Method of producing low-molecular substituted phenylbenzoates

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing low-molecular substituted phenylbenzoates of general formula: , where R1=C3H7O-, C7H15O-, C8H17O-, C7H|5-, R2=-CHO, -CN, -C3H7, X=H-, HO-, through condensation of an acyl chloride of benzoic acid and substituted phenol in a solvent and subsequent separation of the end product, the acyl chloride of benzoic acid used being a compound of formula: , where R1=C3H7O-, C7H15O-, C8H17O-, C7H15-, the substituted phenol used is a compound of formula: , where R2=-CHO, -CN, -C3H7, X=H-, HO-, the solvent used is methylene chloride; condensation is carried out in the presence of triethylamie while exposing the reaction solution to ultrasound at frequency of 25-30 kHz for 1-1.5 hours at room temperature. The end product is obtained with such high purity that it can be used to modify polymer materials without purification. Recrystallisation from ethanol is sufficient to purify the end product when used as a component of liquid crystal compositions.

EFFECT: invention has the following advantages: 3-5 times shorter duration of the condensation process; 1,6 times increase in output of the product; avoiding preparatory operations associated with absolutisation of pyridine; considerably shorter duration and labour input in purification.

1 tbl, 13 ex

 

The invention relates to the field of organic chemistry, namely to obtain low molecular weight substituted phenylbenzoates General formula:

where R1=C3H7O-, C7H15O-, C8H17O-, C7H15-, R2=-CHO, -CN, -C3H7X=H-, HO-.

These compounds can be used for modification of polymer materials and their processing with the purpose of increasing their strength characteristics; as stationary phases in gas-liquid chromatography for the separation of positional isomers of various organic substances; as components of liquid crystal compositions used in devices based on electro-optic effects; for further chemical modification with the aim of obtaining new potentially mesogenic compounds.

The level of technology

Low molecular weight substituted phenylbenzoate due to their specific properties are promising for the practical application of the compounds. Derivatives of phenylbenzoates with chemically active substituents are effective stabilizers of polyethylene and polyvinyl chloride. These compounds are well combined with the molecules of the polymer and protect the material from damage when exposed to high temperatures and UV radiation.

Interest is replaced by phenylbenzoate is m, exhibiting liquid crystalline properties, is determined by the possibility of their use in gas-liquid chromatography for solving a variety of analytical tasks and, above all, the spatial separation of the various isomers of organic substances. Liquid crystal mixtures based phenylbenzoate are of interest for use in means of information display, since they are characterized by a wide interval of existence mesophases, low viscosity and high dielectric anisotropy.

Well-known different ways to obtain low molecular weight substituted phenylbenzoates.

A method of obtaining 4-hydroxyphenyl-4'-alkoxybenzenes, including condensation of acid chlorides 4-alkoxybenzyl acid and hydroquinone in absolute pyridine at room temperature for 42 hours, the selection of target products ice water and filtered, cleaned by first washing soda solution, then three times with distilled water and twice by recrystallization from ethanol. The yield of the target products 75-80% [Maut, Schroeder D.., Schroeder J. - P. J. J. Org. Chem.,V.37, 1972, p.1425-1428].

A method of obtaining 4,4'-substituted of phenylbenzoates, including condensation of acid chlorides 4-substituted benzoic acid and 4-substituted phenols in absolute pyridine at first for 24 hours at 0°C, then for 30 minutes is at 70°C, the selection of target products by distillation of the pyridine under reduced pressure, purification of the target product first two column chromatography on silica gel (eluent ether-chloroform or hexane-chloroform) and then by recrystallization from ethanol [D. Coates, G.W.Grey. Mol. Cryst. Liq. Cryst, 1976, V.37, p.249-262].

A method of obtaining 4-alkyl-4'-cyanophenylacetic, including condensation of acid chlorides 4-alkylbenzoic acid and 4-cyanophenyl in absolute pyridine at room temperature for 24 hours, the selection of target products ice water, filtering, cleaning target phenylbenzoate column chromatography and recrystallization from methanol. A yield of about 60% [Jan W. Baran et al. Biuletyn Wojskowej Akademii Technicznej im. J. Dabrowskiego, Rok XXVIII, nr 9(325), 1979, p.69-80).

A method of obtaining substituted phenylbenzoates, including condensation of acid chlorides substituted biphenylcarbonic acid and 4-cyanophora in absolute benzene in the presence of triethylamine for 12 hours at boiling temperature, the selection of target products by diluting the reaction mixture with water, separating the organic layer and distillation of the solvent. For purification of the target products twice recrystallized from a mixture of etelaat with petroleum ether, then stirred for 12 hours in benzene or ethyl acetate at room temperature in the presence of hexamethylditin the curtain, the solvent is distilled off and the product is recrystallized from a mixture of ethyl acetate and petroleum ether [US Patent 4,162,988. Maze, et al., July 31, 1979].

