Method for production of n-(3-phenyl-2-norcamphanyl)-n-etnylamine hydrochloride

FIELD: organic chemistry.

SUBSTANCE: claimed method includes reduction of 2-nitro-3-phenyl-Δ5-norcamphene with active hydrogen obtaining by reaction of aluminum containing in nickel-aluminum alloy with potassium hydroxide, wherein 1 N potassium hydroxide solution and powdered nickel-aluminum alloy are added to 2-nitro-3-phenyl-Δ5-norcamphene solution in tetrahydrofurane followed by treatment thereof with ethanol in presence of skeletal nickel catalyst forming in reduction step to produce N-3-phenyl-2-norcamphanyl)-N-etnylamine followed interaction thereof with hydrogen chloride and isolation of target product. Compound of present invention is useful in medicine as active ingredient of preparations with tonic action.

EFFECT: new method for production of N-(3-phenyl-2-norcamphanyl)-N-etnylamine hydrochloride.

1 cl, 1 ex

 

The invention relates to the field of synthesis of derivatives of 2-nonconforming specifically to a method for producing M-(3-phenyl-2-norcamphor)-N-ethylamine hydrochloride

which finds application in medicine as the active principle of medicinal drugs Fencamfamin, Avital, Reactive with timoanalepticheskoe and tonic effect.

A method of obtaining N-(3-phenyl-2-norcamphor)-N-ethylamine hydrochloride of 2-nitro-3-phenyl-Δ5-Narkomfin. 2-Nitro-3-phenyl-Δ5-Narkomfin restored iron filings in hydrochloric acid in 2-amino-3-phenyl-Δ5-Narkomfin (yield 47%) [Kenneth Johnson, Ed. F. Degering. The Utilization of Aliphatic Nitro Compounds. (I) The Production of Amines and (II) The Production of Oximes1J. Am. Chem. Soc.; 1939; 67 (11); 3194-3195], which is then reduced with hydrogen in the presence of a platinum catalyst in 2-amino-3-phenylmercaptan (yield 81%) [William E. Parham, William T. Hunter, Roberta Hanson. endo-5-Aminobicyclo[2,2,1]heptene-2. J. Am. Chem. Soc.; 1951; 75 (11); 5068-5070]. The latter is treated with acetaldehyde and hydrogen in the presence of a platinum catalyst with the formation of N-(3-phenyl-2-norcamphor)-N-ethylamine, which by treatment with hydrochloric acid is converted into the hydrochloride (yield 35%) [Thesing J., Seitz G., Hotovy R., Sommer S. Improvements in or relating amino-norcamfane compounds. Pat. UK No. 913866, Publ. 28.12.1960]. The total yield of N-(3-phenyl-2-norcamphor)-N-ethylamine hydrochlor is Yes based on 2-nitro-3-phenyl-Δ 5-Narkomfin is about 13%.

The disadvantages of this method are a significant number of the stages of synthesis and relatively low overall yield of the target product.

The closest is a method of obtaining N-(3-phenyl-2-norcamphor)-N-ethylamine hydrochloride by catalytic hydrogenation of 2-nitro-3-phenyl-Δ5-Narkomfin in the presence of skeletal Nickel under a hydrogen pressure of 160 kgf/cm2(yield 69%) [William E. Parham, William T. Hunter, Roberta Hanson. endo-5-Aminobicyclo[2,2,1]heptene-2. J. Am. Chem. Soc.; 1951; 73(11); 5068-5070] with subsequent treatment of the obtained 2-amino-3-phenylmercaptan the acetaldehyde and hydrogen in the presence of a platinum catalyst [J. Thesing, Seitz G., Hotovy R., Sommer S. Improvements in or relating amino-norcamfane compounds. Pat. UK No. 913866, Publ. 28.12.1960]. The resulting N-(3-phenyl-2-norcamphor)-N-ethylamine is converted into hydrochloride by the action of hydrochloric acid. The total yield of N-(3-phenyl-2-norcamphor)-N-ethylamine hydrochloride for 2-nitro-3-phenyl-Δ5-Narkomfin is about 24%.

This method, despite its relative simplicity and economy, has significant disadvantages: low total yield of N-(3-phenyl-2-norcamphor)-N-ethylamine hydrochloride, and the need for hydrogenation reactions in hard conditions: at high pressure and temperature.

The objective of the proposed technical solution is is to develop a new technological method of producing N-(3-phenyl-2-norcamphor)-N-ethylamine hydrochloride in good yield and high purity, allowing to carry out the synthesis under mild conditions using a cheap source connections.

The technical result is a simplification of the production method, as well as increase the yield of the proposed product. This technical result is achieved in a method of producing N-(3-phenyl-2-norcamphor)-N-ethylamine hydrochloride by restoring 2-nitro-3-phenyl-N-Narkomfin hydrogen to obtain 2-amino-3-phenylmercaptan and its subsequent processing in the presence of a catalyst to obtain N-(3-phenyl-2-norcamphor)-N-ethylamine and its interaction with hydrogen chloride with the separation of the target product, and recovering 2-nitro-3-phenyl-Δ5-Narkomfin conduct active hydrogen formed by the reaction of aluminum contained in the Nickel-aluminum alloy with potassium hydroxide, adding to the solution of 2-nitro-3-phenyl-Δ5-Narkomfin in tetrahydrofuran 1N aqueous solution of potassium hydroxide and powdered Nickel-aluminum alloy, and the obtained 2-amino-3-phenylmercaptan treated with ethyl alcohol in the presence of skeletal Nickel catalyst, formed at the stage of recovery.

