The way to obtain 9-(4-methoxy-2,3,6-trimetilfenil)-3,7 - dimethyl-2e,4e,6e,8e-nonatetraenovoy acid

 

(57) Abstract:

The inventive product - 9-(4-methoxy-D-trimetilfenil)-3,7-dimethyl-2E. 4E, 6E, 8E-noniterative acid, so PP 228-230° C. the yield 88.5% Reagent 1 : 2. 3, 5-trimethylphenol Reagent 2: methyl iodide reaction Conditions: in aqueous-alcoholic solution of KOH, followed by formirovanie formed 2.3, 5-trimethylamine to obtain 4-methoxy-2,3,6-trimethylbenzaldehyde. condensation of this aldehyde with acetone with the formation of 4-(4-methoxy-2, 3, 6-trimetilfenil)-3-butene-2-it is the hydrogenation of the latter with hydrogen in the presence of skeletal Nickel catalyst by itinerarium obtained 4-(4-methoxy-2. 3, 6-trimethylphenyl-butane-2-she acetylene in liquid ammonia in the presence of an alcoholic solution of caustic potash, obtained by condensation of acetylene carbinol with metaliterary ether in the presence of an acid catalyst, protoparmelia acid, followed by treatment of the reaction mixture with a water-alcohol solution of alkali with the formation of 8-{4-methoxy-2, 3. 6-trimetilfenil)-6-methyl-25-octadien-2-it, by condensation of the latter with isobutyl ether monochloracetic acid in the presence of isobutyrate potassium and further treatment of the reaction mixture sometim phosphorus and dehydrobrominated intermediate derived directly in the reaction mass dimethylacetamide. further saponification is obtained isobutyl ester of 9-{4-methoxy-2,3.b-trimetilfenil)-3.7-Dimethyl-2E. 4E, 6E 8E-nonteratogenic §

 

Same patents:

FIELD: organic chemistry.

SUBSTANCE: invention relates to improve method for production of trans-alkyl-substituted cyclohexanecarboxylic acids of general formula 1 , wherein R is C1-C10-alkyl and trans-4-(C1-C10-alkyl)cyclohexyl radical, by hydration of respective 4-alkyl-substituted benzoic acids. In aqueous-alkali solution at elevated temperature and elevated hydrogen pressure of 0.5-15 MPa in presence of catalyst followed by isomerization at 200-400°C and isolation of reaction products by mixture acidifying. As catalyst ruthenium-nickel catalyst on carbon carrier is used, wherein catalyst contains 5 mass % of metal calculated as total catalyst mass and Ni/Ru mass ratio is (0.01-1.5):(8.5-9.99). Process is carried out at 20-150°C for 0.25-1 h, and isomerization is carried out in inert gas atmosphere in several steps after mixture filtration to separate catalyst. Compounds of present invention represent value products in production of liquid crystal materials and biologically active materials.

EFFECT: accelerated process with reduced cost and increased effectiveness.

1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to improved method of salicylates of alkaline earth metals for application as detergents for lubricating materials. Method of obtaining alkylated salicytates of alkaline earth metals includes following stages: A) alkylating salicylic acid with linear α-olefin, containing, at last, 14 carbon atoms, in presence of water-free methane sulfonic acid with formation of oil-soluble alkylated salicylic acid; B) neutralisation of oil-soluble alkylated salicylic acid; C) excessive alkalisation of oil-soluble alkylated salicylic acid by carboxylating lime by means of CO2 in presence of oxygen-containing organic solvent and surface-active substance; D) filtration of stage (C) product; and E) removal of solvent by distillation. Alternatively, alkylsalicylic acid can be subjected to interaction with preliminary processed with alkali highly-alkaline sulfonate of earth alkaline metal, for instance, with calcium sulfonate, in order to obtain salicylate salts of earth alkaline metals with different per cent content of dispersed salts of alkaline earth metals carbonates. In claimed method it is not necessary to filter end product which is preferable doe industry.

EFFECT: obtaining salicylates of alkaline earth metals for application as detergents for lubricating materials.

