RU2475473C1 - 3-phenoxyphenyl-containing 1,3-diketones as starting compounds for producing chelate complexes thereof with copper (ii) ions and method of producing 3-phenoxyphenyl-containing 1,3-diketones - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to the chemistry of diphenyl oxide derivatives and specifically to novel 3-phenoxyphenyl-containing 1,3-diketones, intermediate compounds in synthesis of a wide range of biologically active substances of general formula

, for example as starting compounds for producing chelate complexes thereof with copper (II) ions of general formula

, which have potential for use as extraction agents, analytical reagents of rare-earth elements, vital semiproducts in synthesis of probable biologically active substances. The invention also relates to a method of producing 3-phenoxyphenyl-containing 1,3-diketones, involving reaction of 3-phenoxybenzonitrile with lower alcohols: methanol, ethanol in molar ratio 1:4.245, respectively, in the presence of concentrated sulphuric acid for 7-8 hours, to form alkyl-3-phenoxybenzoate, and subsequent reaction thereof with ketones selected from: acetone, 2-butanone, acetophenone in molar ratio 2.0:1, respectively, in a medium of pure cyclohexane at boiling point thereof in the presence of catalytic amounts of sodium hydride for 2.5-3 hours, followed by extraction of the end product.

EFFECT: wider range of diphenyl oxide derivatives and obtaining 3-phenoxyphenyl-containing 1,3-diketones and chelate complexes thereof with copper (II) ions with high output.

2 cl, 6 ex

Description

The invention relates to the chemistry of diphenyl oxide derivatives, and in particular to a method for producing 3-phenoxyphenyl-containing 1,3-diketones, intermediate compounds in the synthesis of a wide range of substances having biological activity of the general formula

which can be used as starting compounds for the preparation of their chelate complexes with copper (II) ions of the general formula

which are of interest as extractants, analytical reagents of REE, the most important intermediates in the synthesis of probable biologically active substances. In particular, 1,3-diketones are synthones for 3-hydroxyketones, pyrazoles [R.J. Light, C.R. Hauser. J. Am. Chem. Soc., Vol. 26, 1961, p.1716-1724], N-substituted aminopyridones [G.H. Elgemeie, A.M. Elzanate Synthetic communications. Vol.33, No. 12, 2003, p.2087-2094], flavones [Heterocyclic compounds: In 8 vol .: T.2 / Ed. Elderfield R. - M.: Publishing house of foreign literature, 1954. - P.177], isoxazoles [Heterocyclic compounds: In 8 volumes: V.5 / Ed. Elderfield R. - M .: Publishing house of foreign literature, 1961. - P.369], diazepines, benzofuran-4-ones [Ellis, G.P. Ed .; J. Chem. Soc. Chem. Commun. Interscience: New York; Vol. 33, 1984, p. 495], 1-acyl-1H-pyrroles [Michael P. Sammes. J. Chem. Soc. Chem. Commun. Vol. 33, 1984, p. 354-355]. It has been established that benzyl-containing 1,3-diketones have pronounced antiviral activity against DNA and RNA viruses. As multifunctional ligands, 1,3-diketones are used to solve practical problems in analytical chemistry when determining, separating and concentrating rare-earth elements [β-diketones / Peshkova V.M., Melchakova N.V. - M .: Nauka, 1986. - P.35]. Chelate complexes formed by 1,3-diketones with metals are of practical importance in connection with their use in the chemical vapor deposition method for producing thin metal films and composite materials [Dudek M., Clegg J.K., C.R.K. Glasson Crys. Growth Des. 11, 2011, p. 1697-1704]. In the literature, information on methods for producing compounds of the claimed structural formula are absent.

A known method for producing 1-phenyl-3- (2-pyridyl) -1,3-propanedione and its chelate complex with copper (II) ions, in which the starting compound is acetophenone, which is reacted with methyl picolinate in the presence of catalytic amounts of sodium amide . The interaction is carried out in absolute tetrahydrofuran at room temperature for 6 hours. The chelate complex is synthesized by treating the obtained 1-phenyl-3- (2-pyridyl) -1,3-propanedione with sodium carbonate first for 1 hour, then copper (II) nitrate for 2 hours at a temperature of 35 ° C. Both reagents are used as suspensions in absolute tetrahydrofuran medium [Dudek M., Clegg J.K., C.R.K. Glasson Crys. Growth Des. 11, 2011, p. 1697-1704].

