x 100 ml of 2N hydrochloric acid, the combined hydrochloric acid extracts are made alkaline with sodium hydroxide and extracted with chloroform. The chloroform solution is washed with water, dried over sodium sulfate and the concentrate is concentrated to dryness in a vacuum. The remaining precipitate of crude 1-(4-amino-3-bromo-5-fluorophenyl)-2-cyclobutylaminoethanol is dissolved in isopropanol and acidified with an ether solution of hydrochloric acid to pH 5. After adding the ether, crystallization occurs. The precipitated hydrochloride of the desired compound is recrystallized from isopropanol. Melting point 164-166°C (decomposition). Example LXVIII. 1-(4'-amino-3'-bromo-5'-fluorophenyl)-2-cyclopentylaminoethanol Prepared from 4'-amino-3'1bromo-2-cyclopentylamino-5'-fluoroacetophenone and sodium borohydride, analogously as in example LXVII. Melting point of the hydrochloride 167-170°C (decomposition). Example LXIX. 1-(4'-amino-3'-brpmo-5'-fluorophenyl)-2-cyclohexylaminoethanol Prepared from 4'-amino-3'-bromo-2-cyclohexylamino-5'-fluoroacetophenone and sodium borohydride , similarly to Example LXVII. Melting point of the hydrochloride: 191-195°C (decomposition). Example LXX. 1-(4'-amino-3'-bromo-5'-fluorophenyl)-2-cycloheptylaminoethanol17 90 221 18 Prepared from 4'-amino-3'-bromo-2-cycloheptylamino-5'-fluoroacetophenone and sodium borohydride, "analogously to example LXVII. Melting point of the hydrochloride 187-189°C (decomposition). Example LXXI. 1-(4'-amino-3'-fluoro-5'-iodophenyl/-2 -cyclopropylaminoethanol Prepared from 4'-amino-2-cyclopropylamino-3'-fluoro-5'-iodoacetophenone and sodium borohydride, analogously to Example LXVII. Melting point of the hydrochloride 199-201°C (decomposition). Example LXXII . 1-(4'-amino-3'-fluoro-5'-iodophenyl)2-isopropylaminoethanol Prepared from 4'-amino-3'-fluoro-2-isopropylamino-5'-iodoacetophenone and borohydride sodium, analogously to Example LXVII. Melting point of the hydrochloride 203-205°C (decomposition). Example LXXIII. 1-(4'-amino-3'-fluoro-5'-iodophenyl)-2-cyclobutylaminoethanol. Prepares composed of 4'-amino-2-cyclobutylamino-3'-fluoro-5'-iodoacetophenone and sodium borohydride, analogously to Example LXVII. Melting point of the hydrochloride: 197-199°C (decomposition). Example LXXIV. 1-(4'-amino-3'-fluoro-5'-iodophenyl)-2-tert.butylaminoethanol Prepared from 4'-amino-2-tert.butylamino-3'-fluoro- 5'-iodoacetophenone and sodium borohydride, analogously to Example LXVII. Melting point of sodium hydrochloride: 207-209°C. Example LXXV. 1-(4'-amino-3'-fluoro-5'-iodophenyl)-2-(hydroxy-tert.butylamino-ethanol) Prepared from 4'-amino-3'-fluoro-2-(hydroxy) -III-butylamino-5'-iodoacetophenone and sodium borohydride, analogously to Example LXVII. Melting point of the hydrochloride 200-202°C (decomposition). Example LXXVI. 2-ethylamino-1-/4' -amino-3'-cyano-5'-fluorophenyl)-ethanol. Prepared from 2-ethylamino-4'-amino-3'-cyano-5'-fluoroacetophenone and sodium borohydride, analogously to Example LXVII. Melting point of the hydrochloride 216-218° C. (decomposition) Example LXXVII 1-(4'-amino-3'-cyano-5'-fluorophenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino-3'- cyano-2-cyclopropylamino-5'-fluoroacetophenone and sodium borohydride, analogously to Example LXVII. Melting point of the hydrochloride 188-190°C {decomposition). Example LXXVIII. 1-(4'-amino-3'- cyano-5'-fluorophenyl-2-isopropylaminoethanol. Prepared from 4'-amino-3'-cyano-5'-fluoro-2-isopropylaminoacetophenone and sodium borohydride, analogously to Example LXVII. Melting point of the hydrochloride: 182-184°C (decomposition). Example LXXIX. 1-(4'-3'-cyano-5'-fluoro-phenyl)-2-cyclobutylaminoethanol Prepared from 4'-amino-3'-cyano-2-cyclobutylamino-5'-fluoroacetophenone and sodium borohydride, analogously as in example LXVII. Melting point of the hydrochloride 222-224°C (decomposition. Example LXXX. 1-(4)-amino-3'-cyano-5'-fluorophenyl/-2^III-butylaminoephanol. Prepared from 4'-amino -2-III-butylamino-3'-cyano-5'-fluoroacetophenone and sodium borohydride, analogously to Example LXVII, Melting point of the hydrochloride 242-243°C (decomposition). Example LXXXI. 