The method of obtaining a mixture of dihydrocoumarin and coumarin


(57) Abstract:

Usage: as a flavouring compounds in perfumery and food industry. The inventive product: mixture of dihydrocoumarin and coumarin. Reagent 1: methyl or butyl ether 2-oxacyclohexadecan acid. Process conditions: reagent 1 is subjected to dehydrocyclization at 230 to 260°C. in a mixture of normal paraffins structure composition C11-C20with so Kip. 240 - 300°C in the presence as catalyst of palladium supported on carbon or alumina without additives or with the addition of inorganic salts or metal oxide II of the periodic system at atmospheric pressure inert gas and a temperature of 230 - 260°C in the presence of additives alkali metal salt of higher aliphatic acids C12-C18taken in the amount of 0.5 - 5 wt. % by weight of catalyst in the mixture of hydrocarbons, normal structure of the structure of C11-C20with a boiling point of 240 to 300°C and after separation of the catalyst of the target product are split layers of the cooled filtrate. This method allows you to speed up the process 2 - 3 times and simplify the process by eliminating the separation of high-boiling solvent by vacuum d is a (II), used as flavouring substances.

A method of obtaining a mixture of I and II liquid-phase dehydrogenation of 1 on Pd, Pt, Rh and Ni catalysts at a temperature of 200-350aboutWith [1].

However, this method is based on the use of dihydrocoumarin formed in turn in the two-stage process of esters of 2-oxacyclopropane acid, which significantly complicates the process and increases its duration.

Known more simple way to obtain a mixture of I and II, which consists in a liquid-phase dehydrocyclization 2-oxacyclopropane acid (III) in the presence of catalyst (5% Pd/C at 235about[2].

Playing this way (due to the lack of data in the patent) showed that complete conversion III is only for 18-20 hours At this selectivity education I and II does not exceed the amount of 60%.

The closest technical solution is the method of obtaining a mixture of I and II in which dehydrocyclization esters of 2-oxacyclopropane acid (IV) in the high-boiling organic solvent, for example, in diphenyloxide at 230-260aboutOn Pd/Al2O3modified inorganic salts or OK is MESI I and II, according to GC, reaches 91.5% at 99,2% conversion of the starting compound. The duration of the process is 25-38 h [3].

The disadvantage of this method is the long duration of the process and difficulties of the selection of the final product associated with the need for distillation of high-boiling solvent by vacuum distillation.

The aim of the invention is the intensification and simplification of the process. This goal is achieved by a method of obtaining a mixture of dihydrocoumarin and coumarin-dehydrocyclization esters of 2-oxacyclopropane acid in the presence of palladium catalysts or palladium catalysts with the addition of salts or oxides of metals of the II-IV, VIII groups of the periodic system in an atmosphere of inert gas in an organic solvent at atmospheric pressure and a temperature of 230-260aboutWith subsequent separation of the catalyst by filtration and isolation of the target product.

A distinctive feature of the method is that the solvent, a mixture of normal hydrocarbons of the structure of the composition WITH11-C20with a boiling point 240-300aboutAnd the process is conducted in the presence of additives of salts of alkali metals higher elevations the t distinguish the separation layer after separation of the catalyst and cooling the filtrate.

The hydrocarbon solvent used in a 1.5-fold excess relative to the weight of the original ester IV.

Control over the transformation of the ester IV lead by GLC. Depending on the catalyst complete conversion of the ester IV occurs within 3-7 hours at a temperature of 230-260about(In nitrogen atmosphere). The selectivity of the formation of mixtures I and II for the full conversion reaches 67,6-91,9%.

Complete mutual solubility of the reaction product and taken hydrocarbon fraction WITH11-C20occurs when 110-115aboutC. It allows without appreciable loss of the target product to separate the catalyst by filtration on a heated Druk-filter at a higher temperature, after which the reaction product stands out from the cooled to 20aboutFrom the filtrate in the form of oily lower layer.

The top layer is a hydrocarbon solvent without any pre-processing can be reused for dehydrocyclization new portions of ether IV.

The advantage of this method consists in the following:

reduced duration of response in 2-3 times with 15-38 h to 3.5-7 PM

simplified technology by eliminating the stage of distillation of vysokokipjashchie solvent. The simultaneity is eagerly flask with a capacity of 200 ml, equipped with a stirrer, a thermometer, a nozzle Dean-stark (for distillation of low-boiling reaction products) and a gas-feeding tube placed 0,163 mole of methyl or butyl ether 2-oxacyclopropane acid, of General formula

where R = CH3; C4H9.

a 1.5-fold mass amount of a mixture of hydrocarbons of normal structure WITH11-C20with a boiling point 240-300aboutWith 25% of catalyst by weight is taken ether and alkali metal salts of higher aliphatic acids WITH12-C18. The mass is stirred at 230-260aboutWith in a stream of nitrogen at atmospheric pressure until complete conversion of the original broadcast. The reaction mass analyzed every 30 min by GLC.

