The method of obtaining adamantiadis-diketones and ketoesters

 

(57) Abstract:

The invention relates to the chemistry of adamantane derivatives, and in particular to a new method of obtaining-dicarbonyl derivatives of adamantane General formula

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where R=CH3:R1=CH3OC2H5; R=C6H5: R1=OC2H5C6H5, CF2H

R=CF3:R1=C6H5n-C6H4C1

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which are the products for the synthesis of biologically active substances. The connection is produced by interaction of 1,3-dehydroalanine with the appropriate-diketone or Betaferon when the molar ratio of reactants is 1: 1.5 to 2, in an inert solvent is diethyl ether at a temperature of its boiling within 1-3 hours Method allows us to simplify obtaining the target product with the release 81-98%.

The invention relates to the chemistry of adamantane derivatives, and in particular to a new process for the preparation of carbonyl-containing adamantane derivatives of General formula

< / BR>
where R=CH3:R1=CH3OC2H5; R=C6H5: R1=OC2H5C6H5, CF2H

R=CF3:R1=C6H5n-C6H4C1,

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the treatment-diketones and ketoesters, consisting in the interaction of cobalt complexes-dicarbonyl compounds with 1-bromoguanine in boiling chlorobenzene. [A. Gonza1ez, F. Cue11, J. Marquet, and Moreno-Manas, Tetrahedron Lett., 1985, 26, 3735].

The disadvantages of this method are primarily the difficulty of obtaining the source of the cobalt complex, relatively low outputs of a number of target products (in the case of receiving ether 2-adamant-1-yl occaisonally acid output was 31%), inability to obtain fluorine-, chlorine-diketones.

Closest to the proposed invention is a method for the preparation of 3-(1-substituted)-2,4-pentanedione, which is the interaction of nitroacetophenone in a solution of concentrated sulfuric acid and nitromethane with acetylacetone. Exit 3-(1-substituted)-2,4-pentanedione was 37% [Klimushkin Y. N., T. C. Tilly., N. To. Moiseev. - Zhur.org.chem., 1988, so-24, vol. 8, S. 1780-1781.

The disadvantages of this method is to conduct the process in a very acidic, and low yield of the final product and the long duration of synthesis (48 h).

The task of the invention is to develop technological molestating method of synthesis adamantiades-diketones and ketoesters, including fluorine, Ksenia output of the claimed compounds simplified method of obtaining.

The technical result is achieved in a new method of obtaining adamantiades-diketones and ketoesters of General formula

< / BR>
where R=CH3:R1=CH3OC2H5; R=C6H5: R1=OC2H5C6H5, CF2H

R=CF3:R1=C6H5n-C6H4CL,

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which consists in joining the adamantane derivative of the corresponding-dicarbonyl compounds, characterized in that as adamantane derivative use 1,3-dehydroalanine. and as-dicarbonyl compounds - -diketones of the series: acetylacetone, dibenzoylmethane, 1-(phenyl)-4,4,4-Cryptor-1,3-butandiol; 1-(phenyl)-4,4-debtor-1,3-butandiol; 1-(4-chlorophenyl)-4,4,4-Cryptor-1,3-butandiol; 1-(1,3-benzodioxol-5-yl)-4,4,4-Cryptor-1,3-butandiol; 1-(3,4-acid)-4,4,4-Cryptor-1,3-butandiol; 1-(2-thienyl)-4,4,4-Cryptor-1,3-butandiol; 1-(2-furyl)-4,4,4-Cryptor-1,3-butandiol or ketoesters of the series: ethyl ester of acetoacetic acid, ethylbenzylamine and the process is carried out at a molar ratio of 1,3-dehydroalanine and-dicarbonyl compounds is 1:1.5 to 2, in an inert solvent is diethyl ether under those is the adamantane-diketones or ketoesters in methylene carbon atom:

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The high nucleophilicity of 1,3-dehydroalanine allows you to get the products attach data-diketones or ketoesters with high yields in a fairly mild conditions.

The advantage of this method is the high output (81-98%), as well as the possibility of obtaining almost any homologues of this series, which are also intermediates for the synthesis of biologically active substances.