1-(4'-amino-3'-cyano-5'-fluorophenyl)-2-cyclopentylaminoethanol Prepared from 4'-amino-3'-cyano-2-cyclopentylamino-5'-fluoroacetophene and sodium borohydride, analogously to Example LXVII. Melting point of the hydrochloride 184-186°C (decomposition). Example LXXXII. 1-(4'-amino-3'-cyano-5'-fluorophenyl/-2-III-pentylaminoethanol). It is prepared from 4'-amino-3'-cyano-5'-fluoro-2-tertiary pentylaminoacetophenone and sodium borohydride, analogously to Example LXVII. Melting point of the hydrochloride 172-175°C. (dec. ¬ example).Example LXXXIII. 1-(4'-amino-3'-cyano-5'-fluorophenyl)-2-dimethylaminoethanol. Prepared from 4'-amino-3'-cyano-2-dimethylamino-5 '-fluoroacetophenone and sodium borohydride, analogously to Example LXVII. Oil, the structure of the compound is confirmed by the nuclear resonance spectrum (CD8OD): 2.2 - 2.65 ppm multiplet, [8 protons, N-CH8], 4.6 - 4.9 ppm multiplet, [4 proton - ny, 3 exchangeable protons]; 7.15 - 7.4 ppm multiplet [2 aromatic protons]. Example LXXXIV. 1-(4'-amino-3'-cyano-5'-fluorophenyl)-2-diethylaminoethanol Prepared from 4'-amino-3'-cyano-2-diethyl-amino-5'-fluoroacetophenone and sodium borohydride, similarly to example LXVII. Oil, the structure of the compound is confirmed by the nuclear resonance spectrum (CD3OD): 0.85 - 1.2 ppm triplet, [6 protons, -N/CH2 -CH3/2], 2.45 - 2.85 ppm multiplet [6 protons, -N/CHg—CH8/2—CH—CH2—N=], 4.5 - 4.85 ppm singlet and triplet [4 protons, 3 exchangeable protons and CH/OH—CH2—/ , 7.1^- 7.4 ppm multiplet (2 aromatic protons). Example LXXXV. 1-(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-2-(cyclopropylmethylamino)-ethanol Prepared from 4'-amino-3'-chloro-2-(cyclopropylmethylamino) /-5'-trifluoromethylacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of hydrochloride 186--187°C (decomposition). Example LXXXVI. 1-(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-2-cyclopentylaminoethanol ^ Prepared from 4'-amino-3'-chloro-2-cyclopentylamino-5'-trifluoromethylacetophenone and boron sodium oxide, analogously to example LXVI. Melting point of hydrochloride 188-190°C (decomposition). 55 Example LXXXVII. 1-(4-amino-3-chloro-5-trifluoromethylphenyl)-2-cyclohexylaminoethanol Prepared from 4'-amino-3'-chloro-2-cyclohexylamino-5'-trifluoromethylacetophenone and sodium borohydride, analogously as in example LXVI. 60 Melting point of hydrochloride 213-214°C (decomposition). Example LXXXVIII. 1r(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-2-cyclohephtylaminoethanol Prepared from 4'-amino-3'-chloro-2-cycloheptyl-65-65amino-5'-trifluoromethylacetophenone and boron-96 221 19 sodium hydride, similarly to Example LXVI. Melting point of the hydrochloride 163-165°C. Example LXXXIX. 1-(4'-amino-3'-bromo-5'-trifluoromethylphenyl)-2-(cyclopropylmethylamino)-ethanol # 5 Prepared from 4'-amino-3'-bromo-2-(cyclopropylmethylamino) /-5'-trifluoromethylacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of hydrochloride 173--175°C (decomposition). 10 XC example. 1-(4'-amino-3'-chloro-5'-cyano-phenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino-3'-chloro-5'-cyano-2-cyclopropylaminoacetophenone and so- du, similarly to example LXVI. Melting point of the hydrochloride 175-177°. XCI example. 1-(4'-amino-3'-chloro-5'-cyanophenyl)-2-propylaminoethanol Prepared from 4'-amino-3'chloro-5'-cyano-2-propylaminoacetophenone and sodium borohydride, 20 similarly to Example LXVI. Melting point of the hydrochloride 187-189°C. Example XCII. 1-(4'-amino-3'-chloro-5'-cyanophenyl)-2-cyclobutylaminoethanol Prepared from 4'-amino-3'-chloro-5'-cyano-2-25-cyclobutylaminoacetophenone and sodium borohydride , similarly to example LXVI. Melting point of the hydrochloride: 178-180°C. Example XCIII. 1-(4'-amino-3'-chloro-5'-cyanophenyl/-2-tert.-butylaminoethanol 30 Prepared from 4'-amino-2-sec.