Once the mass is filtered in a nitrogen atmosphere at Druk-filter with a temperature of 120aboutC. the Filtrate is transferred into a separating funnel, cooled to 20-25aboutWith standing for 1 h, the lower oil layer is separated and distilled in vacuum, targeted product at 150-154aboutWith a residual pressure of 6.6 to 7.0 GPA. The top layer is a hydrocarbon solvent is used again.

The results of the experiment are presented in the table.

As can be seen from the table the 5 wt.%.

Dosage them in the amount of 0.5% by weight of catalyst (op.10) can reduce the duration of the process only until 7 PM So the use of such salts in smaller amounts is not justified.

The increase of the admixture to 20% (op.9) do not contribute to greater acceleration process and is therefore inadvisable.

1. The METHOD of OBTAINING a MIXTURE of DIHYDROCOUMARIN AND COUMARIN liquid-phase dehydrocyclization esters of 2-oxacyclopropane acid in the presence of palladium catalyst or palladium catalyst containing the additive salt or oxide of a metal of group II of the Periodic system, in an organic solvent at atmospheric pressure inert gas and a temperature of 230 - 260oWith subsequent separation of the catalyst by filtration, characterized in that, in order to strengthen and simplify the process, as organic solvent, a mixture of normal hydrocarbons of the structure of the composition WITH11- C20with a boiling point of 240 - 300oAnd the process is conducted in the presence of additives alkali metal salt of higher aliphatic acids WITH12- C18taken in the amount of 0.5 - 5% by weight of the catalyst.

2. The method according to p. 1, characterized in that after the CTD is


Same patents:

The invention relates to a method for producing novel compounds that have biological activity similar to the activity retinova acid, more specifically, to methods and intermediate products used in the synthesis dogsleding acetylene compounds with similar retinova acid activity

FIELD: organic chemistry, chemical technology, catalysts.

SUBSTANCE: invention relates to a method for preparing acetic acid by gas-phase oxidation of ethane and/or ethylene with oxygen using catalyst comprising molybdenum and palladium. For realization of method gaseous feeding comprising ethane, ethylene or their mixture and oxygen also are contacted at enhanced temperature with catalyst that comprises elements Mo, Pd, X and Y in combination with oxygen of the formula (I): MoaPdbXcYd wherein X and Y have the following values: X means V and one or some elements optionally taken among the following group: Ta, Te and W; Y means Nb, Ca and Sb and one or some elements optionally taken among the following group: Bi, Cu, Ag, Au, Li, K, Rb, Cs, Mg, Sr, Ba, Zr and Hf; indices a, b, c and d mean gram-atom ratios of corresponding elements wherein a = 1; b = 0.0001-0.01; c = 0.4-1, and d = 0.005-1. Niobium is added to the catalyst structure using niobium ammonium salt. Preferably, niobium ammonium salt is used as the niobium source. The continuance of contact time and composite values of the parent gaseous mixture are so that taken to provide output value by acetic acid to be above 470 kg/(m3 x h). The selectivity of oxidation reaction of ethane and/or ethylene to acetic acid is above 70 mole %. Invention provides enhancing stability and output of catalyst.

EFFECT: improved preparing method.

14 cl, 1 tbl, 6 ex

FIELD: petrochemical synthesis catalysts.

SUBSTANCE: invention discloses a method for preparation of palladium catalyst comprising impregnation of alumina carrier with palladium chloride solution in presence of aqueous hydrochloric acid, treatment with reducing agent (hydrogen), washing with water, and drying, said carrier being preliminarily decoked exhausted catalyst containing alumina and group I and/or II, and/or VI, and/or VIII metals and subjected to washing with aqueous hydrochloric or nitric acid and then with water. Exhausted ethylene oxide production catalyst or methylphenylcarbinol dehydration catalysts can also be suitably used.

EFFECT: increased selectivity and activity of catalyst.

2 cl, 2 tbl, 21 ex

FIELD: supported catalysts.

SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.

EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.

