The method of obtaining 2-hydroxy-4-(meth)acryloylmorpholine

 

(57) Abstract:

The inventive product 2-hydroxy-4-(meth)acryloylmorpholine. BF C17H14O4so pl. 76C, yield 85%. Reagent 1: 2,4-dioxybenzene. Reagent 2: (meth)akriloilkhlorida. Reaction conditions: heating 40 - 60C, in the presence of diethylaniline with subsequent isolation of the desired product from the reaction mixture by precipitation with alcohol C1-C3.

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

OMBF and AABF is the raw material for the synthesis of polymers with UV absorbers that are used to protect various materials from the harmful effects of UV radiation. The known method of synthesis OABF of Na-salt of 2,4-dioxybenzene and acryloid and in benzene [1] This way besides the fact that it is complicated stage of the preparation of Na-salt of the original product, is unsatisfactory because of the low (64%) of the output.

The closest in technical essence and the achieved results is another method [2] which OMBF obtained from 2,4-dioxybenzene and methacryloylamido in the presence of tertiary amine, the mixture is mixed and heated to 70-80aboutC. is then the solvent is distilled off and the product is recrystallized, so pl. 76aboutC. Despite the high yield of the product in this case (about 84%) method is not promising for applications in industry due to the large volume of water flows (more than 60 tons per 1 ton of product) containing about 3% of harmful substances (pyridine, metakrilovoy acid). Disposal of this quantity of waste water requires high energy costs, and dropping them into the drain is unacceptable from the point of view of ecology.

In the light of the specified task was the development of receipt OABF and OMBF suitable for applications in industry, including requirements as to achieve a high product yield and eco-friendly process. In line with this purpose, we have developed the proposed method. In this way OABF and OMBF obtained from 2,4-dioxybenzene and methacryloylamido in the presence of tertiary amine-diethylamine and subsequent precipitation of the product from the reaction mixture with alcohol1-C3. The application of this process diethylaniline as bases, and alcohols as the precipitating product allows you to get OABF and OMBF high yield (80-85) with a small amount of easily recyclable waste.

In the known traditional methods acelerou islenos water. Based on known from the literature data it was impossible to suppose that the combination as a tertiary amine diethylaniline and the solvent precipitator alcohol (C1-C3) will provide a high yield of product. Found the system components of the process gave the opportunity not only with high efficiency to carry out the acylation of dioxybenzone, but to get a small amount of recyclable waste. When the distillation of the mother liquor is regenerated alcohol and diethylaniline that again in the process. Thus, the proposed method proved to be both highly efficient and environmentally friendly.

P R I m e R 1. Synthesis of 2-hydroxy-4-methacryloyloxyethyl, 10.7 g of 2,4-dioxybenzene mixed with 5.5 g of methacryloylamido and 7.5 g of diethylaniline and the mixture is heated with stirring at 40 to 60aboutC for 2-3 hours Then added to the mixture about 80 to 98% methanol and the mass cooled. The product is filtered and recrystallized from methanol. The product yield 11.9 g (85%), so pl. 76aboutWith data from the literature so pl. 76aboutWith (2).

From the mother of solutions obtained in the experiment, distilled methanol, the residue is treated with alkali, and then distilled off diethylaniline. Selected by distillation is, what about instead of methanol used isopropanol. Yield 83% so pl. 76aboutC.

P R I m e R 3. The synthesis was carried out as in example 1, but instead of methanol used ethanol. The product yield was 82.3% so pl. 76aboutC.

P R I m e R 4. Synthesis of 2-hydroxy-4-acryloylmorpholine. The synthesis was carried out according to the method of example 1, but instead of methacryloyl - chloride taken 4.7g of akriloilkhlorida. Output 83,5% so pl. 80-81aboutWith literature data 80-81aboutWith (2).