-butylamino-3'-chloro -5'-cyanoacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the dihydrochloride: 190-191°C. / Example XCIV. 1-(4'-amino-3'-chloro-5'-cyanophenyl)-2-(hydroxy-tert.butylamino)-ethanol Prepared from 4'-amino-3'-chloro-5' -cyano-2-(hydroxy-tertiary-butylamino)-acetophenone and sodium borohydride, analogously to Example LXVI. Melting point of hydrochloride 228-40-230°C (decomposition). Example XCV. 1-(4'-amino-3'-chloro-5'-cyanophenyl)-2-cyclopentylaminoethanol Prepared from 4'-amino-3'-chloro-5'-cyano-2-cyclopentylaminoacetophenone and sodium borohydride 45 du, similarly to example LXVI. Melting point of the hydrochloride 138-144°C. Example XCVI. 1-(4'-amino-3'-chloro-5'-cyanophenyl/-2-tert-pentylaminoethanol. Prepared from 4'-amino-/-3-chloro-5'-cyano-2-50 -III-pentylaminoacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the hydrochloride: 218-220°C (decomposition). Example XCVII. 1-(4'amino-3'-chloro-5'-cy- 55 janophenyl)-2-cycloheptylaminoethanol Prepared from 4'-amino-3'-chloro-5'-cyano-2-cycloheptylaminoacetophenone and sodium borohydride du, similarly to example LXVI. Melting point of the hydrochloride: 235-237°C (decomposition). Example X£VIII. 1-(4'amino-3'-chloro-5'-cyanophenyl)-2r[W3,4-methyldioxyphenyl/-2-propylaminoj-ethanol Prepared from 4'-amino-3'-chloro-5 '-cyano-2- in -[l-(3,4-methyldioxyphenyl)-2-propylamineOj-acetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the chlorohydride 189-192°C. Example bromo-5'-cyano-2-cyclobutylaminoacetophenone and sodium borohydride, similarly to Example LXVI. Melting point of the hydrochloride 215-216°C (decomposition). Example C. 1-(4'-amino-3'-bromo) -5'-cyano-phenyl(-2-(hydroxy-tert.-butylamino)-ethanol. Prepared from 4'-amino-3'-bromo-5'-cyano-2-(hydroxy-tert.-butylamino) butylamino-acetphenone and sodium borohydride, analogously to Example LXVI. Melting point of the hydrochloride 221--222° C. Example CI: 1-(4'-amino-3'-bromo-5'-cyanophenyl) 2-cyclopentylaminoethanol. Prepared from 4'-amino-3'-bromo-5'-cyano-2-cyclopentylaminoacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the hydrochloride: 177°C. Example CII. -/4'-amino-3'-bromo-5'-cyanophenyl/-2-III-pentylaminoethanol Prepared from 4'-amino-3'-bromo-5'-cyano-2- -III- preferably pentylaminoacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the hydrochloride 202-204°C (decomposition). Example CIII. 1-(4'-amino-3'-bromo-5'-cyanophenyl)-2-cyclohexylaminoethanol Prepared from 4'-amino-3'-bromo-5'-cyano-2-cyclohexylaminoacetophenone and sodium borohydride du, similarly to example LXVI. Melting point of the hydrochloride: 209-210°C (decomposition). CIV example. 1-(4'-amino-3',5'-dicyanophenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino-2-cyclopropylamino-3',5'-dicyanoacetophenone and sodium borohydride, analogously to the example LXVI. Melting point of hydrochloride 222-223°C (decomposition). CV example. 1-(4'-amino-3',5'-dicyanophenyl)-2-isopropylaminoethanol. Prepared from 4'-amino-3',5'-dicyano-2-isopropylaminoacetophenone and sodium borohydride, analogously as in example LXVI. Melting point of the hydrochloride: 224-226°C (decomposition). CVI example. 1-/4'-amino-3',5'-dicyanophenyl/-2-cyclobutylaminoethanol Prepared from 4'-amino-2-cyclobutylamino-3',5'-dicyanoacetophenone and sodium borohydride, analogously to the example LXVI. Melting point of the hydrochloride salt: 258°C (decomposition). Example CVII. 1-(4'-amino-3',5'-dincyano-phenyl)-2-second-butylaminoethanol Prepared from 4'-amino-2-second-butylamino-3',5'-dincyanoacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the hydrochloride salt 197-199°C. Example CVIII, 1-(4'-amino-3',5'-dicyanophenyl)-2-Ii;i-butylaminoethanol. Prepared from 4'-amino- 2-III-butylamino-3',5'-dicyanoacetophenone and sodium borohydride,17 2 4'-amino-3'-bromo-2-cycloheptylamino-5'-fluoroacetophenone and sodium borohydride are prepared, analogously to in example LXVII. Melting point of the hydrochloride 187-189°C (decomposition). Example LXXI. 1-(4'-amino-3'-fluoro-5'-iodo-phenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino-2-cyclopropylamino-3'-fluoro-5'-iodoacetophenone and sodium borohydride, similarly to example LXVII. Melting point of the hydrochloride: 199-20°C (decomposition). Example LXXII. 