A method of obtaining 4-formylphenyl-4'-nonyloxy - and 4'-underoccupation, including condensation of acid chlorides 4-nonyl - or 4-undecalactone acid and 4-oxybenzaldehyde in absolute pyridine at 100°C for 6 hours, the selection of target products ice water followed by filtration and purification by double recrystallization from ethanol [Kuvshinova S.A. and other Liquid crystals and their practical use, 2008, issue 3(25), pp.5-12].

The closest creature to the invention, i.e. the prototype, is a method of obtaining 4-formylphenyl-4'-hexyloxybenzoic by condensation of the acid chloride of benzoic acid and substituted phenol in the solvent and subsequent selection of the target product. As the acid chloride of benzoic acid using acid chloride 4-hexyloxybenzoic acid, as substituted phenol used 4-formylphenol, in the solvent used absolute pyridine, the condensation is carried out at 100°C for 5 hours. The target product was then purified by recrystallization from ethanol and column chromatography on alumina (eluent - chloroform). The yield of the target product is 60%. [Alexandria CENTURIES and others]. higher education institutions. Chemistry and chem. technology., 2002,Vol.45, No. 2, p.14-16].

However, this method has the following disadvantages:

1. A significant duration of the condensation process is not less than 5 hours.

2. Not a high yield of the target product is not more than 60%.

3. Significant complexity and duration of the preparatory operations, necessitated by the use of absolute pyridine. For the absolute pyridine his first dry potassium hydroxide in 2-5 days, and then distilled under reduced pressure.

4. The duration and complexity of treatment, because in the process of condensation is allocated hydrogen chloride, contributing to the formation of by-products and hydrochloric acid, and the staining of the target products. All this leads to the fact that the cleaning stage, including chromatography was carried out on a column of alumina or silica gel, the Stripping of the solvent and a double recrystallization takes 6-8 days. High complexity due to the Assembly of the installation for the distillation of the solvents, the preparation of chromatographic columns and replacement of alumina or silica gel columns after chromatography was carried out each portion of the product.

The invention

Inventive task was to find a way to obtain low molecular weight substituted phenylbenzoates General formula

where R1=C3H 7O-, C7H15O-, C8H17O-, C7H15-, R2=-CHO, -CN, -C3H7X=H-, HO-, by condensation of the acid chloride of benzoic acid and substituted phenol in the solvent and subsequent selection of the target product, which would reduce the duration and intensity of the process and increase the yield of the target product.

This goal is achieved by a method of obtaining low molecular weight substituted phenylbenzoates General formula

,

where R1=C3H7O-, C7H15O-, C8H17O-, C7H15-, R2=-CHO, -CN, -C3H7X=H-, HO-, by condensation of the acid chloride of benzoic acid and substituted phenol in the solvent and subsequent selection of the target product, in which the acid chloride of benzoic acid using the compounds of formula

,

where R1=C3H7O-, C7H15O-, C8H17O-, C7H15-as substituted phenol using the compounds of formula

where R2=-CHO, -CN, -C3H7X=H-, HO-, in the solvent used methylene chloride, condensation is carried out in the presence of triethylamine under simultaneous exposure to the reaction solution of ultrasound with a frequency of 25-30 kHz for 1-1,5 hours is ri room temperature.

The purity of the target product is 99% and can be used without purification. If you want a higher purity of the target product, only one recrystallization from ethanol.

The invention provides the following advantages:

1. 3-5 times to reduce the duration of the condensation process.

2. 1.6 times to increase output.

3. To exclude preparatory operations associated with the absolutization of pyridine, and the dehydration of potassium hydroxide and distilled under reduced pressure. In the claimed method in the solvent used methylene chloride, which does not require absolutism.

4. Significantly reduce the duration and complexity of treatment. The target product is obtained such high purity that for the modification of polymeric materials can be used without purification. When using the target product as components of liquid crystal compositions for cleaning, one recrystallization from ethanol.