Found that the yield of the target-diketones and ketoesters affects the structure of the source reagent. So, with the same conditions in the case of the interaction of 1,3-dehydroalanine with acetylacetone yield of the target product was 81%, and in the case of dibenzoylmethane 96%. This can be explained by the high mobility of the protons of the Central methylene group. The mobility of protons depends on the nature of substituents at the carbonyl carbon atoms: CH3groups give the lowest yield of the target compounds is 81%, and a strong acceptor substituents, such as C6H5, CF2N, CF3- 93-98%. Thus it is found that the optimal technological and condition of the reaction accession-diketones and ketoesters to 1,3-dehydroalanine is its implementation in triketones (cetefor) 1: 1,5-2. Further increase in the content-diketones and ketoesters did not affect the yield of target products was inappropriate. The optimal reaction temperature is the boiling point of the inert solvent is diethyl ether. The optimal duration of response 1-2 hours a Further increase in the duration of the reaction is impractical because it does not lead to a significant increase in the yield of the target product. The course of this reaction is extremely sensitive to the polarity of the solvent. Not recommended for use as a solvent compounds such as pentane, hexane and other nonpolar substances. Also prohibited the use of such solvents as alcohols, carboxylic acids, amines containing reactive towards dehydroalanine group.

The method is as follows.

To 1.5-2 fold molar excess-diketone or keeeper dissolved in boiling inert solvent (diethyl ether) is poured a solution of 1,3-dehydroalanine in the same solvent. A mixture of 1,3-dehydroalanine and-diketone or keeeper heated for 1-2 hours at the boiling temperature of the solvent, after which the solvent and excess-d is EN for reuse in the same synthesis. Thus, in the industry, you can organize a recycling-diketone or keeeper with the addition of the calculated amount of fresh reagent. Synthesized adamantylidene-diketones or ketoesters after the distillation of the raw materials are sent to the stage of cleaning. The output of these products is up to 98%.

The invention is illustrated by the following examples.

Example 1.

Synthesis of 3-(adamant-1-yl)-2,4-pentanedione.

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To 7 g (0,056 mol) of acetylacetone in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 4 g (0.03 mol) svezheosazhdennoi 1,3-DGA (the molar ratio of 1,3 DHA: -diketone = 1:1,9) in 20 ml of absolute diethyl ether, and then bring the temperature of the reaction mixture up to the boiling point of the solvent, after which it was incubated 2 h until the disappearance of the insoluble b-diketone 1,3-DCA.

Upon completion of the reaction, the solvent and the excess source-diketone is removed by distillation, the residue is vacuum to remove unreacted 1,3-DCA, after which the product is recrystallized from isopropanol and get 6,23 g (0,024 mol, 81%) of 3-(adamant-1-yl)-2,4-pentanedione representing a white crystalline material, MP.=90oC.

Example 2.

Synthesis of ethyl ester of 2-(adamant-yl) 3-occaisonally acid.

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To 8 g (0,051 mol) of ethyl ester of acetoacetic acid in the atmosphere of dry nitrogen at room temperature was added dropwise a solution of 4 g (0.03 mol) svezheosazhdennoi 1,3-DGA (the molar ratio of 1,3 DHA: ketoester = 1:1,7) in 20 ml of absolute diethyl ether, and then bring the temperature of the reaction mixture up to the boiling point of the solvent, after which it was incubated 2 h until the disappearance insoluble in ketoamine 1,3-DCA.

Upon completion of the reaction, the solvent and the excess of the original keeeper removed by distillation, the residue is vacuum to remove unreacted 1,3-DCA, after which the product is distilled (BP. = 180-181/4 mm RT. Art.) and gain of 7.3 g (0,025 mol, 85%) of ethyl ester of 2-adamant-yl 3-aksesuarlari acid, representing a clear liquid with a characteristic odor, nD=1,5104.

The infrared spectrum , cm-1: 2904, 1716, 1696, 1616, 1380, 1352, 1276

Mass spectrum, m/e): 264 (M+that 8.5%), 135 (Ad+, 100%), 43 (AU+, an 18.4%)

Example 3.