1-(4'-amino-3'-fluoro-5'-iodophenyl)-2-isopropylaminoethanol Prepared from 4'-amino-3'-fluoro-2-isopropylamino-5'-iodoacetophenone and sodium borohydride , similarly to example LXVII. Melting point of hydrochloride 203-205°C (decomposition). Example LXXIII. 1-(4'-amino-3'-fluoro-5'-iodophenyl)-2-cyclobutylaminoethanol Prepared from 4'-amino-2-cyclobutylamino-3'-fluoro-5'-iodoacetophenone and sodium borohydride, similarly to example LXVII. Melting point of the hydrochloride: 197-199°C (decomposition). Example LXXIV. 1-(4'-amino-3'-fluoro-5'-iodophenyl)-2-tert.butylaminoethanol Prepared from 4'-amino-2-tert.butylamino-3'-fluoro- 5'-iodoacetophenone and sodium borohydride, analogously to Example LXVII. Melting point of sodium hydrochloride: 207-209°C. Example LXXV. 1-(4'-amino-3'-fluoro-5'-iodophenyl)-2-(hydroxy-III-butyIbamino-ethanol) Prepared from 4'-amino-3'-fluoro-2-(hydroxy) -III-butylamino(-5'-iodoacetophenone) and sodium borohydride, similarly to Example LXVII. Melting point of the hydrochloride: 200-202°C (decomposition). Example LXXVI. 2-ethylamino-1-(4'-amino-3'-cyano-5'-fluorophenyl)-ethanol Prepared from 2-ethylamino-4'-amino-3'-cyano-5'-fluoroacetophenone and sodium borohydride , similarly to example LXVII. Melting point of the hydrochloride 216-218°C (decomposition). Example LXXVII. 1-(4'-amino-3'-cyano-5'-fluorophenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino-3'-cyano-2-cyclopropylamino-5'-fluoroacetophenone and sodium borohydride, similarly to example LXVII. Melting point of the hydrochloride: 188-190°C (decomposition). Example LXXVIII. 1-(4'-amino-3'-cyano-5'-fluorophenyl-2-isopropylaminoethanol. Prepared from 4'-amino-3'-cyano-5'-fluoro-2-isopropylaminoacetophenone and sodium borohydride, analogously as in example LXVII. Melting point of the hydrochloride: 182-184°C (decomposition). Example LXXIX. 1-(4'-3'-cyano-5'-fluoro-phenyl)-2-cyclobutylaminoathanol Prepared from 4'-amino-3'-cyano-2-cyclobutylamino-5'-fluoroacetophenone and sodium borohydride, analogously as in example LXVII. Melting point of the hydrochloride 222-224°C (decomposition. Example LXXX. 1-(4'-amino-3'-cyano-5'-fluorophenyl)-2-tertiary-butylaminoethanol. Prepared from 4'-amino -2-III-butylamino-3'-cyano-5'-fluoroacetophenone and sodium borohydride, analogously to Example LXVII. Melting point of the hydrochloride 242-243°C (decomposition). Example LXXXI. 1-(4'*amino-3'-cyano-5'-fluorophenyl)-2-cyclopentylaminoethanol Prepared from 4'-amino-3'-cyano-2-cyclopentylamino-5'-fluoroacetophenone and borohydride sodium, analogously to Example LXVII. Melting point of the hydrochloride 184-186°C (decomposition). Example LXXXII. 1-(4'-amino-3'-cyano-5'-fluorophenyl/-2-tert. pentylaminoethanol. It is prepared from 4'-amino-3'-cyano-5'-fluoro-2-tertiary pentylaminoacetophenone and sodium borohydride, analogously to Example LXVII. Melting point of the hydrochloride 172-175°C (dissolv. clade).Example LXXXIII. 1-(4'-amino-3'-cyano-5'-fluorophenyl)-2-dimethylaminoethanol. Prepared from 4'-amino-3'-cyano-2-dimethylamino-5' -fluoroacetophenone and sodium borohydride, analogously to Example LXVII. Oil, the structure of the compound is confirmed by the nuclear resonance spectrum (CD3OD): 2.2 - 2.65 ppm multiplet, [8 protons, N-CHS], 4.6 - 4.9 ppm multiplet, [4 proton - ny, 3 exchangeable protons]; 7.15 - 7.4 ppm multiplet [2 aromatic protons]. Example LXXXIV. 1-(4'-amino-3'-cyano-5'-fluorophenyl)-2-diethylaminoethanol Prepared from 4'-amino-3'-cyano-2-diethyl-amino-5'-fluoroacetophenone and sodium borohydride, similarly to example LXVII. Oil, the structure of the compound is confirmed by the nuclear resonance spectrum (CDsOD): 0.85 - 1.2 ppm triplet, [6 protons, -N/CH2 -CH3/2], 2.45 - 2.85 ppm multiplet [6 protons, -N/CHj—CH,/2—CH—CH2—N=], 4.5 - 4.85 ppm singlet and triplet [4 protons, 3 exchange protons and CH/OH—CH2— /, 7.1 - 7.4 ppm multiplet (2 aromatic protons). Example LXXXV. 