The disadvantage of this method is the long duration of the synthesis. And also the result is compounds of a different structure than in the present invention.

A known method for producing 1,1,1,2,2,3,3,7,7,7-decafluoro-4,6-heptanedione by condensation of ethyl heptafluorobutyrate with trifluoroacetone in the presence of catalytic amounts of sodium methylate in hexane at room temperature. The chelate complex of the formed diketone with copper (II) ions was synthesized by treating the product with an aqueous solution of copper (II) sulfate pentahydrate. The yield of the target 1,1,1,2,2,3,3,7,7,7-decafluoro-4,6-heptanedione was 40% [V.N. Smith, R. W. Moisher, R.E. Sievers. J. Org. Chem. Vol. 35, No. 5, 1970, p. 1696-1698].

This method does not lead to the production of substances of the claimed structural formula.

The literature describes a method for producing substituted 1,4-diphenylbutane-1,3-diones, which consists in the sigmatropic rearrangement of aromatic α-bromoketones in the presence of the Furakava reagent (ethyl zincmethyl iodide) under the conditions of the Reformatsky reaction [L. Li, P. Cai, D. Xu. J. Org. Chem. Vol. 72, 2007, p.8131-8134].

This method does not lead to the production of substances of the claimed structural formula. In addition, among the shortcomings of the method, the use of flammable diethylzinc and the relatively low yields of the target products can be noted.

There is a method for producing 1-phenyl-2-methyl-1,3-pentanedione by acylating sodium pentan-3-one with benzoic acid chloride in the cold. The starting sodium pentan-3-one is obtained by reacting the corresponding ketone with sodium amide in ammonia [B.O. Linn, C.R. Hauser. J. Org. Chem. Vol.V. 78, 1956, p.6066-6070].

The above method gives compounds of a completely different structure compared to the invention. The disadvantages of this method include multi-stage, low process selectivity due to the formation of tricarbonyl compounds, as well as O-acyl derivatives of 1,3-diketones.

The objective of the invention is to develop a method for the synthesis of 3-phenoxyphenyl-containing 1,3-diketones and their chelate complexes with copper ions (II).

The technical result is the expansion of the range of diphenyl oxide derivatives, as well as the preparation of 3-phenoxyphenyl-containing 1,3-diketones and their chelate complexes with copper (II) ions in high yield.

The technical result is achieved by the fact that the proposed 3-phenoxyphenyl-containing 1,3-diketones of the General formula

as starting compounds for the preparation of their chelate complexes with copper (II) ions of the general formula

and method for producing 3-phenoxyphenyl-containing 1,3-diketones of general formula

consisting in the interaction of 3-phenoxybenzonitrile with lower alcohols: methanol, ethanol in a molar ratio of 1: 4,245, respectively, in the presence of concentrated sulfuric acid for 7-8 hours with the formation of alkyl-3-phenoxybenzoate, its subsequent interaction with ketones from the series: acetone, 2-butanone, acetophenone in a molar ratio of 2.0: 1, respectively, in absolute cyclohexane at its boiling point in the presence of catalytic amounts of sodium hydride for 2.5-3 hours and the subsequent isolation of the final product.

To obtain 3-phenoxyphenyl-containing 1,3-diketones, 3-phenoxybenzonitrile is chemically reacted with lower alcohols: methanol, ethanol in a molar ratio of 1: 4,245, respectively, in the presence of concentrated sulfuric acid for 7-8 hours to form alkyl-3-phenoxybenzoate according to pattern

its subsequent interaction with ketones from the series: acetone, 2-butanone, acetophenone according to the scheme

at a molar ratio of 2.0: 1, respectively, in absolute cyclohexane at its boiling point in the presence of catalytic amounts of sodium hydride for 2.5-3 hours, followed by isolation of the final product. The yields of 3-phenoxyphenyl-containing 1,3-diketones were 50-74%.