8 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing α-hydroxycarboxylic acids, particularly a novel method of producing 2-hydroxy-carboxyalkyladamantanes of general formula where R=H, CH3, which can be used as intermediate products in synthesis of adamantyl-containing amino acids and heterocyclic compounds. The method includes reacting adamantanone-2 with dilithium salts of acetic or propionic acid, obtained in situ by reacting lithium acetate or propionate with lithium hexamethyldisilylamide, obtained beforehand from hexamethyldisilazane and phenyllithium, in the medium of dry tetrahydrofuran at 20-45°C and molar ratio hexamethyldisilazane: lithium acetate or propionate: adamantanone-2 of 1.3-1.4:1.8-2.1:1.

EFFECT: wider range of compounds of the disclosed structural formula and obtaining products with high output and high degree of purity.

2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining highly fluorinated carboxylic acids and their salts, as well as substances-precursors, which includes an impact on a highly fluorinated olefin, which has the general formula (I): Rf-(O)n-(CF2)m-CF=CF2 of a formic acid derivative in accordance with the general formula (II): HCOR in the presence of a radical initiator to form a substance-precursor of carboxylic acid in the form of O-ethers, S-ethers or an amide adduct of the general formula (III): Rf-(O)n-(CF2)m-CFH-CF2-COO and, optionally, in case of an acid obtaining, hydrolysis of an adduct of formula (III) to form carboxylic acid or its salts with the general formula (IV): Rf-(O)n-(CF2)m-CFH-CF2-COO-M+, where in formulas (II) and (III) R represents a residue O-M+, S-M+, OR' or SR' or NR'R", where R' and R" are independent on each other linear or branched or cyclic aliphatic residues, which contain at least one carbon atom and which do not have an alpha-H-atom, where the alpha-H-atom represents a hydrogen atom, bond with a carbon atom, bound with O, S or N in groups OR', SR' or NR'R", and where in formulas (I), (III), (IV) Rf represents H, either a perfluorinated or fluorinated linear or branched alkyl residue which can contain one or several catenary oxygen atoms, and n constitutes 1 or 0, m represents a number from 0 to 6, and M+ represents a cation.

EFFECT: method makes it possible to obtain target compounds with the high output.

8 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for the reaction of formaldehyde or a suitable source thereof with a carboxylic acid or ester to produce an ethylenically unsaturated carboxylic acid or ester, preferably an α,β-position ethylenically unsaturated carboxylic acid or ester, where the catalyst includes a metal oxide having at least two types of metal cations, M1 and M2, where M1 is at least one metal selected from group 3 or 4 in the 4th to 6th periods of the periodic table, group 13 in the 3rd to 5th periods of the periodic table, or the remaining elements in the lanthanide series, namely scandium, yttrium, lanthanide elements, titanium, zirconium, hafnium, aluminium, gallium, indium, and M2 is at least one metal selected from group 5 in the 5th or 6th periods of the periodic table or group 15 in the 4th or 5th periods of the periodic table, namely niobium, tantalum, arsenic and antimony, wherein the ratio of M1:M2 is in the range of 5:1 to 1:5 and wherein the metal oxide based catalyst compound according to the invention does not include other types of metals above the 0.1 mol% level, different from M1, M2 and, optionally, M3 and/or M4. The present invention also relates to the method of producing an ethylenically unsaturated carboxylic acid or ester and to the use of the catalyst (versions).

EFFECT: obtaining the catalyst which provides high catalytic activity in the reaction of formaldehyde or a suitable source thereof with a carboxylic acid or ester to obtain ethylenically unsaturated carboxylic acids or esters.