Information verifying the playback inventions

To implement the method using the following ingredients:

1. Methylene chloride GOST 8728-88

2. The triethylamine TU 6-09-1496-77

3. Ethanol GOST 5964-93

4. 4-formylphenol THE 6-09-15-343-78

5. 4-propylacetophenone acid THAT 6-09-4435-77

6. 4-heptyloxybenzoic acid THAT 6-09-4393-77

. 4-octyloxybenzoic acid THAT 6-09-4441-77

8. Thionyl chloride Fluka, Lot &Filling code: 1122903 13904042

9. 2,4-dioxybenzene ALDRICH CAS 95-01-2, Pcode 101030221, Lot #STBB2079V

10. 4-propilene THE 150-292-88

11. 4-heptylbenzoic acid ABCR GmbH & Co. [38350-87-7] lot 1116849 AB 131521

12. 4-cyanoprop synthesized by the known method [Copyright certificate NRB, CL SS 121/52, No. 26591, Appl. 31.03.78, No. 39249, publ. 26.05.79.

Chloranhydride beiting acid was obtained in a known manner [Jan W. Baran et al. Biuletyn Wojskowej Akademii Technicznej im. J. Dabrowskiego, Rok XXVIII, nr 9(325), 1979, p.69-80).

The method is as follows.

Equimolar amounts of the acid chloride of benzoic acid, substituted phenol and triethylamine dissolved in methylene chloride and stirred at room temperature for 1.0-1.5 hours when exposed to the reaction mixture ultrasound with a frequency of 25-30 kHz. Then the reaction mixture is washed with water, the organic layer is separated, the methylene chloride is distilled off. If necessary, the product is recrystallized from ethanol.

Identification of target products were performed using elemental analysis, IR spectroscopy and NMR.

The yields of the target products derived the claimed method with different parameters of its implementation given in the table.

-CHO
The yields of target products
№ p/pR1R2xOptionsOutput (%)
The ultrasound frequency, kHzProcessing time ultrasound hour.
1.C3H7O-CHOH251,095,8
2.C3H7O-CNH271,196,0
3.C7H15O-CHOH301,296,0
4.C7H15O-CNH261,396,4
5.C8H17OH291,496,2
6.C8H17O-CNH251,596,0
7.C3H7O-C3H7H301,596,1
8.C7H15O-C3H7H291,396,0
9.C8H17O-C3H7H261,495,9
10.C7H15-CNH301,396,4
11 C3H7O-CHOOH251,596,2
12.C7H15O-CHOOH271,096,0
13.C8H17O-CHOOH301,096,0

The method of obtaining low molecular weight substituted phenylbenzoates General formula:

where R1- C3H7O-, C7H15Oh, C8H17O-, C7H15-, R2Is-CHO, -CN, -C3H7X - N-, BUT-, by condensation of the acid chloride of benzoic acid and substituted phenol in the solvent and subsequent selection of the target product, characterized in that as the acid chloride of benzoic acid using the compounds of formula:

where R1- C3H7O-, C7H15O-, C8H17O-, C7H15-as substituted phenol used connection forms the crystals:

where R2Is-CHO, -CN, -C3H7, X - N, BUT, as a solvent used methylene chloride, condensation is carried out in the presence of triethylamine under simultaneous exposure to the reaction solution of ultrasound with a frequency of 25-30 kHz for 1-1 .5 h at room temperature.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention concerns a mix of isomer iso-nonyl ethers of benzoic acid, intended as polymer plastification agents and obtained by benzoic acid etherisation by nonyl alcohols or re-etherisation of one or more alkyl benzoic acid ethers with 1-8 carbon atoms in alkyl residues by nonyl alcohols, the latter containing less than 10 mol % of 3,5,5-trimethylhexanol; a mix intended as polymer plastification agents and containing 1-99 wt % of isomer iso-nonyl ethers of benzoic acid and 1-99 wt % of dialkyl phthalic acid ethers with alkyl residues containing 4-13 carbon atoms, isomer iso-nonyl ethers of benzoic acid obtained by benzoic acid etherisation by nonyl alcohols or re-etherisation of one or more alkyl benzoic acid ethers with 1-8 carbon atoms in alkyl residues by nonyl alcohols, the latter containing less than 10 mol % of 3,5,5-trimethylhexanol; a mix intended as polymer plastification agents and containing 1-99 wt % of isomer iso-nonyl ethers of benzoic acid and 1-99 wt % of alkyl adipine acid ethers with alkyl residues containing 4-13 carbon atoms, isomer iso-nonyl ethers of benzoic acid obtained by benzoic acid etherisation by nonyl alcohols or re-etherisation of one or more alkyl benzoic acid ethers with 1-8 carbon atoms in alkyl residues by nonyl alcohols, the latter containing less than 10 mol % of 3,5,5-trimethylhexanol; a mix intended as polymer plastification agents and containing 1-99 wt % of isomer iso-nonyl ethers of benzoic acid and 1-99 wt % of alkyl cyclohexanedicarboxylic acid ethers with alkyl residues containing 4-13 carbon atoms, isomer iso-nonyl ethers of benzoic acid obtained by benzoic acid etherisation by nonyl alcohols or re-etherisation of one or more alkyl benzoic acid ethers with 1-8 carbon atoms in alkyl residues by nonyl alcohols, the latter containing less than 10 mol % of 3,5,5-trimethylhexanol.