Synthesis of 2-(adamant-1-yl)-1,3-(diphenyl) 1,3-propanedione.

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To 10 g (0,044 mol) dibenzoylmethane in a dry nitrogen atmosphere at room temperature precio diethyl ether, then bring the temperature of the reaction mixture up to the boiling point of the solvent, incubated for 1.5 h

Upon completion of the reaction, the solvent and the excess of the original keeeper removed by distillation, the residue is vacuum to remove unreacted 1,3-DCA, after which the product is recrystallized from isopropanol and receive of 10.25 g (0,028 mol, 96%) of 2-(adamant-1-yl)-1,3-(diphenyl) 1,3-propanedione representing a white crystalline material, MP.=210oC.

The infrared spectrum , cm-1: 2907, 2848, 1696, 1578, 1453, 1288

Mass spectrum, m/e: 358 (M+, 5,5%), 135 (Ad+, 28,8%), 105 (PhCO+, 100%), 79 (Ph+, 43%).

Example 4.

Synthesis of ethyl ether-adamantylamine acid.

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To 12 g (0,062 mol) of ethylbenzylamine in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 4 g (0.03 mol) svezheosazhdennoi 1,3-DGA (the molar ratio of 1,3 DHA: ketoester = 1:2) in 20 ml of absolute diethyl ether, bring the temperature of the reaction mixture up to the boiling point of the solvent, after which it stand 2 hours

Upon completion of the reaction the excess of the original keeeper removed by distillation, the residue is vacuum to remove unreacted 1,3-DCA, then pocasni acid, representing an oily yellow liquid with a fruity odor, nD= to 1.5580.

The infrared spectrum , cm-1: 2904, 2848, 1724, 1688, 1616, 1596, 1448, 1316, 1256, 1208, 1048

PMR-spectrum memorial plaques : 0,98 of 1.28 t (3H, CH3); 1.44MB, 1,60, 1,78, 1,88 4c (15H, Ad); 3,84-4,16 m (2H, och2); 5,44-5,56 d (N, CH); 7,18-of 7.48 m, 7,82-8,02 (5H, Ph).

Example 5.

Synthesis of 2-(adamant-1-yl)-4,4-debtor-1-(phenyl)-1,3-butanedione.

< / BR>
To 10 g (0.05 mol) of 1-(phenyl)-4,4-debtor-1,3-butandione in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 4 g (0.03 mol) svezheosazhdennoi 1,3-DGA (the molar ratio of 1,3 DHA: -diketone = 1:1,7) in 20 ml of absolute diethyl ether, bring the temperature of the reaction mixture up to the boiling point of the solvent, after which it was incubated for 1.5 h

Upon completion of the reaction, excess source-diketone is removed by distillation, the residue is vacuum to remove unreacted 1,3-DCA, after which the product is recrystallized from isopropanol and get RS 9.69 g of 2-(adamant-1-yl)-1-(phenyl)-4,4-debtor-1,3-butandione (0,028 mol, 98%), which is a white crystalline substance. MP.=64oC.

The infrared spectrum , cm-1: 2892, 2848, 1748, 1668, 1596, 1448, 1376, 1344, 1240, 1216, 1152, 1076, 1052

PMR-spectrum M. D.: of 1.97 (3H, Ad); 1,76 (N, Ad); 4,8 (1H, the MES 2-(adamant-1-yl)-1-(phenyl)-4,4,4-Cryptor-1,3-butandione.

< / BR>
To 10 g (0.046 mol) of 1-(phenyl)-4,4,4-Cryptor-1,3-butandione in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 4 g (0.03 mol) svezheosazhdennoi 1,3-DGA (the molar ratio of 1,3 DHA: -diketone = 1:1,5) in 20 ml of absolute diethyl ether, bring the temperature of the reaction mixture up to the boiling point of the solvent, after which it was allowed to stand for 1 h

Upon completion of the reaction, excess source-diketone is removed by distillation, the residue is vacuum to remove unreacted 1,3-DCA, after which the product is recrystallized from isopropanol and obtain 9.7 g (0,027 mol, 93,27%) of 2-(adamant-1-yl)-1-(phenyl)-4,4,4-Cryptor-1,3-butandione, representing a white crystalline material, MP.=95oC.