When choosing a solvent for the condensation reaction of alkyl-3-phenoxybenzoate with ketones from the series: acetone, 2-butanone, acetophenone, the authors took into account the following requirements for the solvent: low toxicity, maintaining the required temperature and inertness with respect to the reagents. The use of polar aprotic solvents (diethyl ether, etc.) is possible, but the process in the environment of these solvents leads to an increase in the number of by-products, that is, reduces the yield of 3-phenoxyphenyl-containing 1,3-diketones. Cyclohexane meets the established requirements: it has low toxicity, is absolutely inert with respect to reagents, and makes it possible to increase the temperature to 80 ° C.

At the initial moment of interaction, there is no need for additional heating, since the reaction starts spontaneously even at room temperature, is accompanied by hydrogen evolution and a slight heating of the reaction mass. Then, to increase the degree of conversion of the starting reagents and accelerating the reaction, additional heating of the reaction mass to the boiling point of the solvent used is required for 2.5-3 hours, since during this time the highest conversion of the starting reagents is achieved.

The use of a 50-100% excess of alkyl-3-phenoxybenzoates in this process compared with the stoichiometric amount is necessary to exclude the possibility of condensation of the initial ketones from the series: acetone, 2-butanone, acetophenone, which have high carbonyl activity. The self-condensation of the starting ketones is minimized by the following order of introduction of the reagents: first, alkyl-3-phenoxybenzoate is slowly added to the suspension of the catalyst in the solvent with strong cooling, and then the ketone is added. The proposed method for producing 3-phenoxyphenyl-containing 1,3-diketones is characterized by simplicity of the experiment, is carried out under fairly mild conditions and provides a high (more than 50%) yield of 3-phenoxyphenyl-containing 1,3-diketones.

The possibility of using 3-phenoxyphenyl-containing 1,3-diketones as starting reagents in the synthesis of compounds is shown by the example of the complexation reaction of 3-phenoxyphenyl-containing 1,3-diketones with copper (II) ions according to the scheme

Complexation occurs under mild conditions: in an aqueous-alcoholic environment at room temperature for 3-4 hours. Due to the ability to keto-enol rearrangement, 3-phenoxyphenyl-containing 1,3-diketones under the action of copper (II) acetate form coordinatively unsaturated chelate complexes with copper (II) ions containing intermolecular bonds. The yields of chelate complexes amounted to 67-89%.

The method is as follows. To obtain alkyl-3-phenoxybenzoate, chemical reaction of 3-phenoxybenzonitrile with lower alcohols is carried out: methanol, ethanol with a molar ratio of 1: 4,245, respectively, in the presence of concentrated sulfuric acid for 7-8 hours. For the synthesis of 3-phenoxyphenyl-containing 1,3-diketones, an anhydrous cyclohexane and a calculated amount of catalyst, sodium hydride, are placed in a nitrogen purged reactor equipped with a mechanical stirrer, a reflux condenser with a calcium chloride tube, a thermometer, and a dropping funnel. With vigorous stirring (450-500 rpm) prepare a suspension of the catalyst in a solvent. To the resulting suspension, with stirring and intensive cooling, alkyl-3-phenoxybenzoate in anhydrous cyclohexane is slowly poured. Then, a ketone from the series is introduced dropwise: acetone, 2-butanone, acetophenone at a molar ratio of 2.0: 1, respectively. At the initial moment of interaction, the process proceeds with a slight heating of the reaction mass and is accompanied by the evolution of hydrogen. If no gas evolution is observed at room temperature, the heating is switched on so that the mixture boils slightly under intense hydrogen evolution. The reaction mass is refluxed until gas evolution ceases (2.5-3 hours), cooled to room temperature, left overnight. A solution of 10% acetic acid is then added in portions until the reaction is slightly acidic. The precipitate is filtered off on a Schott funnel, washed with a small amount of cyclohexane, dried. The organic layer is separated from the filtrate. The aqueous layer was extracted with ether (2 × 50 ml). The combined ether layer was washed with distilled water until neutral, dried with anhydrous sodium sulfate. The solvent is distilled off at atmospheric pressure. The resulting 3-phenoxyphenyl-containing 1,3-diketones are purified by recrystallization from methanol. The yields of the compounds obtained are 50-74% of theoretical.

