Method for synthesis of ethyl ethers of 2-alkyl-4-aryl-3-oxobutanoic acids

FIELD: chemistry.

SUBSTANCE: invention relates to synthesis of 1,3-dicarboxylic compounds, specifically to a method for synthesis of ethyl ethers of 2-alkyl-4-aryl-3-oxobutanoic acids of general formula:

,

where for R=3,5-Me2C6H3, R1=Me, Et, i-Pr; for R=2,6-Cl2C6H3, R1=Me; for R=2- CI-6-FC6H3, R1=Me, involving acylation of di(bromine-magnesium)salt of ethyl ether of 2-alkyl-3,3-dihydroxyacrylic acid, selected from a group comprising di(bromine-magnesium)salt of ethyl ether of 2-methyl-3,3-dihydroxyacrylic acid, di(bromine-magnesium) salt of ethyl ether of 2-ethyl-3,3-dihydroxyacrylic acid and di(bromine-magnesium) salt of ethyl ether of 2-isopropyl-3,3-dihydroxyacrylic acid, obtained in situ from isopropyl magnesium bromide and the corresponding 2-(carbethoxy)alkanoic acid, arylacetyl chloride, selected from 3,5-dimethylphenylacetyl chloride, 2,6-dichlorophenylacetyl chloride and 2-fluoro-6-chlorophenylacetyl chloride, in molar ratio of arylacetyl chloride: di(bromine-magnesium) salt of ethyl ether of 2-alkyl-3,3-dihydroxyacrylic acid equal to 1: 1.6-2.2, in a medium of anhydrous tetrahydrofuran with subsequent treatment of the reaction mass with aqueous solution of citric acid and extraction of the end product.

EFFECT: high output and purity of disclosed compounds.

7 ex

 

The present invention relates to the field of synthesis of 1,3-dicarbonyl compounds, particularly to a process for the preparation of ethyl esters of 2-alkyl-4-aryl-3-of oxobutanoic acids of the formula:

where:

when R=3,5-Me2C6H3R1=Me, Et, i-Pr;

when R=2,6-Cl2C6H3R1=Me;

when R=2-Cl-6-FC6H3R1=Me,

which are used as precursors for antiviral pyrimidine series.

The closest and only described in the literature as the method of obtaining the ethyl ester of 2-alkyl-4-aryl-3-of oxobutanoic acids with branched alkyl radical (for example, isopropyl or sec-bootrom) in position 2 allows only tsinkorganicheskih synthesis blaze [Nawrozkij, MV 5-Alkyl-6-benzyl-2-(2-oxo-2-phenylethylsulfanyl)pyrimidin-4(3H)-ones, a Series of Anti-HIV-1 Agents of the Dihydro-alkoxy-benzyl-oxopyrimidine Family with Peculiar Structure-Activity Relationship Profile [Text] / M.B.Nawrozkij, D.Rotili, D.Tarantino, et.al. // J. Med. Chem. - 2008. - Vol.51. - P.4641-4652]. The latter is based on the interaction of the corresponding nitrile akriluksusnoy acid obtained in situ reagent reformed in absolute tetrahydrofuran (THF), followed by hydrolysis of the reaction product and the target allocation ethyl ester of 2-alkyl-4-aryl-3-oxobutanoic acid.