The infrared spectrum , cm-1: 2912, 2884, 1764, 1448, 1284, 1204, 1148

PMR-spectrum memorial plaques: 1,59, 1,70, 1,92 c (15H, Ad); with a 4.83 (M, CH); 7,40-EUR 7.57 m to $ 7.91, 8,02 (5H, Ph).

Example 7.

Synthesis of 2-(adamant-1-yl)-1-1(4-chlorophenyl)-4,4,4-Cryptor-1,3-butandione.

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To 12 g (0,048 mol) of 1-(4-chlorophenyl)-4,4,4-Cryptor-1,3-butandione in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 4 g (0.03 mol) svezheosazhdennoi 1,3-DGA (the molar ratio of 1,3 DHA: -diketone = 1; 1,6) in 20 ml of absolute diethyl ether, adjusted to temperature the research Institute of the reaction, excess source-diketone is removed by distillation, the residue vacuum to remove unreacted 1,3-DCA, after which the product is recrystallized from isopropanol and receive a 10 g (0,026 mol, 87,5%) of 2-(adamant-1-yl)-1-(4-chloro)phenyl-4,4,4-Cryptor-1,3-butandione representing a white crystalline material, MP.=129oC.

The infrared spectrum , cm-1: 2900, 2848, 1768, 1668, 1588, 1452, 1400, 1300, 1284, 1264, 1240, 1216, 1204, 1172, 1144, 1092, 1032

PMR-spectrum memorial plaques: 1,58-1.83 m (12H, Ad); c 2,0 (3H, Ad); the 4.90 (1H, CH); 7,5-7,95 m (4H, Ph).

Example 8.

Synthesis of 2-(adamant-1-yl)-1-(3,4-acid)-4,4,4-Cryptor-1,3-butandione.

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To 6.2 g (0,022 mol) of 1-(3,4-acid)-4,4,4-Cryptor-1,3-butandione in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 2 g (0.015 mol) svezheosazhdennoi 1,3-DGA (the molar ratio of 1,3 DHA: -diketone = 1:1,5) in 20 ml of absolute diethyl ether, bring the temperature of the reaction mixture up to the boiling point of the solvent, after which it was incubated for 1.5 h

Upon completion of the reaction, excess source-diketone is removed by distillation, the residue is vacuum to remove unreacted 1,3-DCA, after which the product is recrystallized from isopropanol and obtain 5.7 g (0.014 mol, 92%) of 2-(adamant-1-yl)-1-(3,4-acid)-4,4,4-Cryptor-1,3-butandione, performance,%), 165 ((CH3O)2PhCO+, 100%) 135 (Ad+, 42,9%), 79 (Ph+, 20,9%)

PMR-spectrum memorial plaques: 1,58-1,84 m (12H, Ad); to 1.98 (3H, Ad); 3,95 (3H, och3); 3,98 (3H, och3); 4,91 s (1H, CH); 6,92-of 6.96 (1H, Ph); 7,54-to 7.67 m (2H, Ph).

Example 9.

Synthesis of 2-(adamant-1-yl)-1-1(1,3-benzodioxol-5-yl)-4,4,4-Cryptor-1,3-butandiol.

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To 6 g (is 0.023 mol) of 1-(1,3-benzodioxol-5-yl)-4,4,4-Cryptor-1,3-butandione in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 2 g (0.015 mol) svezheosazhdennoi 1,3-DGA (the molar ratio of 1,3 DHA: -diketone = 1:1,5) in 20 ml of absolute diethyl ether, bring the temperature of the reaction mixture up to the boiling point of the solvent, after which it stand 2 hours

Upon completion of the reaction, excess source-diketone is removed by distillation, the residue is vacuum to remove unreacted 1,3-DCA, after which the product is recrystallized from isopropanol and gain of 5.2 g (0,013 mol, 88%) of 2-(adamant-1-yl)-1-(1,3-benzodioxol)-4,4,4-Cryptor-1,3-butandione representing a white crystalline material, MP.=121oC.