Thus, the proposed method ensures the receipt of the products to be eco-friendly, due to the availability of regeneration obtained in the process waste while ensuring high product yield 82-85%

The METHOD of OBTAINING 2-HYDROXY-4-(METH)ACRYLOYLMORPHOLINE of 2,4-dioxybenzene and (meth)akriloilkhlorida in the presence of a tertiary amine by heating, followed by separation of the product from the reaction mass, characterized in that as an amine use diethylaniline, and the selection is carried out by precipitation of the product alcohol C1-3from the reaction mass.

 

Same patents:

The invention relates to methods of producing esters of acrylic acid and can be used for dehydration of methyl acrylate methyl ester propionic acid

The invention relates to organic chemistry, in particular to methods of producing 2,2-bis-[4-(3-methacryloyloxy-2-hydroxyprop-poxy)phenyl] propane (Bis-GMA), used as a crosslinking agent of a composite material, in particular dental, curing when using any system of initiation

The invention relates to acrylic esters, in particular to an improved process for the preparation of acrylate used in organic synthesis

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

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: 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

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 18-25C.

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 18-25C prevents isomerisation of the (2E,4E)-diene system and increases stereochemical purity of the product.

4 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to application of ester compounds of benzoic acid, taken from group, which includes 1-phenylvinyl 4-methoxybenzoate; 1-(4-methoxyphenyl)-vinyl 4-tert-butyl benzoate, 1-(4-tert-butylphenyl)-vinyl 4-methoxybenzoate, 1-phenylvinyl 4-tert-butyl benzoate, 4-benzoyloxy-2-methoxybenzolsulphonic acid, 3-diethylaminophenyl benzoate and 3-(1-pyrrolidinyl) phenyl benzoate and 3-methoxy salicylate, as component for preparing composition for protection of human organism or animal or material from ultraviolet radiation, containing effective quantity at least one of claimed compounds, as component for preparing composition, which is characterised by progressive protection from UV radiation, depending on duration of sun influence and level of sun radiation, as component for preparing composition for individual hygiene, which is characterised by progressive protection from UV radiation, depending on duration of sun influence and level of sun radiation, as component for preparing industrial composition, which is characterised by progressive protection from UV radiation, depending on duration of sun influence and level of sun radiation, and as component for preparing composition, which at photo-regrouping shows quantity of obtained UV-B radiation.

EFFECT: invention also relates to composition for protecting human or animal organism or protection of material from ultraviolet radiation, contains effective quantity of at least one above mentioned ester compound of benzoic acid.

40 cl, 6 dwg, 33 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry and particularly to a method of producing (4E)-tridec-4-en-1-ylacetate. (4E)-tridec-4-en-1-ylacetate is a sex pheromone for tomato moth (Keiferia lycopersicella), which is a dangerous pest for solanaceae. Results of the invention can be useful in chemistry and agriculture. The method of producing (4E)-tridec-4-en-1-ylacetate includes alkylating malonic ester with (E)-1,3-dichloropropene to obtain diethyl[(2E)-3-chloroprop-2-en-1-yl]propanedioate, decarbalkoxylating diethyl[(2E)-3-chloroprop-2-en-1-yl]propanedioate to obtain ethyl(4E)-5-chloropent-4-enoate, Fe-catalysed cross-coupling of the ethyl(4E)-5-chloropent-4-enoate with octylmagnesium bromide to obtain ethyl(4E)-tridec-4-enoate, reducing the ethyl(4E)-tridec-4-enoate to obtain (4E)-tridec-4-en-1-ol, acetylation of the (4E)-tridec-4-en-1-ol to obtain (4E)-tridec-4-en-1-ylacetate. According to the invention, Fe-catalysed cross-coupling of ethyl(4E)-5-chloropent-4-enoate with octylmagnesium bromide to obtain ethyl(4E)-tridec-4-enoate is carried out in the presence of a Fe(acac)2Cl catalyst in a mixture of tetrahydrofuran and N-methylpyrrolidone, wit the following molar ratio of reactants [(ethyl(4E)-5-chloropent-4-enoate]:[octylmagnesium bromide]:[Fe(acac)2Cl]:[tetrahydrofuran ]:[N-methylpyrrolidone]=1:1.15:0.01:12:7 for 30 min at 0-5C.