This method has several significant drawbacks. First, for its realization it is necessary to IP the use of a large (4-5-fold) molar excess of the reagent reformed [Sbardella, G. Does the 2-Methylthiomethyl Substituent Really Confer High Anti-HIV-1 Activity to S-DABO? [Text] / G.Sbardella, A.Mai, M.Artico, S.Massa, et.al. // Med. Chem. Res. - 2000. - Vol.10, No. 1. - P.30-39]. Secondly, in the course of synthesis observed the formation of side 3-oxoethyl that, in some cases, difficult to separate from the desired product of the reaction [Eremicus, A.S. Synthesis and study of new derivatives of 6-(2,6-dehalogenases)-5-alkyl-2-(alkylsulfanyl)-4(3H)-pyrimidinone [Text]: Diss. ... candles. chem. Sciences. / Aserenity. - Volgograd, 2008. - 135 C.]. Third, when conducting the synthesis side is the formation of heterocyclic derivatives of 3,5-dialkyl-6-(arylmethyl)-4-hydroxypyridine-2(1H)-she [Aly, Y.L.Synthesis and anti-HIV-1 Activity of New MKC-442 Analogues with an Alkylnyl-substituted 6-benzyl group [Text] / Y.L.Aly, E.B.Pedersen, P.La Colla, R.Loddo // Arch. Pharm. Chem. Life Sci. - 2007. - Vol.340. - P.225-235]. B fourth, the hydrolysis of the reaction mixture is carried out using an aqueous solution of hydrochloric or sulfuric acid, which makes the method unsuitable for the synthesis of acidogenic ethyl esters of 2-alkyl-4-aryl-3-of oxobutanoic acids. In addition, the outputs of pure ethyl esters of 2-alkyl-4-aryl-3-of oxobutanoic acids obtained in accordance with this method, rarely exceed 60-70%.

The objective of the proposed technical solution is the development of a new technological method of producing ethyl esters of 2-alkyl-4-aryl-3-of oxobutanoic acids, allowing to carry out the synthesis under mild conditions, used with the eating of available reagents and obtaining the desired products in high yield and purity.

The technical result is to increase the yield and purity of the claimed compounds.

This technical result is achieved in a method of producing ethyl esters of 2-alkyl-4-aryl-3-of oxobutanoic acids of the General formula:

where:

when R=3,5-Me2C6H3R1=Me, Et, i-Pr;

when R=2,6-Cl2With6H3R1=Me;

when R=2-Cl-6-FC6H3R1=Me

involves acylation di(romagnieu) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetone acid selected from the group di(romagnieu) salt of the ethyl ester of 2-methyl-3,3-dihydroxyacetone acid, di(romagnieu) salt ethyl ester 2-ethyl-3,3-dihydroxyacetone acid and di(romagnieu) salt of the ethyl ester of 2-isopropyl-3,3-dihydroxyacetone acid, obtained in situ from ISO-propylaniline and the corresponding 2-(carbethoxy)alanovoy acid, arylacetylenes selected from 3,5-dimethylphenylethylamine, 2,6-and 2 dichlorophenylisocyanate-fluoro-6-chlorophenylacetyl, when the molar ratio arylacetylenes: di(bromania) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetone acid of 1:1.6 to 2.2, in the medium of anhydrous THF followed by treatment of the reaction mixture with an aqueous solution of citric acid and isolation of the target product.

The essence of the proposed JV is soba is the acylation of salts and hydrolysis/decarboxylation reaction mass under the action of an aqueous solution of citric acid:

where:

when R=3,5-Me2C6H3R1=Me, Et, i-Pr;

when R=2,6-Cl2C6H3R1=Me;

when R=2-Cl-6-FC6H3R1=Me.

Source di(bromania) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetone acid is obtained in situ by treating the corresponding 2-(carbethoxy)alanovoy acid isopropylacrylamide in the medium of anhydrous THF:

where R1=Me, Et, i-Pr.

The advantage of this method is the possibility of obtaining almost any ethyl esters of 2-alkyl-4-aryl-3-of oxobutanoic acids, exit, close to quantitative, does not require additional purification.

The proposed method is as follows.