Mass spectrum, m/e: 394 (M+, 21%), 149 ((OCH2O)Ph(CO+), l00%) 135 (Ad+, 49,4%), 121 ((OCH2O)Ph+, 46,9%) 78 (Ph+, 30,8%)

PMR-spectrum memorial plaques: 1,57-1.83 m (12H, Ad); 1,97 e (3H, s 2-(adamant-1-yl)-4,4,4-Cryptor-1-(2-thienyl)-1,3-butanedione.

< / BR>
To 6 g (0,025 mol) of 1-(2-thienyl)-4,4,4-Cryptor-1,3-butandione in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 2 g (0.015 mol) svezheosazhdennoi 1,3-DGA (the molar ratio of 1,3 DHA: -diketone = 1:1,7) in 20 ml of absolute diethyl ether, bring the temperature of the reaction mixture up to the boiling point of the solvent, after which it stand 2 hours

Upon completion of the reaction, excess source-diketone is removed by distillation, the residue is vacuum to remove unreacted 1,3-DCA, after which the product is recrystallized from isopropanol and obtain 4.8 g (0.012 mol, 87,2%) of 2-(adamant-1-yl)-4,4,4-Cryptor-1-(2-thienyl)-1,3-butandione representing a white crystalline substance. MP.=112-113oC.

Mass spectrum, m/e): 356 (M+, and 29.9), 259 (AdCH+C(O)C4H3S, 75,5%) 135 (Ad+, 70%), 110 (C4H3S (+), 100%)

PMR-spectrum memorial plaques : 1,58-1.87 m (12H, Ad); l,99-2,0 with (3H, Ad); 4,7 c (1H, CH); 7,17-7,27 m (1H, C4H3S); 7,73-7,82 m (2N, C4H3S).

Example 11.

Synthesis of 2-(adamant-1-yl)-4,4,4-Cryptor-1-(2-furyl)-1,3-butanedione.

< / BR>
To 5.5 g (or 0.027 mol) of 1-(2-furyl)-4,4,4-Cryptor-1,3-butandione in an atmosphere of dry nitrogen at room temperature was added dropwise a solution of 2 g (0.015 mol) - the temperature of the reaction mixture up to the boiling point of the solvent, after which it stand 2 hours

Upon completion of the reaction, excess source-diketone is removed by distillation, the residue is vacuum to remove unreacted 1,3-DCA, after which the product is recrystallized from isopropanol and obtain 4.9 g (0.014 mol, 96,6%) of 2-(adamant-1-yl)-4,4,4-Cryptor-1-(2-furyl)-1,3-butandione representing a white crystalline substance. MP.=56-57oC.

Mass spectrum, m/e): 340 (M+, 7,3%), 320 (F2WITH+C(O)(Ad)SNA(OH)4H3Oh, 69,3%), 243 (AdC+HC(O)C4H3Oh, 81,7%), 135 (Ad+, 77,6%), 95 (C4H3ABOUT(FROM+), 100%)

PMR-spectrum memorial plaques: a 1.25-1.73 m (6H, Ad); 1,78-1,99 m (6H, Ad); 2,09 c (3H, Ad); 4,82 c (1H, CH); 6,60-6,63 m (1H, C4H3O); 7,15-7,39 m (1H, C4H3O); 7,66-to 7.67 (1H, C4H3O).

Conclusions.

Developed technologically melastatin method of synthesis adamantiades-diketones and ketoesters, including fluorine-, chlorine-diketones, and compounds having in its composition cyclic substituents, flowing with high yield. The structure of the described compounds is confirmed by IR, PMR-spectra and elemental analysis.