The synthesis of chelate complexes of 3-phenoxyphenyl-containing 1,3-diketones with copper (II) ions is carried out by a known method [Natin S. Nandurkar, Mayur J. Bhanushali. Synt. Comm. Vol.37: 23, 2007, p.4111-4115] in an aqueous-alcoholic medium at room temperature for 3-4 hours with a ratio of 1,3-diketone: copper (II) acetate equal to 2: 1, respectively. The resulting chelate complexes with copper (II) ions are purified by recrystallization from hexane. The yields of the compounds obtained are 67-89%.

The synthesized compounds were identified by IR-NMR ¹ H - spectroscopy.

For a better understanding of the essence of the proposed technical solution, specific examples of syntheses are given.

Example 1. 1- (3-phenoxyphenyl) -butane-1,3-dione

and its chelate complex with copper (II) ions

Synthesis of methyl 3-phenoxybenzoate.

10 g (0.05 mol) of 3-phenoxybenzonitrile, 6.784 g (0.212 mol) of absolute methyl alcohol, 11.711 g (0.1195 mol) of concentrated sulfuric acid are placed in a round-bottom flask equipped with a reflux condenser with a calcium chloride tube. The mixture was refluxed for 7 hours. Then the reaction mass is cooled and poured into a container containing 50 ml of distilled water. The upper organic layer is separated, diluted with 25 ml of diethyl ether to facilitate separation of the layers in the subsequent washing process. The ether extract is washed carefully with a concentrated aqueous solution of sodium bicarbonate until the evolution of carbon dioxide ceases, then with water until neutral. Dried 10 g of anhydrous sodium sulfate for at least 30-40 minutes. Evaporate the solvent at atmospheric pressure. The final product is purified by vacuum distillation (P _OST = 4 mm Hg). Yield 6.16 g (54.1%). T.kip. 185-186 ° C (4 mm Hg), refractive index n = 1.5718. IR spectrum, υ, cm ^-1 : 1750 (С = О), 2930-3295 (С-Н), 1780, 1250 (С-O), 1298 (С-С, СН ₂ ). ¹ H NMR spectrum, δ, ppm: 0.8-1.32 m (6H, CH ₃ ), 1.8-2.25 m (6H, CH ₃ ), 4.2 m (2H, CH ₂ ), 6.0 s (H, = CH), 6.94-7.76 m (9H, C ₆ H ₅ OC ₆ H ₄ ).

Synthesis of 1- (3-phenoxyphenyl) butane-1,3-dione.

In a four-necked flask purged with nitrogen, equipped with a mechanical stirrer, a reflux condenser with a calcium chloride tube, a thermometer, and a dropping funnel, a suspension of 0.169 g (7.07 mmol) of sodium hydride in 50 ml of anhydrous cyclohexane was prepared and introduced for 30 minutes with stirring (450- 500 rpm) and intensively cooling a solution of 3 g (12.3 mmol) of methyl 3-phenoxybenzoate in 10 ml of cyclohexane. Then a solution of 0.3567 g (6.15 mmol) of dried acetone in 10 ml of anhydrous cyclohexane is slowly added. The reaction begins spontaneously even at room temperature, accompanied by hydrogen evolution and a slight heating of the reaction mass. To complete the process, the mixture is boiled under stirring under reflux until gas evolution ceases (2.5 hours), cooled to room temperature, left overnight. Then the reaction mass is acidified with 10% acetic acid with stirring until slightly acidic reaction, add 50 ml of ice water. The yellow precipitate (0.739 g) was filtered off on a Schott funnel, washed with a small amount of cyclohexane, and dried. The organic layer was separated from the aqueous acid, the aqueous layer was extracted with ether (2 × 50 ml). The combined organic extracts are washed with 200 ml of distilled water until neutral, dried over anhydrous sodium sulfate and the ether is distilled off at atmospheric pressure, cyclohexane in a vacuum of a water-jet pump. The mother liquor is cooled, the resulting crystals (0.39 g) are filtered on a Schott funnel, washed with cyclohexane, dried. The final product is purified by recrystallization from methanol. Total yield 1.137 g (72.8%). Mp 125-130 ° C. IR spectrum, υ, cm ^-1 : 2740-2890 (ОН), 2900-3300 (С-Н), 1780, 1696 (С = O), 1546 (С = С), 1294 (СН ₃ ). ¹ H NMR, δ, ppm .: m 0,8-2,25 (3H, CH _3), 16.0 s (H, OH), 4.2 m (2H, _CH2), 6.03 to (H, = CH), 6.94-7.76 m (9H, C ₆ H ₅ OS ₆ H ₄ ).