EFFECT: application of mixes as plastification agents in polyvinylchloride and PVC plastisols.

12 cl, 1 dwg, 6 tbl, 8 ex

FIELD: organic chemistry, perfumery.

SUBSTANCE: invention relates to an aromatizing composition containing at least compound of the formula (I): as an active component wherein values w, m, P, X, G, Q and n are given in claim 1 of the invention description, and one or more aromatizing component. Also, invention relates to a method for improving, enhancing or modifying odor, to a method for aromatizing surface, method for enhancing or prolonging the diffusion effect of component on surface and to novel compounds of the formula (I) with exception of compounds enumerated in claim 10 of the invention description and to invention relating to aromatizing article using compounds of the formula (I).

EFFECT: valuable cosmetic properties of compounds.

13 cl, 14 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new derivatives of glucopyranosyloxybenzylbenzene represented by the formula (I): wherein R1 represents hydrogen atom or hydroxy(lower)alkyl; R2 represents lower alkyl group, lower alkoxy-group and lower alkylthio-group being each group is substituted optionally with hydroxy- or (lower)alkoxy-group, or to its pharmaceutically acceptable salts. Also, invention relates to pharmaceutical composition eliciting hypoglycemic activity and to a method for treatment and prophylaxis of hyperglycemia-associated diseases, such as diabetes mellitus, obesity and others, and to their intermediate compounds. Invention provides preparing new derivatives of glucopyranosyloxybenzylbenzene that elicit the excellent inhibitory activity with respect to human SGLT2.

EFFECT: valuable medicinal properties of compounds.

13 cl, 2 tbl, 2 ex

The invention relates to an improved process for the preparation of esters of carboxylic acids of General formula (I) esterification of the corresponding acids or anhydrides with alcohols in a molar ratio acid:ethanol=1: 0.35 to 2.2 in the presence of hydrocarbons as solvent and aromatic sulfonic acids or acidic sulfate as a catalyst at the boiling temperature of the reaction mixture by distillation of the formed water, followed by washing of the reaction mixture and neutralizing it with an alkaline solution, taken from 5-20 wt

The invention relates to the synthesis of biologically active chemical compounds and can be implemented in pharmacology, medicine and agriculture

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

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

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

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

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

The invention relates to a method for producing (nitroxymethyl)phenyl esters of derivatives of salicylic acid of the formula (I)

where R1means OCOR3group, where R3means methyl, ethyl or a linear or branched C3-C5alkyl;R2means hydrogen

The invention relates to an improved process for the preparation of acrylates and methacrylates tertiary alcohols adamantanol number used as starting compounds for polymeric materials for 193 nm laser microlithography in the manufacture of semiconductor devices

The invention relates to the synthesis of biologically active chemical compounds and can be implemented in pharmacology, medicine and agriculture

- bromsulfaleinovy acid" target="_blank">

The invention relates to the field of organic and petrochemical synthesis, namely, to obtain ethyl ester-bromsulfaleinovy acid (EEBIC), used in the manufacture of drugs, such as Corvalol, valocordin

The invention relates to the production of alilovic esters dichloracetic acid, and more particularly to methods of producing methyl ester dichloracetic acid
The invention relates to organic chemistry, specifically to methods of producing 2-hydroxy-4-(meth)acryloylmorpholine (OMF or OABF)

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to amide of δ-amino-γ-hydroxy-ω-arylalcane acid of formula and its pharmaceutically acceptable salts. Also described are pharmaceutical compositions, which include said compounds, and application of said compounds for preparation of medication, intended for treatment of pathological states, associated with renin activity, in particular for treatment of hypertension.

EFFECT: obtaining pharmaceutically acceptable salts, which possess rennin-inhibiting ability.

21 cl, 161 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of tetrafluorobenzonitrile of the formula (2): Method involves hydrogenolysis of a single cyano-group of tetrafluorodicyanobenzene of the formula (I): by effect of hydrogen at temperature above 100°C in the presence of the hydrodecyanidation catalyst of platinum group and synthetic zeolite. Invention shows economy profit in the industrial aspect of method for synthesis of tetrafluorobenzonitrile that can be used as agrochemical and medicinal intermediate compound.

EFFECT: improved method of synthesis.

7 cl, 13 ex

Up!