5 cl, 9 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of catalyst comprises applying palladium compound onto silica cloth and heat treatment. Palladium compound is applied by circulation of toluene or aqueous palladium acetate solution through fixed carrier bed until palladium content achieved 0.01 to 0.5%. Palladium is introduced into cloth in dozed mode at velocity preferably between 0.1 and 5.9 mg Pd/h per 1 g catalyst. Heat treatment includes drying at temperature not higher than 150oC under nitrogen or in air and calcination in air or nitrogen-hydrogen mixture flow at temperature not higher than 450oC. Original silica cloth can be modified with 0.6 to 6.5% alumina. Palladium is uniformly distributed in silica cloth and has particle size preferably no larger than 15 Å. Invention can be used in treatment of industrial gas emissions and automobile exhaust to remove hydrocarbons.

EFFECT: deepened oxidation of hydrocarbons.

5 cl, 1 tbl, 4 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: palladium-containing hydrogenation catalyst, which can be used to control rate of autocatalytic hydrogenation reactions, is prepared by hydrogen-mediated reduction of bivalent palladium from starting compound into zero-valence palladium and precipitation of reduced zero-valence palladium on carbon material, wherein said starting material is tetraaqua-palladium(II) perchlorate and said carbon material is nano-cluster carbon black. Reduction of palladium from starting compound and precipitation of zero-valence palladium on carbon material are accomplished by separate portions.

EFFECT: increased catalytic activity, enabled catalyst preparation under milder conditions, and reduced preparation cost.

1 dwg, 1 tbl, 12 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: preparation of catalyst comprises depositing active components on γ-alumina carrier at stirring, carrier being preliminarily treated with concentrated NaOH solution. Active components are deposited consecutively in three steps. In the first step, preliminarily prepared chitosan in acetic acid solution with KCl solution is deposited for 60-65 min; in the second step, sodium tetrachloropaladate(II) trihydrate Na2PdCl4·3H2O solution is deposited for 60-65 min; and, in the third step, hydrazine hydrate solution as reducing agent is added for 180-240 min. After each step, resulting suspension is filtered off, washed, and dried at 293-303K for 1-2 h in vacuum. Catalyst can be used in chemical industry and in processing of industrial and household wastes.

EFFECT: enhanced nitrate hydrogenation efficiency.

6 cl, 1 dwg, 6 ex

FIELD: textile, paper and chemical industries; protection of environment in production of bleachers, biocides and components of oxidizing processes.

SUBSTANCE: proposed catalyst contains one or more metals of platinum group used as active component, one or more polyolefines and activated carbon carrier. It is preferably, that polyolefines have molecular mass above 400 and are selected from ethylene homopolymers and ethylene copolymers with alpha-olefines, propylene homopolymers and propylene copolymers with alpha olefines, butadiene homopolymers and copolymers with styrene and other olefines, isoprene homopolymers and copolymers with other olefines, ethylene-propylene copolymers, ethylene-propylene diolefine three-component copolymers, thermoplastic elastomers obtained from butadiene and/or isoprene and styrene block-copolymers, both hydrogenized and non-hydrogenized. Hydrogen peroxide is produced in presence of said catalyst from hydrogen and oxygen in reaction solvent containing halogenated and/or acid promoter. Proposed catalyst makes it possible to increase degree of conversion and selectivity of process, to obtain aqueous H2O2 solutions at content of acids and/or salts at level of trace amount.

EFFECT: enhanced efficiency.

48 cl, 1 tbl,18 ex

FIELD: industrial organic synthesis and catalysts.

SUBSTANCE: invention relates to a methyl ethyl ketone production process via catalytic oxidation of n-butenes with oxygen and/or oxygen-containing gas. Catalyst is based on (i) palladium stabilized with complexing ligand and (ii) heteropolyacid and/or its acid salts, in particular molybdo-vanado-phosphoric heteropolyacid having following composition: H11P4Mo18V7O87 and/or acid salt Na1.2H9.3Mo18V7O87, said complexing ligand being notably phthalocyanine ligand. Catalyst is regenerated by making it interact with oxygen and/or oxygen-containing gas at 140-190°C and oxygen pressure 1 to 10 excessive atmospheres. Oxidation of n-butenes is conducted continuously in two-stage mode at 15 to 90°C in presence of above-defined catalyst.

EFFECT: enhanced process efficiency due to increased stability of catalyst resulting in considerably increased productivity and selectivity.

7 cl, 1 dwg, 3 tbl, 8 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: catalyst for modifying colophony contains, as carrier, high-porosity cellular α-alumina-based block material and, as active catalyst fraction, sulfated group IV metal oxide and metallic palladium.

EFFECT: increased modification rate due to developed catalyst surface and eliminated disintegration and carry-over of catalyst.