1-(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-2-(cyclopropylmethylamino)-ethanol Prepared from 4'-amino-3'-chloro-2-(cyclopropylmethylamino) /-5'-trifluoromethylacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of hydrochloride 186--187°C (decomposition). Example LXXXVI. 1-(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-2-cyclopentylaminoethanol in Prepared from 4'-amino-3'-chloro-2-cyclopentylamino-5'-trifluoromethylacetophenone and boron sodium oxide, analogously to example LXVI. Melting point of hydrochloride 188-190°C (decomposition). 55 Example LXXXVII. 1-(4-amino-3-chloro-5-trifluoromethylphenyl)-2-cyclohexylaminoethanol Prepared from 4'-amino-3'-chloro-2-cyclohexylamino-5'-trifluoromethylacetophenone and sodium borohydride, analogously as in example LXVI. «o Melting point of hydrochloride 213-214°C (decomposition). Example LXXXVIII. 1-(4'-amino-3'-chloro-5'-trifluoromethylphenyl)-2-cycloheptylaminoethanol Prepared from 4'-amino-3'-chloro-2-cycloheptyl-5'-trifluoromethylacetophenone and boron- 96 221 ii of sodium dodehydrate, analogously to Example LXVI. Melting point of the hydrochloride 163-165°C. Example LXXXIX. 1-(4'-amino-3'-bromo-5'-trifluoromethylphenyl)-2-(cyclopropylmethylamino)-ethanol Prepared from 4'-amino-3'-bromo-2-(cyclopropylmethylamino)- 5'-trifluoromethylacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of hydrochloride 173--175°C (decomposition). XC example. 1-(4'-amino-3'-chloro-5'-cyanophenyl)-2-cyclopropylaminoethanol Prepared from 4'-amino-3'-chloro-5'-cyano-2-cyclopropylaminoacetophenone and sodium borohydride du, similarly to example LXVI. The melting point of the hydrochloride is 175-177°. Example * sodium borohydride, similarly to Example LXVI. Melting point of the hydrochloride 187-189°C. Example XCII. 1-(4'-amino-3'-chloro-5'-cyanophenyl)-2-cyclobutylaminoethanol Prepared from 4'-amino-3'-chloro-5'-cyano-2-cyclobutylaminoacetophenone and sodium borohydride, similarly to example LXVI. Melting point of the hydrochloride: 178-180°C. Example XCIII. 1-/4'-amino-3'-chloro-5'-cyanophenyl/-2-tertiary-butylaminoethanol Prepared from 4'-amino-2-sec.butylamino-3'-chloro- 5'-cyanoacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the dihydrochloride: 190-191°C. Example XCIV. 1-(4'-amino-3'-chloro-5'-cya- phenyl)-2-(hydroxy-tertiary-butylamino)-ethanol Prepared from 4'-amino-3'-chloro-5'- cyano-2-(hydroxy-tertiary-butylamino)-acetophenone and sodium borohydride, analogously to Example LXVI. Melting point of hydrochloride 228--230°C (decomposition). Example XCV. 1-(4'-amino-3'-chloro-5'-cyanophenyl)-2-cyclopentylaminoethanol Prepared from 4'-amino-3'-chloro-5'-cyano-2-cyclopentylaminoacetophenone and sodium borohydride du, similarly to example LXVI. Melting point of the hydrochloride 138-144°C. Example XCVI. 1-(4'-amino-3'-chloro-5'-cyanophenyl/-2-tert.pentylaminoethanol Prepared from 4'-amino-'-3-chloro-5'-cyano-2- - III-pentylaminoacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the hydrochloride: 218-220°C (decomposition). Example XCVII. 1-(4'amino-3'-chloro-5'-cyanoienyl)-2-cycloheptylaminoethanol Prepared from 4'-amino-3'-chloro-5'-cyano-2-cycloheptylaminoacetophenone and sodium borohydride , similarly to example LXVI. Melting point of the hydrochloride: 235-237°C (decomposition). ¦Example XCVIII. 1-(4'amino-3'-chloro-5'-cyanophenyl)-2-[1-(3,4-methyldioxyphenyl)-2-propylaminoj-ethanol Prepared from 4'-amino-3' -chloro-5'-cyano-2--[l-(3,4-methyldioxyphenyl)-2-propylamino]-acetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the hydrochloride 189-192° C. Example XCIX. 1-(4'-airiino-3'-bromo-5'-cy- janophenyl)-2-cyclobutylaminoethanol Prepared from 4'-amino-3'-bromo-5'-cyano-2-cyclobutylaminoacetophenone and sodium borohydride, analogously as in example LXVI. Melting point of the hydrochloride is 215-216°C. (schedule). Example C. 1-(4'-amino-3'-bromo-5'-cyanophenyl)-2-(hydroxy-tert.butylamino)-ethanol Prepared from 4'-amino-3'-bromo- 5'-cyano-2-(hydroxy-tert.butylamino)-acetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the