The method of obtaining esters of carboxylic acids

 

(57) Abstract:

The inventive aldehyde of General formula RC(O)H, where R is lower alkyl, phenyl, optionally substituted with halogen, furyl, optionally substituted with homogena or phenylalaninol group; treated with sodium peroxide in the environment of N,N-dimethylformamide or N,N-dimethylacetamide at 15 - 20oFrom the Obtained reaction mixture is subjected to treatment with carbon dioxide, and then alkyl halide R1X, where R1- (C1-C4) alkyl, and X is an iodine atom or bromine, with 15 - 20oWith in 24 hours. The process is carried out at the following molar ratio of aldehyde components: sodium peroxide: alkyl halide, equal to 1,0:1,0:1,1. table 1.

The invention relates to synthetic organic chemistry, namely to a process for the preparation of esters of carboxylic acids of General formula:

< / BR>
where R is alkyl, aryl, substituted aryl, furyl, substituted furyl

R' is alkyl WITH1-C4.

In synthetic organic chemistry known way to obtain esters with a yield of 75 to 90% by alkylation halide alkilani potassium salts of carboxylic acids in a mixture of ethanol-hexadecanol (see P. E. Pfeffer, T. A. Foglia, P. A. Barr, J. Schmeltz and L. S. Silbert, Tetrahedron Lett. 1972, the Oh dear solvent, as hexadecanol.

Closest to the claimed method for producing esters is the way, which consists in the interaction halide Akilov sodium salts of carboxylic acid in N,N-dimethylformamide, which allows for 24 hours to obtain esters with yields of 80 to 90% (see F. J. Parker, Adv. Org. Chem. 1965, 5, 37) prototype.

The disadvantage of this method is the need to use ready-carboxylic acid.

The aim of the invention is the combination in one reactor three stages:

1) the oxidation of aldehyde to acid,

2) the formation of the sodium salt of the acid during the oxidation (oxidative, salt formation),

3) alkylation of the sodium salt of the acid to complex ether.

Consequently, there is no need for ready carboxylic acid to produce esters.

The method consists in the interaction of the corresponding aldehyde of the General formula where R has the above meanings with sodium peroxide in a molar ratio of aldehyde: Na2O21:1 in the bipolar aprotic solvent (N, N-dimethylformamide, N,N-dimethylacetamide) at a temperature of +15 - 20oC for 1 to 3 hours, with subsequent processing of forming the specified values, X Br, I) within 24 hours at room temperature and molar ratio of reactants: aldehyde: Na2O2: R'-X 1:1: 1,1. The resulting ester produce by conventional methods. The yield of ester is 80 to 95% of the Process of obtaining a complex ester is expressed by the following equations:

< / BR>
In accordance with stage 2) in the reaction mixture before the addition of R'-X, you must enter the CO2for translation of NaOH in NaHCO3avoid alkaline hydrolysis of ester.

Thus, the proposed method can find application in industrial organic synthesis of esters of carboxylic acids from aldehydes.

Example 1. Butyl ester of butyric acid (butylmalonate)

To a suspension of 7.8 g (of 0.085 mol) of 85% Na2O2in 80 ml of N,N-dimethylformamide for 0.5 hours under continuous stirring and at a temperature of +15 20oWith (exothermic process) was added to 6.1 g (of 0.085 mol) butyric aldehyde in 15 ml of N,N-dimethylformamide. Stirred at this temperature until the disappearance of the aldehyde in the mixture (TLC control). Then, at this temperature, skip to 0.2 mol CO2. Then add 12.7 g (0,093 mol) of butyl bromide. The mixture is stirred for 1 hour and left at +20o2SO4. The ether is distilled off and the product distilled in vacuum, collecting the fraction with BP. 60oWith/15 mm RT.article Gain of 9.8 g (80%) butylmalonate, PD201,4072 (lit. data boiling point. 55o/13 mm RT.article PD201,4075 Properties of organic compounds", Directory. L. O. Chemistry, 1984, pages 144 and 145).

Example 2. Methyl ester 5-jodphur-2-carboxylic acid.

To a suspension of 7.8 g (of 0.085 mol) of 85% Na2O2in 80 ml of N,N-dimethylacetamide for 1 hour at +15 20oC and stirring add 18,8 g (of 0.085 mol) of 5-itfuture in 30 ml of N,N-dimethylacetamide. The mixture is stirred at this temperature until the disappearance in a solution of 5-itfuture (TLC control). Then passed into a solution of 0.2 mol CO2. Then add one dose of 13.3 g (0,093 mol) methyl iodide, the mixture is stirred and left at +20oWith 24 hours. The mixture is then diluted with 300 ml of distilled water and treated with a solution as described in example 1. The crystalline product is recrystallized from hexane. Gain of 20.3 g (95%) of methyl ester of 6-jodphur-2-carboxylic acid with Tmelt. 82 - 82,5o(Lit. data Tmelt. 82oTo see Joh, T. 30, vol. 7, 1960, page 2325).