Synthesis of bis [1- (3-phenoxyphenyl) butane-1,3-dionato] copper (II).

To a solution of 1 g (3.93 mmol) of the obtained 1- (3-phenoxyphenyl) butane-1,3-dione in 40 ml of methanol, a solution of 0.4 g (1.965 mmol) of copper (II) acetate in 50 ml of water is added. Stirred for 3 hours. The precipitated green precipitate is filtered off, washed with ice water, and dried. The resulting product was purified by recrystallization from hexane. Yield 0.784 g (70%), mp. 180 ° C. NMR spectrum ¹ H, δ, ppm: 0.792-2.268 m (3H, CH ₃ ), 5.059-5.98 s (H, = CH), 6.94-7.76 m (9H, C ₆ H ₅ OS ₆ H ₄ ).

Example 2

1- (3-phenoxyphenyl) pentane-1,3-dione

and its chelate complex with copper (II) ions.

In a four-necked flask purged with nitrogen, equipped with a mechanical stirrer, reflux condenser with a calcium chloride tube, thermometer, dropping funnel, a suspension of 0.199 g (8.3145 mmol) of sodium hydride in 50 ml of anhydrous cyclohexane is prepared and introduced for 30 minutes with stirring (450- 500 rpm) and intensively cooling a solution of 3.5 g (14.5 mmol) of methyl 3-phenoxybenzoate in 10 ml of cyclohexane. Then a solution of 0.52 g (7.23 mmol) of dried 2-butanone in 10 ml of anhydrous cyclohexane is slowly added. The reaction begins spontaneously even at room temperature and is accompanied by hydrogen evolution and a slight heating of the reaction mass. To complete the process, the mixture is boiled under stirring under reflux until gas evolution ceases (2.5 hours), cooled to room temperature, left overnight. Then the reaction mass is acidified with 10% acetic acid with stirring until slightly acidic reaction, add 50 ml of ice water. The yellow precipitate (0.85 g) was filtered off on a Schott funnel, washed with a small amount of cyclohexane, and dried. The organic layer was separated from the aqueous acid, the aqueous layer was extracted with ether (2 × 50 ml). The combined organic extracts are washed with 200 ml of distilled water until neutral, dried over anhydrous sodium sulfate and the ether is distilled off at atmospheric pressure, cyclohexane in a vacuum of a water-jet pump. The mother liquor is cooled, the resulting crystals (0.45 g) are filtered on a Schott funnel, washed with cyclohexane, dried. The final product is purified by recrystallization from methanol. Total yield 1.3 g (67.5%). _Mp = 142-145 ° C. IR spectrum, υ, cm ^-1 : 2758-2890 (OH), 2920-3300 (С-Н), 1786, 1654 (С = О), 1546 (С = С). ¹ H NMR spectrum, δ, ppm: 1.047-1.3 m (3H, CH ₃ ), 8.780 s (H, OH), 2.98 m (H, = CH), 4.2 s (2H , CH ₂ ), 6.94-7.76 m (9H, C ₆ H ₅ OC ₆ H ₄ ).

Synthesis of bis [1- (3-phenoxyphenyl) -pentane-1,3-dionato] copper (II).

To a solution of 1.1 g (4.1 mmol) of the obtained 1- (3-phenoxyphenyl) -pentane-1,3-dione in 40 ml of methanol, a solution of 0.416 g (2.05 mmol) of copper (II) acetate in 50 ml is added water. Stirred for 3 hours. The precipitated green precipitate is filtered off, washed with ice water, and dried. The resulting product was purified by recrystallization from hexane. Yield 1.09 g (89%), mp. 183 ° C. ¹ H NMR, δ, ppm .: 0.9 m (6H, CH _3), 1.52 m (4H, _CH2), 3.9 m (2H, CH), 6.31 d (4H, CH ₂ = ), 6.94-7.76 m (9H, C ₆ H ₅ OC ₆ H ₄ ).