5 ex

FIELD: reduction-oxidation catalysts.

SUBSTANCE: invention relates to catalytic chemistry and, in particular, to preparation of deep-oxidation supported palladium catalysts, suitable, for example, in afterburning of motor car exhaust. Preparation involves depositing palladium from aqueous solution of palladium precursors followed by drying and calcination. Precursors are selected from nitrite anionic or cationic palladium complexes [Pd(NO2-)(H2O)3]Anx or [Pd(NO2-)n(H2O)m](Kat)y, wherein An are anions of acids containing no chloride ions, Kat is proton or alkali metal cation, n=3-4, m=0-1, x=1-2, and y=1-2. Nitrite ions are introduced into impregnating solution in the form of nitrous acid salts or are created in situ by reducing nitrate ions or passing air containing nitrogen oxides through impregnating solution. Ratio [Pd]/[NO2-] in impregnating solution is selected within a range 1:1 to 1:4.

EFFECT: eliminated chlorine-containing emissions, increased stability of chlorine-free impregnating solutions, reduced their acidity and corrosiveness, and increased catalytic activity in deep oxidation reactions.

2 cl, 1 tbl, 16 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new derivatives of tocopherol, tocotrienol and other derivatives of chroman of the general formula (1): wherein X is taken among the group comprising oxygen and nitrogen atoms; Y is taken among the group comprising oxygen, nitrogen and sulfur atoms wherein if Y represents oxygen or nitrogen atom then n = 1 and if Y represents sulfur atom then n = 0; R1 represents residue of carboxylic acid, carboxamide, ester, alcohol, amine or sulfate; R2 represents methyl; R3 represents methyl; R4 represents methyl; R5 is taken among the group comprising alkyl, alkenyl, alkynyl, carboxyl and ester residue wherein if Y represents nitrogen atom then indicated nitrogen atom is replaced with group R6 wherein R6 represents hydrogen atom or methyl wherein if X represents oxygen atom, Y represents oxygen atom and R5 represents phytyl then R1 doesn't mean butanoic acid. Also, invention relates to a pharmaceutical composition based on these compounds, a method for treatment of cellular-proliferative disease and a method for induction of cells apoptosis. Invention provides preparing new compounds possessing the proliferative effect.

EFFECT: valuable medicinal properties of compounds.

36 cl, 4 tbl, 19 dwg, 19 ex

FIELD: chemistry.

SUBSTANCE: invention relates to use of a therapeutic agent which is an α-amino-amide compound of formula (I):

, in which R is a phenyl ring which is optionally substituted with one or two substitutes independently selected from halogen, hydroxy, cyano, C1-C6-alkyl, C1-C6-alkoxy or trifluoromethyl; R1 is hydrogen or C1-C6-alkyl; R2 and R3 are independently selected from hydrogen, C1-C4-alkyl; R4 and R5 independently denote hydrogen, C1-C6-alkyl; X is O or S; Y and Z, taken together with X and a phenyl ring bonded to Y and X, form a 5-7-member saturated heterocycle containing O or S atoms, or Y and Z denote hydrogen; or its isomers, mixtures and pharmaceutically acceptable salts for preparing a medicinal agent for treating lower urinary tract disorders.

EFFECT: obtaining a pharmaceutical composition based on the said compounds.

8 cl, 6 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: in the given invention, there is offered a method for preparing a compound of formula , where Y is specified of CH3, CH2OH, CH2CH2OH, CH2Br and Br; involving the stages: (1) reaction of the compound of formula where OX represents hydroxy or O-M+ where M+ represents cation chosen of Li+, Na+ and K+ and Y is such as specified above; with trans-cynnamaldehyde , with a secondary amine compound added; then (2) acid treatment of a product from the previous stage to prepare a compound of formula (I). The aforesaid method can be used for preparing tolterodine and fezoterodine which are effective in treating the hyperactive urinary bladder. There are also declared compounds of formulae V, VI and VII.

EFFECT: development of the effective method for preparing the compound.

25 cl, 19 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to a method for producing methyl 1 -[3-(cyclohexylcarbamoyl)-2-oxochroman-4-yl]cyclopentanecarboxylate of formula (1) which consists in boiling 1-bromcyclopentanecarboxylic acid methyl ester with zinc and 2-oxo-2H-chromen-3-carboxylic acid cyclohexylamide in the medium of benzol - ethylacetate - hexamethylphosphorotriamide (10:5:1) for 4 hours.

EFFECT: produced compound is novel and possesses analgesic action.

1 tbl, 2 ex