The method of obtaining adamantiades-diketones and ketoesters of General formula

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where 5, CF2H

R = CF3: R1= C6H5n-C6H4CL,

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which consists in joining the adamantane derivative of the corresponding-dicarbonyl compounds, characterized in that as adamantane derivative use 1,3-dehydroalanine, and as-dicarbonyl compounds - -diketones of the series: acetylacetone, dibenzoylmethane, 1-(phenyl)-4,4,4-Cryptor-1,3-butandiol; 1-(phenyl)-4,4-debtor-1,3-butandiol; 1-(4-chlorophenyl)-4,4,4-Cryptor-1,3-butandiol; 1-(1,3-benzodioxol-5-yl)-4,4,4-Cryptor-1,3-phenylbutazone; 1-(3,4-acid)-4,4,4-Cryptor-1,3-butandiol; 1-(2-thienyl)-4,4,4-Cryptor-1,3-butandiol; 1-(2-furyl)-4,4,4-Cryptor-1,3-butandiol or ketoesters of the series: ethyl ester of acetoacetic acid, ethylbenzylamine and the process is carried out at a molar ratio of 1,3-dehydroalanine and-dicarbonyl compound is 1:1,5-2, in the inert solvent is diethyl ether at a temperature of its boiling within 1-2 hours

 

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Iodinated esters // 2088579

The invention relates to 1-alkyl, 1-alkenyl, and 1-alkynylaryl-2-amino-1,3-propandiol formula 1:

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where R is

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R5represents a group of the formula:

CH3(CH2)mCC-, CH3(CH2)mCH CH-,

CH3(CH2)mCH2-CH2-,< / BR>
,< / BR>
m is from 3 to 15 and n is from 0 to 12

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RCH (OR1)CHN(R2R3)P4whereOSO

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R3is hydrogen, alkyl orOR7where R7is hydrogen or alkyl, or CH2OR8where R8is hydrogen orR6where R6is defined above,

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where R9and R10independently are hydrogen or alkyl

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where R is alkyl, aryl, substituted aryl, furyl, substituted furyl

R' is alkyl WITH1-C4

-adamantylidene aliphatic and fatty-aromatic ketones" target="_blank">

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where R2= H; R1= H; R = CH3t-C4H9WITH6H5; R2= H; R1= CH3; R = CH3C2H5; R2= CH3; R1= CH3; R= i-C3H7which are intermediates for the synthesis of biologically active substances

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where R2= H; R1= H; R = CH3t-C4H9WITH6H5; R2= H; R1= CH3; R = CH3C2H5; R2= CH3; R1= CH3; R= i-C3H7which are intermediates for the synthesis of biologically active substances

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FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing 1,3-diphenylbut-2-2ene-1-one (dypnone) from acetophenone in the presence of cation-exchange polymerizing sulfoacid resin in H+-form as a catalyst at temperature 80-160°C. The process can be carried out in the presence of nonpolar aliphatic hydrocarbon solvent. Acetophenone fraction isolating in the process for the combined preparing propylene oxide and styrene can be used as acetophenone. Method provides selectivity is 84-98.8% by dypnone in consumption of catalyst 3.0-3.4% of acetophenone mass.

EFFECT: improved preparing method.

3 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the method of obtaining new adamantly containing derivatives of symmetric 1,4-diketones with the general formula: where R1=H or CH3, R1-H or CH3, which are potentially biologically active materials. The method consists of connecting to 1,3-dehydroadamantan or 5,7-dimethyl-1,3-dehydroadamantan symmetrical 1,4-diketone: 2,5-hexanedione or 1,4-cyclohexanedione with their molar relation equal to 1:1 at the temperature of 80°C for a period of 5 hours.

EFFECT: it makes it possible to obtain new compounds with a high output.

4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 1-acetyl-4-propionylbenzene, which is starting material for making medicinal agents and dipyrrolylbenzenes, used in synthesis of conducting interlinked polymer systems, which can be used as electrode materials for energy accumulators, biosensors, photoluminescent materials, electroluminescent materials and electromagnetic shields. The method involves using propionyl chloride and ethylbenzene as starting material in an organic solvent medium, and carrying out the reaction in the presence of anhydrous aluminium chloride at temperature between 25 and 40°C for 20 to 60 minutes, with formation of an intermediate product 1-propionyl-4-ethylbenzene, which is separated and oxidised with potassium permanganate in an aqueous solution of magnesium nitrate at temperature between 65 and 80°C for 3 to 5 hours, forming the desired product which is extracted using toluene, with subsequent recrystallisation from n-hexane or petroleum ether. The method uses non-toxic and readily available components, which makes the proposed method suitable for industrial use.