Example 3. Ethyl ether b) para-bromobenzaldehyde, 13.3 g (0,093 mol) of ethyl iodide in N,N-dimethylformamide. Received of 18.3 g (95%) ethyl ester of para-bromobenzoyl acid with BP. 135o/15 mm RT.article PD201,5450 (see Properties of organic compounds. The Handbook. L. O. Chemistry, 1984, pages 148 and 149).

Example 4. Methyl ether, furan-2-carboxylic acid (mailformat).

Analogously to example 2) of 7.8 g (of 0.085 mol) of 85% Na2O2and 8.1 g (of 0.085 mol) of furfural and 13.3 g (0,093 mol) methyl iodide in N,N-dimethylformamide. Obtained 10.0 g (95%) methyl ester furan-2-carboxylic acid with BP. 81 82oC/20 mm RT.article PD201,4872 (lit. data boiling point. 81 82oC/20 mm RT. senior PD201,4875 (see Properties of organic compounds. The Handbook. L. O. Chemistry, 1984, page 390 391).

Example 5. Methyl ester 5-phenylethylene-2-carboxylic acid

Analogously to example 2) of 7.8 g (of 0.085 mol) of 85% Na2O2, 16.7 g (of 0.085 mol) of 5-ventilationperfusion, 13.3 g (0,093 mol) methyl iodide in N,N-dimethylacetamide. The output of the methyl ester 5-phenylethylene-2-carboxylic acid 16.3 g (85%) with Tmelt. 84 85oC (from petroleum ether) (see lit. data Tmelt. 84 85oWith, CHC, N 4, 1990, pages 453 454).

The method of obtaining esters of carboxylic acids of General formula

< / BR>
where R is lower alkyl, phenyl, neo the group;

R1C1-C4-alkyl;

including processing alkyl halide in the environment of an organic solvent, characterized in that the aldehyde of General formula RC(O)H, where R has the above meanings, is subjected to treatment with sodium peroxide in the environment of N,N-dimethylformamide or N,N - dimethylacetamide at a temperature of 15 20oC followed by treatment of the resulting reaction mixture with carbon dioxide, and then alkyl halide of General formula R1X, where R1has the specified values, and X is a bromine atom, or iodine, at a temperature of 15 20oC for 24 h, and the process is carried out at a molar ratio of aldehyde peroxide sodium alkyl halide 1,0 1,0 1,1.

 

Same patents:

The invention relates to methods of producing optically active cyclobutanone the compounds of formula 1, where R3is a protective group

The invention relates to organic chemistry, specifically to a method for producing 2,6-directrories stabilizer (pentaerithrityl-[-(3,5-ditretbutyl-4 oksifenil)] -propionate), which can find application in the polymer industry and agriculture

The invention relates to a derivative of acrylic acid, useful in agriculture and, in particular, suitable for use as fungicides, insecticides or plant growth regulators

The invention relates to methods of producing esters of aryl-substituted propionic acid with high yield and in a short period of time

The invention relates to catalytic organic chemistry and can find application in the pharmaceutical industry to obtain the drug "Validol", which is a 25-30% solution of menthol in mentilovom broadcast isovalerianic acid (1)

The invention relates to the field of esters of unsaturated acids, particularly to a method of obtaining alilovic esters of 3,3-dimethylpentan-4-OIC acid of General formula

CH2=CHC(CH3)2CH2CO2R (1), where R is alkyl WITH1-C2

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to chlorine-containing polymeric composition that can be sued in manufacturing rigid, semi-rigid and soft materials. Method is carried out by interaction of alpha-branched saturated monocarboxylic acids of (C10-C28)-fraction with polyhydric alcohol at 180-230°C in the mole ratio = 1:(1-2) in the presence of metal oxides and their bi- and tri-component mixtures in the mass ratio MgO : CaO (or ZnO, BaO, CdO, PbO) = (0.25-1):(0.5-1) and MgO : CaO : ZnO (or BaO, CdO) = (0.5-1):(0.5-1), respectively, taken in the amount 0.5-2.0 wt.-% of the total reaction mass and without additional stages of neutralization, washing out, clearing and drying the prepared product. Ethylene glycol, glycerol, polyglycerol-vat residue after the glycerol distillation process can be used as a polyatomic alcohol. Invention provides preparing effective lubricants showing additional thermostabilizing capacity by ecologically safety technology, and expanding assortment of additives for polymeric articles also.

EFFECT: improved preparing method.

2 cl, 4 tbl, 32 ex

FIELD: chemistry.