Example 3. 1- (3-phenoxyphenyl) -3-phenylpropan-1,3-dione

and its chelate complex with copper (II) ions.

In a four-necked flask purged with nitrogen, equipped with a mechanical stirrer, reflux condenser with a calcium chloride tube, thermometer, dropping funnel, a suspension of 0.194 g (8.073 mmol) of sodium hydride in 50 ml of anhydrous cyclohexane is prepared and introduced for 30 minutes with stirring (450-500 r / min) and intensively cooling a solution of 3.4 g (14.05 mmol) of methyl 3-phenoxybenzoate in 10 ml of cyclohexane. Then a solution of 0.8424 g (7.02 mmol) of dried acetophenone in 10 ml of anhydrous cyclohexane is slowly added. The reaction begins spontaneously even at room temperature and is accompanied by hydrogen evolution and a slight heating of the reaction mass. To complete the process, the mixture is boiled under stirring under reflux until gas evolution ceases (3 hours), cooled to room temperature, left overnight. Then the reaction mass is acidified with 10% acetic acid with stirring until slightly acidic reaction, add 50 ml of ice water. The precipitate (0.68 g) was filtered off on a Schott funnel, washed with a small amount of cyclohexane, and dried. The organic layer was separated from the aqueous acid, the aqueous layer was extracted with ether (2 × 50 ml). The combined organic extracts are washed with 200 ml of distilled water until neutral, dried over anhydrous sodium sulfate and the ether is distilled off at atmospheric pressure, cyclohexane in a vacuum of a water-jet pump. The mother liquor is cooled, the resulting crystals (0.42 g) are filtered on a Schott funnel, washed with cyclohexane, dried. The final product is purified by recrystallization from methanol. Total yield 1.1 g (50%). _Mp = 152-157 ° C. IR spectrum, cm ^-1 : 2740-2896 (OH), 2900-3300 (С-Н), 1786, 1654 (C = O), 1546 (С = С). ¹ H NMR spectrum, δ, ppm: 7.978 s (H, OH), 3.81 s (2H, CH ₂ ), 6.07 s (H, = CH), 6.92-7.73 m (14H , C ₆ H ₅ OS ₆ H ₄ , C ₆ H ₅ ).

Synthesis of bis [1- (3-phenoxyphenyl) -3-phenylpropane-1,3-dionato] copper (II).

To a solution of 1 g (3.16 mmol) of the obtained 1- (3-phenoxyphenyl) -3-phenylpropane-1,3-dione in 40 ml of methanol, a solution of 0.32 g (1.58 mmol) of copper (II) acetate in 50 ml of water. Stirred for 4 hours. The precipitated green precipitate is filtered off, washed with ice water, and dried. The resulting product was purified by recrystallization from hexane. Yield 0.734 g (67%), mp. 197 ° C. ¹ H NMR, δ, ppm .: 5,059-5,98 with (H, = CH), 7,02-7,66 m (28H, C ₆ H ₅ OC ₆ H _4, C ₆ H ₅₎ .

Example 4. 1- (3-phenoxyphenyl) -butane-1,3-dione.

Synthesis of ethyl 3-phenoxybenzoate.

10 g (0.05 mol) of 3-phenoxybenzonitrile, 9.752 g (0.212 mol) of absolute ethanol, 11.711 g (0.1195 mol) of concentrated sulfuric acid are placed in a round-bottom flask equipped with a reflux condenser with a calcium chloride tube. The mixture was refluxed for 8 hours. Then the reaction mass is cooled and poured into a container containing 50 ml of distilled water. The upper organic layer is separated, diluted with 20-30 ml of diethyl ether to facilitate separation of the layers in the subsequent washing process. The ether extract is washed carefully with a concentrated aqueous solution of sodium bicarbonate until the evolution of carbon dioxide ceases, then with water until neutral. Dried 10 g of anhydrous sodium sulfate for at least 30-40 minutes. Evaporate the solvent at atmospheric pressure. The final product is purified by vacuum distillation (P _OST = 4 mm Hg). Yield 6.63 g (54.8%). T.kip. 195-197 ° C (4 mm Hg), refractive index n = 1.5578. IR spectrum, υ, cm ^-1 : 1745, 1696 (С = О), 2975-3545 (С-Н), 1294 (С-С, СН ₂ ). ¹ H NMR spectrum, δ, ppm: 0.8-1.32 m (6H, CH ₃ ), 1.8-2.25 m (6H, CH ₃ ), 4.2 m (2H, CH ₃ ), 6.0 s (H, = CH), 6.94-7.76 m (9H, C ₆ H ₅ OC ₆ H ₄ ).