33 cl, 13 ex, 6 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to method for obtaining α, β ethylene-unsaturated carboxylic acids or esters, which contains stages, where induced is contact of formaldehyde or its suitable source with carboxylic acid or ester of formula R3-CH2-COOR4, where R4 stands for hydrogen or alkyl group, and R3 stands for hydrogen, alkyl or aryl group, in presence of catalyst and possibly in presence of alcohol, where said catalyst contains nitrided metal oxide, which has, at least, two types of cations of metals M1 and M2, where M1 is selected from metals or metalloids of groups 3, 4, 13 (also called IIIA) or 14 (also called IVA) of Periodic table, with M2 being selected from metals metalloids or phosphorus of group 5 or 15 (also called VA) of Periodic table. The invention also relates to catalytic system for reaction of formaldehyde or its suitable source with carboxylic acid or ester of formula R3-CH2-COOR4, where R4 stands for hydrogen or alkyl group, and R3 stands for hydrogen, alkyl or aryl group, optionally in presence of alcohol, with obtaining α, β ethylene-unsaturated carboxylic acids or esters, where said catalyst contains nitride metal oxide, which has, at least, two types of cations of metals M1 and M2, where M1 is selected from, at least, two metals or metalloids of group 2, 3, 4, 13 (also called IIIA), 14 (also called IVA) of Periodic table, with M2 being selected from, at least, one metal of group 5 or, at least, one metal or metalloid of group 15 (also called VA) in 4th-6th of Periodic table.

EFFECT: obtaining target products with high selectivity is achieved.

16 cl, 6 tbl, 22 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing acrylic acid from methanol and acetic acid, which involves following operations: through a first reaction zone A, which is loaded at least one oxidation catalyst A, passing a stream of reaction gas mixture A, containing reagents – methanol and molecular oxygen, as well as at least one inert gas diluent, different from water vapour, and when passing said reaction zone A methanol contained in supplied reaction gas mixture A, in conditions of heterogeneous catalysis is oxidised to formaldehyde and water vapour, so as to form a gaseous mixture of products A, containing formaldehyde, water vapour, at least one inert gas diluent, differing from water vapour, and optionally, excess molecular oxygen, and stream of gaseous mixture of products A exits reaction zone A, wherein to reaction gas mixture A passing through reaction zone A, on its path through reaction zone A can optionally be supplied additional molecular oxygen and/or additional inert gas diluent, optionally a stream of gaseous mixture of products A, leaving reaction zone A, is fed into separation zone T*, and in said separation zone T* from gaseous mixture of products A is optionally separated unreacted methanol still contained in gaseous mixture of products A, wherein remains gaseous mixture of products A*, containing formaldehyde, and a stream of gaseous mixture of products A* exits reaction zone A, from stream of gaseous mixture of products A or from stream of gaseous mixture of products A*, as well as at least one other stream of substances containing acetic acid, is obtained a stream of incoming reaction gas mixture B containing acetic acid, water vapour, at least one inert gas diluent, different from water vapour, formaldehyde and optionally molecular oxygen, in which is contained molar amount of acetic acid nHAc greater than molar amount of formaldehyde nFd contained therein, through second reaction zone B, in which is loaded at least one catalyst for aldol condensation B, is passed a stream of incoming reaction gas mixture B, and when passing said reaction zone B formaldehyde contained in supplied reaction gas mixture B, together with acetic acid contained in supplied reaction gas mixture B, under conditions of heterogeneous catalysis is condensed to acrylic acid and H2O, to form a gaseous mixture of products B containing acrylic acid, acetic acid, water vapour, at least one inert gas diluent, different from water vapour, and optionally molecular oxygen, and a stream of gaseous mixture of products B comes out of reaction zone B, wherein to reaction gas mixture B passing through reaction zone B, on its path through reaction zone B, may be supplied additional molecular oxygen and/or additional inert gas diluent, stream of gaseous mixture of products B, leaving reaction zone B is fed into separation zone T, and in said separation zone T is divided at least into three streams substances – X, Y and Z, wherein stream of acrylic acid contained in stream of substances X, is greater than stream of acrylic acid contained in streams of substances Y and Z, taken together, stream of acetic acid contained in stream of substances Y is greater than streams of acetic acid contained in streams of substances X and Z, taken together, stream of inert gas diluent, different from water vapour, contained in stream of substance Z, is greater than streams of inert gas diluent, different from water vapour contained in streams of substances X and Y taken together, and stream of substance Y is returned into reaction zone B and is additionally used for producing incoming reaction gas mixture B.

EFFECT: disclosed is a method of producing acrylic acid from methanol and acetic acid.

21 cl

FIELD: chemistry.