The essence of the proposed method is the recovery of 2-nitro-3-phenyl-Δ5-Narkomfin active hydrogen formed by the reaction of aluminum Nickel-aluminum is Plava with potassium hydroxide:

During this process, the aluminum in the alloy reacts with the alkali and forms an aqueous solution of potassium aluminate and hydrogen. The latter acts as a reductant in relation to 2-nitro-3-phenyl-Δ5-norcamphor. At the same time, the formation of skeletal forms of Nickel with catalytic activity.

Thus obtained 2-amino-3-phenylmercaptan enter into interaction with ethanol in the presence of skeletal Nickel catalyst:

In the course of the synthesis is a catalytic dehydration of ethanol to form acetaldehyde. The latter reacts with 2-amino-3-phenylmercaptan with the formation of h. Azomethine, in turn, is catalytically reduced with hydrogen, ottseplyayuschimsya by dehydration of ethyl alcohol. This produces N-(3-phenyl-2-norcamphor)-N-ethylamine, which under the action of hydrogen chloride is converted into hydrochloride N-(3-phenyl-2-norcamphor)-N-ethylamine:

The proposed method allows to obtain the hydrochloride of N-(3-phenyl-2-norcamphor)-N-ethylamine under mild conditions in good yield using available reagents.

The method is as follows.

Synthesis of 2-amino-3-feilner ampana

In the reactor of 2 liters, equipped with a mechanical stirrer with glycerin shutter, reflux condenser and tube, was placed a solution of 21.5 g (0.1 mol) of 2-nitro-3-phenyl-Δ5-Narkomfin in 450 ml of tetrahydrofuran and 700 ml of 1N aqueous solution of potassium hydroxide. To the obtained mixture under vigorous stirring, in small portions, add 147 g of powdered Nickel-aluminum alloy. When this reaction mass boils and boils moderately. The addition of all of the alloy should be performed within 4 hours When the exothermic reaction subsides, the reaction mass is boiled for a further 2 hours under stirring, filtered hot, the residue on the filter is washed three times with 100 ml portions of tetrahydrofuran. The filtrates are combined to the upper phase is separated, and the lower - extracted with toluene (4 x 75 ml). Tertrahydrofuran ring fluid is concentrated under reduced pressure, the residue is mixed with toluene extracts are washed with water (3 x 75 ml). The organic phase is extracted with 2 N aqueous HCl solution. The acid extracts are re-extracted with toluene (3 times 50 ml), and then brought to a highly alkaline environment by the addition of solid NaOH. Amin released in the form of oil, is extracted with toluene (4 x 75 ml), the organic phase is dried solid NaOH, filtered, remove the toluene under reduced pressure, and the residue is distilled in vacuum. In the course of 16.4 g (88%). TKIP-175°With (20 mm RT. Art.). n20D=1.556, which corresponds to literature data [William E. Parham, William T. Hunter, Roberta Hanson. endo-5-Aminobicycio[2,2,1]heptene-27. Am. Chem. Soc.; 1951; 73 (11); 5068-5070].

The filtered catalyst is completely leached and used in the next stage.

Synthesis of N-(3-phenyl-2-norcamphor)-N-ethylamine hydrochloride

In a round bottom flask was placed 15 g (0.08 mol) of 2-amino-3-phenylmercaptan, 45 ml of ethanol and 10 g of skeletal Nickel catalyst. The resulting mixture is boiled for 15 hours under vigorous stirring with protection from moisture, filtered, the filter cake washed with ethanol (3 x 75 ml) and the filtrate concentrated under reduced pressure. The residue is distilled in vacuum. Fraction with TKIP-200°With (20 mm RT. Art.) dissolved in ether (150 ml) and neutralized with saturated solution of hydrogen chloride in isopropyl alcohol. The precipitation is filtered, dried and crystallized. Yield 12.9 g (64%). TPL-193°C (acetone), which corresponds to literature data [Thesing J., Seitz G., Hotovy R., Sommer S. Improvements in or relating amino-norcamfane compounds. Pat. UK No. 913866, Publ. 28.12.1960].

As follows from the data, we proposed a method of obtaining N-(3-phenyl-2-norcamphor)-N-ethylamine hydrochloride is workable and allows to obtain the target product with high yield and purity.

5-Narkomfin hydrogen to obtain 2-amino-3-phenylmercaptan and its subsequent processing in the presence of a catalyst to obtain N-(3-phenyl-2-norcamphor)-N-ethylamine and its interaction with hydrogen chloride with the separation of the target product, characterized in that the recovery of 2-nitro-3-phenyl-Δ5-Narkomfin conduct active hydrogen formed by the reaction of aluminum contained in the Nickel-aluminum alloy with potassium hydroxide, adding to the solution of 2-nitro-3-phenyl-Δ5-Narkomfin in tetrahydrofuran 1N aqueous solution of potassium hydroxide and powdered Nickel-aluminum alloy, and the obtained 2-amino-3-phenylmercaptan treated with ethyl alcohol in the presence of skeletal Nickel catalyst, formed at the stage of recovery.



 

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