Obtaining the ethyl ester of 2-alkyl-4-aryl-3-of oxobutanoic acids

In trekhgolovy reactor with a magnetic stirrer, equipped with internal thermometer, addition funnel with pressure compensator and a waterproof tube, was placed a solution of 70 mmol 2-(carbethoxy)alanovoy acid in anhydrous THF (50 ml). The resulting mixture was stirred under ice cooling. When the temperature of the mixture reaches 0°C, the reaction mass is added dropwise 150 ml of 1M solution of isopropylacrylamide in anhydrous THF and stirring is continued for another 30 minutes at the same temperature. Then to the reaction the mass under stirring and cooling with ice with salt added dropwise a solution of 35 mmol of arylacetylenes in anhydrous THF (50 ml). Thus there is a slight increase in the temperature of the reaction mass and its subsequent reduction to 0°C. After addition of all solution arylacetamide the reaction mass is stirred for further 1 hour at 0°C. Then the cooling bath removed and the reaction mass is stirred until until its temperature reaches room temperature. At this temperature the reaction mass is stirred for further 1 hour. Then the reaction mixture is poured into 400 ml of 10%aqueous solution of citric acid monohydrate (intensive foaming at the expense of the carbon footprint!). The obtained two-phase system is intensively stirred for 20 minutes and extracted with ether (3×150 ml). The combined organic extracts washed with water, 5%sodium carbonate solution and again with water, then dried with anhydrous magnesium sulfate. After filtration of the drying agent through a thin layer of silica gel for thin-layer chromatographie (TLC) the solvent is distilled off and the residue is pure ethyl ester of 2-alkyl-4-aryl-3-oxobutanoic acid.

The invention is illustrated by the following examples.

Example 1. Ethyl ester of 4-(3, 5dimethylphenyl)-3-oxo-2-isopropylmalonic acid

In trekhgolovy reactor with a magnetic stirrer, equipped with internal thermometer, addition funnel with pressure compensator and vegasas is based tube placed a solution of 12.2 g (70 mmol) of 2-(carbethoxy)-3-methylbutanoic acid in anhydrous THF (50 ml). The resulting mixture was stirred under ice cooling. When the temperature of the mixture reaches 0°C, the reaction mass is added dropwise 150 ml of 1M solution of isopropyl-minibrain in anhydrous THF and stirring is continued for another 30 minutes at the same temperature. Then to the reaction mass with stirring and ice cooling with salt added dropwise a solution of 6.4 g (35 mmol) of 3,5-dimethylphenylcarbamate in anhydrous THF (50 ml). Thus there is a slight increase in the temperature of the reaction mass and its subsequent reduction to 0°C. After addition of all solution of 3,5-dimethylphenylcarbamate the reaction mass is stirred for further 1 hour at 0°C. Then the cooling bath removed and the reaction mass is stirred until until its temperature reaches room temperature. At this temperature the reaction mass is stirred for further 1 hour. Then the reaction mixture is poured into 400 ml of 10%aqueous solution of citric acid monohydrate (intensive foaming at the expense of the carbon footprint!). The obtained two-phase system is intensively stirred for 20 minutes and extracted with ether (3×150 ml). The combined organic extracts washed with water, 5%sodium carbonate solution and again with water, then dried with anhydrous sulfate is magnesium. After filtration of the drying agent through a thin layer of silica gel for TLC, the solvent is distilled off and the residue is pure ethyl ester of 2-alkyl-4-aryl-3-oxobutanoic acid. The output of the ethyl ester of 4-(3, 5dimethylphenyl)-3-oxo-2-isopropylmalonic acid - 8.7 g (90%). Rf=0.82, system - C6H14-EtOAc (9:1) (plate - Alugram NanoSil UV254).

1H NMR (300 MHz, chloroform-d) δ ppm 0.79 (d, J=6.84 Hz, 3H) 0.87 (d, J=6.84 Hz, 3H) 1.08-1.25 (m, 3H) 2.21 (s, 6H) 2.31-2.44 (m, 1H) 3.25 (d, J=9.40 Hz, 1H) 3.64 (s, 2H) 3.97-4.14 (m, 2H) 6.69-6.86 (m, 3H).

Ratio of initial reagents: arylacetylenes: di(bromania) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetone acid is 1:2.

Example 2. Ethyl ester of 4-(3, 5dimethylphenyl)-3-oxo-2-isopropylmalonic acid

Perform analogously to example 1 except the ratio of initial reagents: arylacetylenes:di(bromania) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetone acid is 1:1.6.

Output ethyl ester ethyl ester 4-(3, 5dimethylphenyl)-3-oxo-2-isopropylmalonic acid - 86%.

Example 3. Ethyl ester of 4-(3, 5dimethylphenyl)-3-oxo-2-isopropylmalonic acid

Perform analogously to example 1 except the ratio of initial reagents: arylacetylenes: di(bromania) salt of the ethyl ester of 2-alkyl-3,3-dihydroxy iloveu acid is 1:2.2.