Synthesis of 1- (3-phenoxyphenyl) butane-1,3-dione.

In a four-necked flask purged with nitrogen, equipped with a mechanical stirrer, a reflux condenser with a calcium chloride tube, a thermometer, and a dropping funnel, a suspension of 0.169 g (7.07 mmol) of sodium hydride in 50 ml of anhydrous cyclohexane was prepared and introduced with stirring (450-500 rpm ) and intensively cooling a solution of 3 g (12.3 mmol) of ethyl 3-phenoxybenzoate in 10 ml of cyclohexane. Then a solution of 0.3567 g (6.15 mmol) of dried acetone in 10 ml of anhydrous cyclohexane is slowly added. The reaction begins spontaneously even at room temperature and is accompanied by hydrogen evolution and a slight heating of the reaction mass. To complete the process, the mixture is boiled under stirring under reflux until gas evolution ceases (2.5 hours), cooled to room temperature, left overnight. Then the reaction mass is acidified with 10% acetic acid with stirring until slightly acidic reaction, add 50 ml of ice water. The precipitate formed is filtered off (0.733 g) on a Schott funnel, washed with a small amount of cyclohexane, and dried. The organic layer was separated from the aqueous acid, the aqueous layer was extracted with ether (2 × 50 ml). The combined organic extracts are washed with 200 ml of distilled water until neutral, dried over anhydrous sodium sulfate and the ether is distilled off at atmospheric pressure, cyclohexane in a vacuum of a water-jet pump. The mother liquor is cooled, the resulting crystals (0.42 g) are filtered on a Schott funnel, washed with cyclohexane, dried. The final product is purified by recrystallization from methanol. Total yield 1.16 g (74%). Mp 125-130 ° C. IR spectrum, υ, cm ^-1 : 2740-2890 (ОН), 2900-3300 (С-Н), 1780, 1696 (С = О), 1546 (С = C), 1294 (СН ₃ ). ¹ H NMR, δ, ppm .: m 0,8-2,25 (3H, CH _3), 16.0 s (H, OH), 4.2 m (2H, _CH2), 6.03 to (H, = CH), 6.94-7.76 m (9H, C ₆ H ₅ OC ₆ H ₄ ).

Example 5. 1- (3-phenoxyphenyl) pentane-1,3-dione.

In a four-necked flask purged with nitrogen, equipped with a mechanical stirrer, a reflux condenser with a calcium chloride tube, a thermometer, and a dropping funnel, a suspension of 0.199 g (8.3145 mmol) of sodium hydride in 50 ml of anhydrous cyclohexane was prepared and introduced with stirring (450-500 rpm ) and intensively cooling a solution of 3.5 g (14.5 mmol) of ethyl 3-phenoxybenzoate in 10 ml of cyclohexane. Then a solution of 0.52 g (7.23 mmol) of dried 2-butanone in 10 ml of anhydrous cyclohexane is slowly added. The reaction begins spontaneously even at room temperature and is accompanied by hydrogen evolution and a slight heating of the reaction mass. To complete the process, the mixture is boiled under stirring under reflux until gas evolution ceases (2.5 hours), cooled to room temperature, acidified and left overnight. Then the reaction mass is acidified with 10% acetic acid with stirring until slightly acidic reaction, add 50 ml of ice water. The yellow precipitate (0.88 g) was filtered off on a Schott funnel, washed with a small amount of cyclohexane, and dried. The organic layer was separated from the aqueous acid, the aqueous layer was extracted with ether (2 × 50 ml). The combined organic extracts are washed with 200 ml of distilled water until neutral, dried over anhydrous sodium sulfate and the ether is distilled off at atmospheric pressure, cyclohexane in a vacuum of a water-jet pump. The mother liquor is cooled, the resulting crystals (0.46 g) are filtered on a Schott funnel, washed with cyclohexane, dried. The final product is purified by recrystallization from methanol. Yield 1.34 g (69%). _Mp = 142-145 ° C. IR spectrum, υ, cm ^-1 : 2758-2890 (OH), 2920-3300 (С-Н), 1786, 1654 (С = O), 1546 (С = С). ¹ H NMR spectrum, δ, ppm: 1.047-1.3 m (3H, CH ₃ ), 8.780 s (H, OH), 2.98 m (H, = CH), 4.2 s (2H , CH ₂ ), 6.94-7.76 m (9H, C ₆ H ₅ OS ₆ H ₄ ).