SUBSTANCE: invention relates to a process of preparing α ethylenically unsaturated β carboxylic acid or an ester thereof, comprising the steps of driving the formaldehyde contact or a usable source with a carboxylic acid or its ester in the presence of a catalyst and optionally in the presence of an alcohol, wherein the catalyst contains crystals of barium phosphate shaped leaf plates or similar sheets or plates, or a suitable source for use is capable of forming crystals in situ under the reaction conditions. The invention also relates to a catalyst system of the reaction of formaldehyde, or a suitable source for use with a carboxylic acid or an ester thereof to obtain α,β-ethylene-unsaturated carboxylic acid or an ester thereof containing a catalyst based on crystalline barium phosphate and, optionally, a catalyst carrier, wherein the barium phosphate is in the form of crystals having the form of leaves or plates similar to plates or leaves, or suitable for use source capable of forming crystals in situ under the reaction conditions.

EFFECT: high level of selectivity of the above reactions.

61 cl, 9 dwg, 1 tbl, 8 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to novel intermediate compounds and inmproved method for synthesis of compound of the formula (C): . Proposed method is based on using inexpensive parent substances and provides synthesis of intermediate compounds with the high yield and high purity degree being without carrying out procedures for chromatographic purification and can be realized in large-scale industry manufacture. Invention relates to improved methods for synthesis of compound of the formula (I): , compound of the formula (II): , compound of the formula (III): , compound of the formula (VIII): , compound of the formula (IX): , and to a reagent consisting of boron tribromide and 2,6-dimethylpyridine. Method is used for a sparing and selective splitting a methyl group in aromatic methyl ethers.

EFFECT: improved method of synthesis.

12 cl, 8 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to novel derivatives of carboxylic acid represented by the general formula (I): , their pharmaceutically acceptable salts or esters wherein values Y, L, X, T, Z, M, R1, W and are given in the invention claim. Proposed compounds possess insulin-sensitizing effect and they are double agonists with respect to PPARα and γ, and triple agonists with respect to PPARα, β(δ) and γ. Except for, the invention relates to a medicinal agent and pharmaceutical compositions based on the claimed derivatives of carboxylic acid, to methods for prophylaxis or treatment of diseases, and to using derivatives carboxylic acid for preparing a medicinal agent.

EFFECT: valuable medicinal properties of compounds and pharmaceutical compositions.

56 cl, 2 tbl, 609 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method for asymmetrical hydrogenation, catalysed by transition metals, acrylic acid derivatives of formula (I), in which R1 denotes H or optionally substituted C1-C20-alkyl, C5-C20-aryl or C5-C20-heteroryl radical, R2 denotes optionally substituted C1-C20-alkyl, C5-C20-aryl or C5-C20-heteroaryl radical, and R3 denotes H or C1-C6-alkyl radical, which involves hydrogenation of compounds of formula (I), optionally in a solvent, in the presence of one or more hydrogen donors, using a catalyst system which contains a transition metal selected from ruthenium, rhodium and iridium and a combination of a chiral phosphoric ligand of formula (II), in which Cn, together with two oxygen atoms and a phosphorus atom, form an optionally substituted ring, having 2-6 carbon atoms, and R4 denotes an optionally substituted alkyl, aryl, alkoxy- or aryloxy-radical or a NR5R6 group in which R5 and R6 can be independently hydrogen or optionally substituted alkyl, aryl, aralkyl or alkaryl radical, or together with a nitrogen atom can form a ring, and an achiral phosphinic ligand of formula (III), in which R is optionally substituted alkyl or aryl radical, to obtain corresponding compounds of formula (IV) in which each R1, R2 and R3 are as described above. Formula (I), Formula (II), Formula P(R)3 (III), Formula (IV).

EFFECT: improved method for asymmetrical hydrogenation.