hydrochloride 221--222°C. Example CI. 1-(4'-amino-3'-bromo-5'-cyano^phenyl)-2-cyclopentylaminoethanol Prepared from 4'-amino-3'-bromo-5'-cyano-2-cyclopentylaminoacetophenone and sodium borohydride du, similarly to example LXVI. Melting point of the hydrochloride salt is 177°C. Example CII. 1-(4'-amino-3'-bromo-5'-cyano-phenyl/-2-III-pentylaminoethanol Prepared from 4'-amino-3'-bromo-5'-cyano-2-III -pentylaminoacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the hydrochloride 202-204°C (decomposition). Example CIII. 1-(4'-amino-3'-bromo-5'-cyanophenyl)-2-cyclohexylaminoethanol Prepared from 4'-amino-3'-bromo-5'-cyano-2-cyclohexylaminoacetophenone and sodium borohydride du, similarly to example LXVI. Melting point of the hydrochloride: 209-210°C (decomposition). CIV example. 1-(4'-amino-3',5'-dicyanophenyl)-2-cyclopropylaminoethanol 4o Prepared from 4'-amino-2-cyclopropylamino-3',5'-dicyanoacetophenone and sodium borohydride, analogously to example LXVI. Melting point of hydrochloride 222-223°C (decomposition). CV example. 1-(4'-amino-3',5'-dicyanophenyl)-2-isopropylaminoethanol Prepared from 4'-amino-3',5'-diacyano-2-isopropylaminoacetophenone and sodium borohydride, anal gically as in example LXVI. Melting point of the hydrochloride: 224-226°C (decomposition). 50 Example CVI. 1-(4'-amino-3',5'-dicyanophenyl)-2-cyclobutylaminoethanol. Prepared from 4'-amino-2-cyclobutylamino-3',5'-a"wucyanoacetophenone and sodium borohydride, analogously to in Example LXVI. Melting point of the hydrochloride salt: 258°C (decomposition). Example CVII. 1-(4'-amino-3',5'-dicyano-phenyl/-2-second-butylaminoethanol. Prepared from 4 '-amino-2-II-butylamino-3',5'-dicyanoacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the hydrochloride 197-199°C. Example CVIII. 1-/4' -amino-3',5'-dincyano-phenyl/-2-tert.butylaminoethanol. Prepared from 4'-amino-2-tert.butylamino-5-3',5'-dincyanoacetophenone and sodium borohydride, M291 reacts analogously to Example LXVI. Melting point of the hydrochloride 251-253°C (decomposition). Example CIX: 1-(4'-amino-3',5'-dicyanophenyl/-2- (hydroxy-HI-butylamino)-ethanol. Prepared from 4'-aminp-3',5'-diacyano-2-(hydroxy-III-butylamino)-acetophenone and sodium borohydride, analogously as in example LXVI. Melting point of the hydrochloride 240-241°C (decomposition). CX example. 1-(4'-amino-3',5'-dicyanophenyl)-2-cyclopentylaminoethanol Prepared from 4'-amino-2-cyclopentylamino-3',5'-dicyanoacetophenone and sodium borohydride, similarly to the example LXVI. Melting point of the hydrochloride 214-216°C. Example CXI. 1-(4'-amino-3',5'-dicyanophenyl/-2-tert.pentylaminoethanol. Prepared from 4'-amino-3',5'-diacyano-2-tert.pentylaminoacetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the hydrochloride: 231-233°C (decomposition). Example CXII. 1-(4'-amino-3',5-dicyanophenyl)-2-[l-(3,4-methylenedioxyphenyl)-2-propylamino]-ethanol Prepared from 4'-amino-3', 5'-dicyano-2-[l-(3,4-methylenedioxyphenyl)-2-propylamino]-acetophenone and sodium borohydride, analogously to Example LXVI. Melting point of the hydrochloride 219-222°C (decomposition). Example CXIII. 1-(4'-amino-3'-chloro-5'-di-ethylaminomethyl-phenyl)-2-tert.-butylamino-ethanol Prepared from 4'-amino-2-tert.-butylamino-3 '-Chloro-5'-diethylaminomethylacetophenone and sodium borohydride, analogously to Example LXVI. Melting point 65-69°C. Example CXIV. 1-(4'-amino-3'-bromo-5'-diethylaminomethyl-phenyl)-2-tert.butylamino-ethanol Prepared from 4'-amino-3'-bromo-2-tert. .bu^ tylamino-5'-diethylaminomethylacetophenone and sodium borohydride, analogously to Example LXVI. Melting point 96-100°C. Example CXV. 1-(4'-amino-3'-chloro-5'-nitrophenyl)-2-tert.butylaminoethanol Prepared from 4'-amino-2-tert.butylamino-3'-chloro- 5'-nitroacetophenone and sodium borohydride, analogously to Example LXVI. Melting point 148-149°C. Example CXVI. l-/4'-amino-3'-bromo-5'-nitrophenyl/-2-tert.butylaminoethanol Prepared from 4'-amino-3'-br.omo-2-tert.bu - tylamino-5'-nitróacetophenone and sodium borohydride, analogously to Example LXVI. Melting point 151-152°C. Example CXVII. 