EFFECT: design of a simple industrial method of producing 1-acetyl-4-propionylbenzene.

4 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing 1-acetyladamantane, which is used in synthesis of several substituted adamantanes and is starting material in preparation of medicinal agents having antibacterial and antiviral activity, the most common of which is Remantadin. Also, alkyladamantyl ketones (including 1-acetyladamantane) are recommended for use in veterinary medicine for treating Newcastle disease. The method involves reacting 1-chloroadamantane with ethyledene diacetate (EDA) in a medium of carbon tetrachloride in the presence of a nickel-containing catalyst (Ni(acac)2, NiBr2(PPh3)2, NiCl2(PPh3)2 or NiCl2(PBu3)2), activated with acetonitrile, at temperature 160-180°C for 5-7 hours, in molar ratio [1-chloradamantane] : [EDA] : [CCl4] : [catalyst] : [CH3CN]=100:100-200:200:3-5:10-15.

EFFECT: invention enables production of the end product using a simple method with output of 85-90%.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing fluorine-containing tetraketones of general formula: , where I) R1=CHCH(CH3)2; R2=CH3; II)R1=CH2; R2=Ph III) R1=CHCH2CH3; R2=Ph, which can be used as synthons for producing their fluorine-containing aza- and thio-analogues, β-hydroxyketones, pyrazoles, isoxazoles, as well as biologically active substances. The method involves reacting a diester of perfluoro-dicarboxylic acid with an alkylketone in the presence of sodium hydride in the medium of an organic solvent. The diester of perfluoro-dicarboxylic acid used is dimethyl ester of perfluoro-dodecane dicarboxylic acid and the alkylketone used is: acetophenone, methyl isobutyl ketone or propyl phenyl ketone, and the process is carried out in the presence of a catalyst - dibenzo-24-crown-8 ester, in molar ratio diester of perfluoro-dicarboxylic acid: alkylketone: sodium hydride: catalyst equal to 1 : (2-3.5) : 1 : (0.00025-0.0005).

EFFECT: method enables to obtain desired products with high output in a single step.

1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing (C60-Ih)[5,6]fullero[2',3':1,9]cyclopropan-1'-yl(cycloalkyl)methanones of general formula (1): n=1; 2; 3, which can be used as components of high-energy fuels, as well as nanomaterials for preparing modern additives for heavily loaded mechanisms and machines and starting substances in production of medicinal agents. The method involves reaction of C60-fullerene with 2-oxo-2-cycloalkyl diazoethanes (N2CHC(O)cycloalkyl) in o-dichlorobenzene (o-DCB) in the presence of a three-component catalyst {Pd(acac)2 : 2PPh3:4Et3Al}, taken in molar ratio C60:2-oxo-2-cycloalkyl diazoethane:Pd(acac)2:PPh3:Et3Al = 0.01:(0.03-0.07):(0.001-0.003):(0.002-0.006):(0.004-0.012), preferably 0.01:0.05:0.002:0.004:0.008, at temperature 80°C for 0.5-1.5 hours.

EFFECT: method enables to obtain desired products with high output.

1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: method involves reaction of 1-chloroadamantane with ethylidene diacetate (EDA), where the catalyst used is a manganese-containing compound selected from Mn(acac)3 or Mn(OAc)2 or Mn2(Co)10, activated with acetonitrile in a tetrachloromethane medium in molar ratio [1-chloroadamantane] : [EDA] : [CCl4] : [catalyst] : [CH3CN]=100 : 100-200 : 200 : 3-5 : 10-15 at temperature 160-180°C for 5-7 hours. Under optimum conditions with 85-90% conversion of 1-chloroadamantane, the only reaction product is 1-acetyladamantane.

EFFECT: improved method.

1 tbl, 8 ex

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