20 cl, 3 tbl, 29 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to novel compounds of formula III or to its pharmaceutically acceptable salts, in which: R1 and R2 are independently selected from group, consisting of: (a) H, (b) (C2-C6)alkyl, (c) C1-C6 alkyl, interrupted by one or more groups -O-, (d) (C0-C3)alkyl-(C3-C7)cycloalkyl and (e) (CH2)nQ, where n=1-2 and where Q stands for aromatic ring system, which has from 5 to 6 ring atoms C, and Q can be independently substituted with groups up to 3 in number, selected from halogen, on condition that R1 and R2 simultaneously do not stand for H, and each alkyl of R1 and R2 can be independently substituted with one or more groups, selected from group, consisting of halogen, hydroxy, cyano, CF3 or C1-C4 alkyl, or R1 and R2 together with carbon, to which they are attached, form 3-7-member cycloalkyl or 6-member heterocycloalkyl ring, including one oxygen atom and which in case of necessity carries C1-C4 alkyl substituent, or R1 and R2 together with carbon, to which they are connected, form 3-7-member cycloalkyl ring, substituted with R20 and R21, and R20 and R21 together with carbon or carbons, to which they are connected, form 3-7-member cycloalkyl ring; R6 stands for C1-C6 alkyl; each R7 independently stands for C1-C6 alkyl; Y stands for -O-; R4 is selected from group, consisting of: (a) (C0-C3)alkyl-(C3-C7)cycloalkyl, (b) trifluoroethyl, and (c) trifluoropropyl; Z stands for phenyl or bicyclic ring system, which has 9 ring atoms, independently selected from C, N, O and S, on condition that not more than 3 ring atoms in any single ring differs from C, and said ring system can carry to 3 substituents, independently selected from group, consisting of R6, CF3 and SR6; and R5 is selected from group, consisting of NO2, NH2, F, Cl, Br, CN, SR6, S(O)2N(R7)2 and (C1-C4)alkyl, and each alkyl can be independently substituted with one or more halogens or CF3. Invention also relates to pharmaceutical composition for treatment of neurodegenerative disorder or improvement of cognitive function, containing therapeutically effective quantity of said compound; as well as to method of treatment of neurodegenerative disorder, for instance Alzheimer's disease, or improvement of cognitive function.

EFFECT: compounds act as modulators of gamma-secretase.

31 cl, 14 tbl, 3147 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to novel co-crystalline form of tramadol in form of free base and naproxen, or co-crystalline form of solvate methanol containing tramadol and naproxen, wherein molecular ratio of tramadol to naproxen makes 1:2. Co-crystalline form can be applied to pain treatment, preferably, acute pain, chronic pain, neuropathic pain, heavy or moderate pain, allodynia, hyperalgesia, or cancer pain, including diabetic neuropathy or diabetic peripheral neuropathy and osteoarthritis, fibromyalgia; rheumatoid arthritis, ankylosing spondylitis, scapulohumeral periarthritis, or ischialgia. Co-crystalline form mainly contains enantiomeric forms of naproxen and tramadol, in particular (S)-naproxen or (R)-naproxen and (-)-tramadol or (+)-tramadol. Proposed co-crystalline forms are characterised by X-ray powder diffraction data, as well as by indices of monoclinic elementary cell and indices of endometric acute peak, corresponding to melting point, which has start at 82-84°C.

EFFECT: invention also relates to method for producing co-crystalline form and pharmaceutical composition based thereon.

12 cl, 11 dwg, 5 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: method for alkoxyphenol production comprises O-alkylation of at least one hydroxyphenol to form at least one alkoxyphenol, at that, the said reaction is carried out using an O-alkylating agent, an aqueous solvent containing a Bronsted base and an organic solvent with a base/O-alkylating agent ration in the range of 0.5 to 1.5 moles of base per mole of O-alkylating agent, with an O-alkylating agent/hydroxyphenol ratio in the range of 0.5 to 2 moles of O-alkylating agent per mole of hydroxyphenol and with an organic solvent/hydroxyphenol ratio of less than 280 ml, preferably in the range of 10 to 250 ml and more preferably in the range of 50 to 150 ml of an organic solvent per mole of hydroxyphenol. One of the versions of the alkoxyhydroxybenzaldehyde production method comprises preparation of alkoxyphenol from hydroxyphenol by the foregoing method and a reaction of the aldehyde group addition to the resulting alkoxyphenol to obtain the corresponding alkoxyhydroxybenzaldehyde, preferably by condensation reaction between alkoxyphenol and glyoxylic acid, followed by oxidation of the resulting compound.

EFFECT: proposed method for alkoxyphenol production allows the desired product to be obtained in good yield and high purity with high conversion of initial hydroxyphenol.

11 cl, 3 dwg, 7 ex

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