1-(4'-amino-3'-cyanophenyl)-2-cyclobutylaminoethanol. It is prepared from 4-amino-3-cyano-α-cyclobutylaminoacetophenone hydrochloride and sodium borohydride analogously to Example I. Melting point of the hydrobromide above 193°C (decomposition). The following compounds are prepared analogously: 1-(4'-amino-3'-cyanophenyl)-2-tertiary pentylaminoethanol with a melting point of 143°C, 1-(4'-amino-3'-trifluoromethylphenyl) 2-tert.- batylaminoethanol, melting point of the hydrochloride 172-174°C (decomposition), 1-(4'-amino-3M-trifluoromethylphenyl)-2-tert.- pentylaminoethanol. Melting point of the hydrobromide 174-174°C (decomposition). Example CXVIII. d-1-(4'-amino-3'-bromo-5'-fluorophenyl)-2-tert.butylaminoethanol and 1-1-(4'-amino-3'-bromo-5'-fluorophenyl) 2-tert-butyl aminoethanol 205 g of d,l-l-(4'-amino-3'-bromo-5'-fluorophenyl)-2-tert-butylaminoethanol and 118 g of di-benzoyl-D- acid tartaric acid is dissolved in 2.5 liters of hot ethanol, filtered and left for one day at room temperature to crystallize. The obtained product is recrystallized six times from the methanol ether system to obtain pure dibenzoyl-D-tartrate d-1-(4,-amino-3'-bromo-5'-fluorophenyl/-2-III-bu-* o tylaminoethanol with a melting point of 206-208°C (decomposition), [a] ^-332.9° (c = 2.0 methanol). The salt is dissolved on heating in methanol and concentrated ammonia and the base is crystallized by adding water. The obtained base is dissolved in absolute ethanol, neutralized with hydrochloric acid in absolute ethanol and crystallization is completed by adding ether. The obtained d-1-(4'-amino-3'-bromo-5'-fluorophenyl)-2-tertiary-butylamino-ethanol hydrochloride melts at 234-235°C (decomposition), [a] 3^ = +132.0° (c = 2.0.methanol). The mother liquors from the precipitation of dibenzoyl-D-tartrate and the first crystallization are combined, concentrated to a small volume and the base is precipitated by adding concentrated* ammonia and water. 140 g of the obtained 1-(4'-amino-3'-bromo-5'-fluorophenyl)-2-tert-butylaminoethanol (abundant in form 1) are dissolved in 1.8 liters of absolute ethanol and a solution of 82 g of dibenzoyl-L-tartaric acid* in 500 ml of absolute ethanol, concentrate to a volume of 1 liter and leave to crystallize for 3 days at room temperature. The product obtained is recrystallized six times from the methanol/ether system, dibenzoyl-L-tartrate of 1-1^^amino-S^bromo-S^-fluorophenyl(^-III-butylaminoethanol) is obtained in pure form. Melting point 204-206°C (decomposition), [a ] 364 = = -330° (c = 2.0 methanol). The salt dissolves in methanol and concentrated ammonia on heating and precipitates the base - by: so adding water. The obtained base is dissolved in absolute ethanol, neutralized with hydrochloric acid in absolute ether and by adding ether crystallize 1-(4'-amino-3'-bromo-5'-fluorophenyl)-2-tert-butylaminoethanol hydrochloride. Melting point 218-220°C (decomposition), [a]30° = 133.9° (c = 2.0 methanol). Example CXIX. d-l-(4'-amino-3'-chloro-5'-fluorophenyl)-2-tert-butylaminoethanol Prepared from d,l-l-(4'-amino-3'-chloro-5'-fluorophenyl) /-2-III-butylaminoethanol by fractionated crystallization of dibenzoyl-D-tartrate, 31 40 5596 2 23 analogously to example CXX. Melting point of the hydrochloride: 210-211°C (decomposition). [a]364 = +1397° (c = 2° methanol). l-l-(4'-amino-3'-chloro-5'-fluorophenyl)-2-tert.butylamirio-5 ethanol Prepared from d,l-l-/4'-amino-3'-chloro-5'- fluorophenyl/-2-tert-butylaminoethanol by fractional crystallization of dibenzoyl-L-tartrate, analogously to Example CXX. Melting point of the hydrochloride 209-210°C (decomposition). 90 [a]gg4 = -139.2° (c = 2.0 methanol). CXX example. d-l-(4'-amino-3'-chloro-5'-cyanophenyl)-2-tert.butylaminoethanol Prepared from d,l-l-(4'-amino-3'-chloro-5'-cya- 15 nophenyl/-2-tert-butylaminoethanol by fractional crystallization of dibenzoyl-D-tartrate, analogously to Example CXX. Melting point of the hydrochloride: 197-199°C (decomposition). 20 [ l-l-(4'-amino-3'-chloro-5'-cyanophenyl)-2-tert-butylaminoethanol Prepared from l-l-(4'-amino-3'-chloro-5'-cya) - nophenyl/-2-tert-butylaminoethanol by fractional crystallization of dibenzoyl-L-tartrate, analogously to Example CXX. Melting point of the hydrochloride: 199-202°C (decomposition). 90 [a]gg4 = -59.85° (c = 2.0 methanol).PL PL