The output of the ethyl ester of 4-(3, 5dimethylphenyl)-3-oxo-2-isopropylmalonic acid - 90%.

Example 4. Ethyl ester of 4-(3, 5dimethylphenyl)-3-oxo-2-methylbutanoic acid

Perform analogously to example 1, except for using di(romagnieu) salt of the ethyl ester of 2-methyl-3,3-dihydroxyacetone acid as di(romagnieu) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetophenone acid.

Ratio of initial reagents: arylacetylenes: di(bromania) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetone acid is 1:2.

The output of the ethyl ester of 4-(3, 5dimethylphenyl)-3-oxo-2-methylbutanoic acid - 94%. Rf=0.82, system - C6H14-EtOAc (9:1) (plate - Alugram NanoSil UV254).

1H NMR (300 MHz, chloroform-d) δ M. D. 1.14-1.31 (m, 6H) 2.16-2.32 (m, 4H) 2.24 (s, 6H) 3.49-3.64 (m, 1H) 3.65-3.80 (m, 2H) 4.06-4.23 (m, 2H) 6.72-6.87 (m, 3H).

Example 5. Ethyl ester of 4-(3, 5dimethylphenyl)-3-oxo-2-ethylbutanol acid

Perform analogously to example 1, except for using di(romagnieu) salt ethyl ester 2-ethyl-3,3-dihydroxyacetone acid as di(romagnieu) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetophenone acid.

Ratio of initial reagents: arylacetylenes:di(bromania) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetophenone be 1:2.

The output of the ethyl ester of 4-(3, 5dimethylphenyl)-3-oxo-2-ethylbutanol acid - 94%. Rf=0,87, system - C6H14-EtOAc (9:1) (plate - Alugram NanoSil UV254).

1H NMR (300 MHz, chloroform-d) δ ppm 0.74-0.84 (m, 3H) 1.11-1.28 (m, 3H) 1.73-1.87 (m, 2H) 2.14-2.31 (m, 3H) 2.22 (s, 6H) 3.35-3.50 (m, 1H) 3.67 (s, 2H) 4.03-4.19 (m, 2H) 6.70-6.86 (s, 3H).

Example 6. Ethyl ester of 4-(2,6-dichlorophenyl)-3-oxo-2-methylbutanoic acid

Perform analogously to example 1, except for using di(romagnieu) salt of the ethyl ester of 2-methyl-3,3-dihydroxyacetone acid as di(romagnieu) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetophenone acid and 2,6-dichlorophenylisocyanate as arylacetylenes.

Ratio of initial reagents: arylacetylenes: di(bromania) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetone acid is 1:2.

The output of the ethyl ester of 4-(2,6-dichlorophenyl)-3-oxo-2-methylbutanoic acid - 90%. TPL 98-99°C (hexane), which corresponds to [Mai, A. 5-Alkyl-2-(alkylthio)-6-(2,6-dihalophenylmethyl)-3,4-dihydropyrimidin-4(3H)-ones: Novel Potent and Selective Dihydro-alkoxy-benzyl-oxopyrimidine Derivatives [Text] / A.Mai, M.Artico, G.Sbardella, S.Massa, et.al. //J. Med. Chem. - 1999. - Vol.42, No. 4. - P.619-627].

Example 7. Ethyl ester of 4-(2-fluoro-6-chlorophenyl)-3-oxo-2-methylbutanoic acid

Perform analogously to example 1, except for using di(romagnieu) salt etiolog the ester of 2-methyl-3,3-dihydroxyacetone acid as di(romagnieu) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetone acid and 2-fluoro-6-chlorophenylacetyl as arylacetylenes.

Ratio of initial reagents: arylacetylenes: di(bromania) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetone acid is 1:2.