Example 6. 1- (3-phenoxyphenyl) -3-phenylpropane-1,3-dione.

In a four-necked flask purged with nitrogen, equipped with a mechanical stirrer, reflux condenser with a calcium chloride tube, thermometer, dropping funnel, a suspension of 0.194 g (8.073 mmol) of sodium hydride in 50 ml of anhydrous cyclohexane is prepared and introduced for 30 minutes with stirring (450-500 r / min) and intensively cooling a solution of 3.4 g (14.05 mmol) of ethyl 3-phenoxybenzoate in 10 ml of cyclohexane. Then a solution of 0.8424 g (7.02 mmol) of dried acetophenone in 10 ml of anhydrous cyclohexane is slowly added. The reaction begins spontaneously even at room temperature and is accompanied by hydrogen evolution and a slight heating of the reaction mass. To complete the process, the mixture is boiled under stirring under reflux until gas evolution ceases (3 hours), cooled to room temperature, left overnight. Then the reaction mass is acidified with 10% acetic acid with stirring until slightly acidic reaction, add 50 ml of ice water. The yellow precipitate (0.74 g) that formed was filtered off on a Schott funnel, washed with a small amount of cyclohexane, and dried. The organic layer was separated from the aqueous acid, the aqueous layer was extracted with ether (2 × 50 ml). The combined organic extracts are washed with 200 ml of distilled water until neutral, dried over anhydrous sodium sulfate and the ether is distilled off at atmospheric pressure, cyclohexane in a vacuum of a water-jet pump. The mother liquor is cooled, the resulting crystals (0.41 g) are filtered on a Schott funnel, washed with cyclohexane, dried. The final product is purified by recrystallization from methanol. Total yield 1.15 g (52%). _Mp = 152-157 ° C. IR spectrum, cm ^-1 : 2740-2896 (OH), 2900-3300 (С-Н), 1786, 1654 (C = O), 1546 (С = С). ¹ H NMR spectrum, δ, ppm: 7.978 s (H, OH), 3.81 s (2H, CH ₂ ), 6.07 s (H, = CH), 6.92-7.73 m (14H , C ₆ H ₅ OC ₆ H ₄ , C ₆ H ₅ ).

findings

A method for the synthesis of 3-phenoxyphenyl-containing 1,3-diketones and their chelate complexes with copper (II) ions has been developed. The structure of the synthesized compounds was confirmed by IR, NMR ¹ H-spectroscopy.

Claims (2)

1. 3-Phenoxyphenyl-containing 1,3-diketones of the General formula

as starting compounds for the preparation of their chelate complexes with copper (II) ions of the general formula

2. The method of obtaining 3-phenoxyphenyl-containing 1,3-diketones of the General formula

consisting in the interaction of 3-phenoxybenzonitrile with lower alcohols: methanol, ethanol in a molar ratio of 1: 4,245, respectively, in the presence of concentrated sulfuric acid for 7-8 hours, with the formation of alkyl-3-phenoxybenzoate, and its subsequent interaction with ketones from the series: acetone, 2-butanone, acetophenone in a molar ratio of 2.0: 1, respectively, in absolute cyclohexane at its boiling point in the presence of catalytic amounts of sodium hydride for 2.5-3 hours, followed by isolation of the final product but.