SUBSTANCE: invention concerns lubricants for polyvinylchloride compositions which can be applied in production of rigid, semirigid and soft materials. Metal-containing lubricants are obtained in a single stage by interaction of oleic or stearic acid with glycerin at mol ratio of 1:1 in the presence of zinc or magnesium oxide or their mix at 0.25-1:0.25-1 mass ratio, in amount of 0.5-2.0 wt % of the total reaction mass, at 130-160°C for 4-5 hours. Process is performed until acid value of reaction mass is under 10 mg of KOH/g.

EFFECT: simple, cost-effective method with increased output of target product, reduced temperature and duration of synthesis; lubricant for polyvinylchloride ensures good melt fluidity and high heat resistance of polymer composition due to the presence of zinc and magnesium carboxylates in lubricant composition.

3 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing esters through etherification of a mixture of mono- and dicarboxylic acids C2-C6 (containing 53 to 60% adipic acid), obtained from evaporating acid waste water from caprolactam production, on acid catalysts in the presence of a third component (benzol) at temperature ranging from 80 to 90°C until release of water stops completely, with subsequent neutralisation of the catalyst and unreacted acid, washing with water from the formed salts, separation of the organic layer from water, extraction of the product through distillation, consisting of a distillate of the benzol fraction, distillate of the alcohol fraction, vacuum distillation of highly volatile esters, thereby obtaining a product as vat, where the etherifying agent used is cyclohexyl alcohol (at least 99.8% purity) or an alcohol fraction which contains 70 to 75% mixture of amyl, isoamyl and cyclohexyl alcohols, also a waste product from caprolactam production. The desired product, which is a mixture of esters, has good plasticising properties, flash point≥185°C; can be used as plasticiser for PVC compositions, rubber products in place of EDOS (3rd class of hazard) and dioctylphthalate (3rd class of hazard dioctylphthalate).

EFFECT: considerably low cost price, 4th class of hazard.

1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to synthesis of esters from the alcohol fraction of caprolactam. The method of producing esters from caprolactam production wastes is realised via esterification of organic acid and alcohol in autocatalytic heat release conditions which support the esterification reaction at temperature 40-130°C using a catalyst in form of cation-exchange resin which is pre-treated with sulphuric acid in amount of 0.4-2 wt % of the weight of the loaded material with cooling down of the reaction mixture before separating the two phases.

EFFECT: high efficiency of the method.

2 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing esters of (C15-C22) fatty acids and (C1-C5) aliphatic alcohols, used as viscosity regulators for polyvinyl chloride compositions and industrial rubber articles. The method is characterised by that said compounds are obtained through re-esterification of a mixture of glycerine esters of C15-C22 fatty acids contained in renewable plant material with C1-C5 alcohols in molar ratio of oil to alcohol equal to 1:5, on alkaline catalysts, at temperature limited by the boiling point of alcohol, separating glycerine and then vacuum distillation, with output 95-98% of theoretical output with 95% oil conversion in 3 hours.

EFFECT: improved method.

1 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry and particularly to a method of producing (2E,4E)-dodeca-2,4-diene-1-ylisovalerate, involving hydroalumination-halogenation of 1-nonyne to obtain (1E)-1-halogennon-1-ene, cross-coupling (1E)-1-halogennon-1-ene with methyl acrylate to obtain methyl ether of (2E,4E)-dodeca-2,4-dienic acid, reducing methyl ether of (2E,4E)-dodeca-2,4-dienic acid with lithium aluminium hydride to obtain (2E,4E)-dodeca-2,4-diene-1-ol, acylating (2E,4E)-dodeca-2,4-dien-1-ol with an acyl chloride of isovaleric acid to obtain (2E,4E)-dodeca-2,4-dien-1-ylisovalerate, where synthesis of methyl ether of (2E,4E)-dodeca-2,4-dienic acid is carried out in by reacting (1E)-1-iodonon-1-ene, which is obtained by hydroalumination-iodination of 1-nonyne, with methyl acrylate in the presence of Pd(OAc)2, K2CO3, Bu4NCl in the medium of N-methyl pyrrolidone with the following molar ratio [(1E)-1-iodonon-1-ene] : [methyl acrylate] : [Pd(OAc)2] : [K2CO3] : [Bu4NCl] : [N-methyl pyrrolidone] = 1:2: 0.02 : 2.5 : 1 : 5.5 for 8 hours in the atmosphere of argon at 18-25°C.

EFFECT: method has the following advantages: higher output of (2E,4E)-dodeca-2,4-dien-1-ylisovalarate, and conducting the cross-coupling reaction without heating at 18-25°C prevents isomerisation of the (2E,4E)-diene system and increases stereochemical purity of the product.