Claims (8)

Patent claims 1. A method for the preparation of new aminophenylethanolamines of general formula I, in which Rj is hydrogen, chlorine or bromine, R2 is a straight or branched alkyl group with 1-5 carbon atoms, hydroxyalkyl, aminoalkyl groups, dialkylaminoalkyl, trifluoromethyl, alkoxy, nitrile, carboxyl, carboxylic or carbamyl, R3 and R4 are the same or different and represent hydrogen atoms, straight or branched alkyl group with 1-6 carbon atoms, cycloalkyl, alkenyl or optionally alkynyl groups the substituted aralkyl group and their physiologically acceptable inorganic or organic acid addition salts, such as acetophenone of the general formula (II) in which Rt - R2 are as defined above, is reduced in a solvent and the resulting compound of formula overall 1 is optionally converted into a physiologically acceptable addition salt with an inorganic or organic acid. 2. The method according to claim A process as claimed in claim 1, characterized in that the reductions are carried out with a complex metal hydride, aluminum isopropanol or catalytically activated hydrogen at a temperature from 24-20 ° C to the boiling point of the solvent used. 3. Process for the preparation of the new aminophenylethanolamines of general formula I, in which Rj is a fluorine or iodine atom or a nitrile group, R2 is a nitro group, R3 is an optionally substituted straight or branched alkyl group with 1 to 6 carbon atoms, optionally substituted with a hydroxyl radical. , a cycloalkylalkyl or methylenedioxyphenylalkyl group and R4 is a hydrogen atom or an alkyl group of 1-3 carbon atoms and their physiologically acceptable addition salts with inorganic or organic acids, characterized in that acetophenone of general formula II, in which R1 - R 4 has the meaning given above, is reduced in a solvent and the resulting compound of formula I is optionally converted into a physiologically acceptable addition salt with an inorganic or organic acid. 4. The method according to p. 3. A process as claimed in claim 3, characterized in that the reductions are carried out with a complex metal hydride, aluminum isopropoxide or catalytically activated hydrogen at a temperature from -20 ° C to the boiling point of the solvent used. 5. Process for the preparation of compounds 1 and 1 of the general formula I, "wherein Rt is hydrogen, chlorine or bromine, R2 is fluoro, trifluoromethyl or nitrile, and R3 is a straight or branched alkyl group of 3-5 atoms. carbon or a cycloalkyl group of 3-5 carbon atoms, and R4 is hydrogen and the salts of their physiologically acceptable addition salts with inorganic or organic acids, characterized by the compound of formula II in which R1-R4 is as follows: the meaning given is reduced in a solvent and the resulting racemic mixture of the compound of general formula I is separated into optically active antipodes and the resulting compound d or 1 is optionally converted into a physiologically acceptable addition salt with an inorganic or organic acid. 6. The method according to p. 5. The method of claim 5, characterized in that the racemate is split by fractionated crystallization of diastereomeric salts. 7. The method according to p. 6. A process as claimed in claim 6, characterized in that D / - / - tartaric acid, L / + / - tartaric acid, dibenzoyl-D-tartaric acid, dibenzoyl-L-tartaric acid, / + / - camphor- are used as auxiliary optically active acids. 10-sulfonate, d- / - / - apple, L / + / - almond, dahromocamphoro-rc-sulfone or 1-quinone. 8. The method according to p. 5, characterized in that the racemate is split by column chromatography on an optically active medium. 96 221 OH CH-ChU-N ^ 3 \ Formula 1 co-ch9-nC 3 XR4 Formula 0R7 ch-ch, -nC 2 X Pattern