The output of the ethyl ester of 4-(2-fluoro-6-chlorophenyl)-3-oxo-2-methylbutanoic acid 96%. TKIP-128°C (1 mm Hg), which corresponds to [Eremicus, A.S. Synthesis and study of new derivatives of 6-(2,6-dehalogenases)-5-alkyl-2-(alkylsulfanyl)-4(3H)-pyrimidinone [Text]: Diss. ... candles. chem. Sciences. / Aserenity. - Volgograd, 2008. - 135 C.].

It follows from the presented examples, we proposed a method of obtaining ethyl esters of 2-alkyl-4-aryl-3-of oxobutanoic acid is a technology that allows to obtain a wide range of these compounds with high yield and high purity.

The method of obtaining the ethyl ester of 2-alkyl-4-aryl-3-of oxobutanoic acids of the General formula:

where R=3,5-Me2With6H3R1=Me, Et, i-Pr;
when R=2,6-CL2With6H3 R1=Me;
when R=2-CL-6-FC6H3R1=Me,
involves acylation di(romagnieu) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetone acid selected from the group di(romagnieu) salt of the ethyl ester of 2-methyl-3,3-dihydroxyacetone acid, di(romagnieu) salt ethyl ester 2-ethyl-3,3-dihydroxyacetone acid and di(romagnieu) salt of ethyl ether 2-from the propyl-3,3-dihydroxyacetone acid, obtained in situ from isopropylacrylamide and the corresponding 2-(carbethoxy)alanovoy acid, arylacetylenes selected from 3,5-dimethylphenylethylamine, 2,6-dichlorophenylisocyanate and 2-fluoro-6-chlorophenylacetyl, when the molar ratio arylacetylenes: di(bromania) salt of the ethyl ester of 2-alkyl-3,3-dihydroxyacetone acid of 1:1.6 to about 2.2, in the medium of anhydrous tetrahydrofuran THF followed by treatment of the reaction mixture with an aqueous solution of citric acid and isolation of the target product.



 

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The invention relates to organic chemistry, specifically to methods of producing 2-hydroxy-4-(meth)acryloylmorpholine (OMF or OABF)

FIELD: organic chemistry, in particular polymers.

SUBSTANCE: invention relates to new method for production of vic-dichlorofluoroanhydride useful as intermediate of starting monomer for fluorinated polymers with good yield from available raw material. Claimed method includes fluorination of starting material (I): (RH1-EH1-)CRH2RH3CH2-0CORHB in liquid phase to form compound of formula (II): (CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB; ester bond splitting of formula (II) in gaseous phase under solvent absence to form compound of formula (III): (CF2ClCFCl-EF1-)CRF2RF3COF or compound of formula (III) and compound of formula (IV): FCORFB, wherein RH1 is CX1X2ClCX3Cl- or CClX4=CCl, wherein each X1-X4 independently is hydrogen; RH2 and RH3 independently are hydrogen or linear or branched alkyl, optionally substituted with one or more oxygen; EH1 is alkylene, optionally substituted with one or more oxygen; EF1 = EH1 wherein perfluoroalkylene group is optionally substituted with one or more oxygen; RHB = RFB and are linear or branched perfluoroalkyl group, optionally substituted with chlorine one or more oxygen; RF2 is fluorinated RH2; RF3 is fluorinated RH3; with the proviso, that RF2 is fluorinated RH2; RF3 is fluorinated RH3, i.e. RF2 and RF3 represent RH2 or RH3 with at least one fluorinated hydrogen. Also disclosed are new compounds, represented in claims of invention.

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to industrially useful fluorine-containing compounds such as fluorinated ester compounds and acyl fluoride compounds. Invention, in particular, provides ester compound wherein all C-H groups are fluorinated and which is depicted by general formula RAFCFR1FOCORBF (4), where RAF, CFR1, and RBF are specified elsewhere. Preparation of the ester compound comprises fluorination of ester (4), which has hydroxyl group(s), acyl fluoride group(s) and which has a structure allowing compound to be fluorinated in liquid phase, fluorination being effected in mixture of ester compound and compound having acyl fluoride group(s). Method does not involve environmentally unfriendly solvent such as, for instance, R-113.

EFFECT: enabled fluorination requiring no specific solvent for each reaction and which can be carried out without separation of solvent before next stage.

9 cl, 8 ex

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