4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an acid addition salt of a compound of formula (1), formed by L-lactic acid. The compound (1) can be used as a Hsp90 inhibitor. Described are methods of producing a compound of formula (1), intermediate compounds used to produce a compound of formula (1) and methods of producing the intermediate compounds.

EFFECT: obtaining an acid addition salt of a compound of formula (1), formed by L-lactic acid.

10 cl, 22 dwg, 4 dwg, 22 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: claimed are compounds of general formula I , where values of radicals are given in description, possessing inhibiting action on sodium-dependent cotransporter of glucose SGLT. Present invention also claims pharmaceutical compositions, possessing inhibiting effect with respect to SGLT, and methods of obtaining said compounds and synthetic intermediates, as well as methods of obtaining said compounds per se or in combination with other therapeutic agents for treatment of diseases or states, subjected to impact of SGLT inhibition, for instance such disease as type 1 and 2 diabetes mellitus, hyperglucemia, diabetic complications, insulin resistance, metabolic syndrome, hyperinsulinemia, hypertension, hyperuricemia, obesity, edemas, dislipidemia, chronic heart failure and atherosclerosis.

EFFECT: increasing efficiency of application of derivatives.

21 cl, 23 ex, 1 tbl, 8 dwg

FIELD: food industry.

SUBSTANCE: composition is concentrated in terms of compound ethers of pinosylvine and produced by way of crude tall oil distillation or evaporation; the compound ethers acidic residue is formed by linoleic, linolenic, oleic acid or tricyclic, aliphatic or aromatic carboxylic acid. Stilbenes are extracted from the crude tall oil distillation or evaporation fraction containing stilbenes compound ethers; the fraction is concentrated. Then the stilbenes compound ethers are modified into the desired stilbenes by way of stilbenes compound ethers separation from their compound ether group. The crude tall oil distillation or evaporation fractions contain pinosylvine or its compound ethers in an amount of 5 - 95 % of the total weight of the composition.

EFFECT: invention relates to fat-and-oil industry, in particular, to a composition suitable for stilbenes production, to its production method, to a method for extraction of stilbenes from crude tall oil, to a compound ether of resin acid and pinosylvine or to its simple monomethyl ether.

26 cl, 1 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a surfactant, containing 1-2 residues of 1,3-cyclopentanediil directly connected or separated with hydrocarbon chains containing 0-20 methylene groups, wherein the said surfactant is characterised by a general formula, where m is integer from 2 to 20; n and k independently denote integers from 0 to 20; total (m + n + k) is an integer ranging from 5 to 20 inclusively; and a equals to 0 or 1; and p is a polar group.

EFFECT: these surfactants are characterised by a wide operating temperature range and allow using in aggressive media without risks to environmental safety.

1 cl, 1 tbl, 58 ex, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to derivatives of 3-aminocaprolactam of formula (I): , where X represents -CO-R1 or -SO2-R2, R1 represents alkyl (with the exception of 5-methylheptanyl and 6-methylheptanyl, where radical R1 is bonded to carbonyl in position 1), halogenalkyl, alkoxy (with the exception of tret-butyloxy), alkenyl, alkinyl or alkylamino radical from 4-20 carbon atoms (for example, from 5-20 carbon atoms, 8-20 carbon atoms, 9-20 carbon atoms, 10-18 carbon atoms, 12-18 carbon atoms, 13-18 carbon atoms, 14-18 carbon atoms, 13-17 carbon atoms) and R2 is alkyl radical from 4-20 carbon atoms (for example, from 5-20 carbon atoms, 8-20 carbon atoms, 9-20 carbon atoms, 10-18 carbon atoms, 12-18 carbon atoms, 13-18 carbon atoms, 14-18 carbon atoms, 13-17 carbon atoms); or to its pharmacologically acceptable salt. Invention also relates to application and pharmacological composition, which has anti-inflammatory activity, based on said compounds.

EFFECT: obtaining new compounds and based on them pharmacological composition, which can be applied for obtaining medications for treatment, relief or prevention of inflammatory disease symptoms.

57 cl, 62 ex

FIELD: chemistry.

SUBSTANCE: method of alkyl ester obtainment involves, for instance: mixing of triglyceride-containing oil source with primary alcohol or secondary alcohol in organic solvent to obtain a solution; where each organic solvent molecule includes 4-8 carbon atoms and heteroatom; triglyceride reaction with primary alcohol or secondary alcohol in the presence of lipase immobilised on a carrier, to obtain alkyl ester, where solution does not undergo phase separation in the course of reaction, and glycerin is produced as a by-product; and obtainment of alkyl ester by phase separation in alkyl ester and glycerin after extraction of organic solvent and unreacted primary or secondary alcohol by condensation.

EFFECT: obtainment of mix with high content of high-purity alkyl esters.

46 cl, 8 ex

Up!