EFFECT: advantage of the disclosed method is higher output of (4E)-tridec-4-en-1-ylacetate.

3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for the production of 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate, comprising an interaction under reaction conditions between 5-tert-butyl-3-methylcatechol (BMC) and triethylamine and a member selected from the group consisting of an aromatic carboxylic acid and an aromatic carboxylic acid derivative, where the derivative of the aromatic carboxylic acid is an aromatic acyl halide, an aromatic anhydride, an aromatic carboxylate salt or any combination thereof; and where the aromatic carboxylic acid is benzoic acid; and forming a composition comprising 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate (BMPD). Synthesis pathways for a precursor to 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate are provided. The precursor is 5-tert-butyl-3-methylcatechol.

EFFECT: simple and cost-effective method with high yield.

10 cl, 2 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to substituted aromatic phenylenediether of structure

,

in which groups R1-R14 are similar or different , group R1 does not represent isopropyl or tertiary alkyl group, and each of groups R1 and R3 is selected from the group, consisting of non-substituted alkyl group, containing from 1 to 20 carbon atoms, non-substituted alkenyl group, containing from 1 to 20 carbon atoms, halogenated hydrocarbon group, halogen atom, silicon-containing hydrocarbon group and their combinations; and each of groups R2, R4 and R5-R14 is selected from the group, consisting of hydrogen atom, non-substituted hydrocarbon groups, consisting from 1 to 20 carbon atoms, halogen atom and their combinations, on condition that R2 and R4 do not represent bromine simultaneously. Invention also relates to substituted aromatic phenylenediether of structure (II), in which groups R1-R14 are similar or different, group R2 represents alkyl group, containing from 2 to 20 carbon atoms, and each of groups R5-R14 is selected from the group, consisting of hydrogen atom, non-substituted hydrocarbon group, containing from 1 to 20 carbon atoms, halogenated hydrocarbon group, halogen atom, silicon-containing hydrocarbon group and their combinations; and all groups R2, R7 and R12 do not represent tert-butyl groups simultaneously. Invention also relates to substituted aromatic phenylenediether of structure (II), in which groups R1-R14 are similar or different, each of groups R1, R3, R4 represents hydrogen atom, group R2 represents hydrocarbon group, containing from 1 to 20 carbon atoms, at least, one of groups R7 and R12 is selected from the group, consisting of halogen atom, primary hydrocarbon group, containing from 1 to 20 carbon atoms, which can optionally contain halogen or silicon atoms or alkoxygroup as substituents, and secondary hydrocarbon group, containing from 1 to 20 carbon atoms, which can optionally contain halogen atoms, silicon atoms or alkoxygroup as substituents; and each of groups R5-R6, R8-R11 and R13-R14 is selected from the group, consisting of hydrogen atom, non-substituted hydrocarbon group, containing from 1 to 20 carbon atoms, halogenated hydrocarbon group, halogen atom, silicon-containing hydrocarbon group and their combinations.

EFFECT: said compounds are prospective components of improved catalytic systems for production of polymers, based on olefins, which have improved properties.

7 cl, 1 tbl

FIELD: pharmacology.

SUBSTANCE: ophthalmic composition contains a formula compound, where the values for R1 and R2 groups are given in the claims, and an ophthalmologically acceptable carrier. The invention also relates to a method for dry eye treatment, comprising local administration of a therapeutically effective amount of the ophthalmic composition to the eye of the subject in need.

EFFECT: increased efficiency.

20 cl, 6 dwg, 6 ex

FIELD: chemistry of organophosphorus compounds.

SUBSTANCE: invention relates to compounds with the bond C-P, namely to phosphorus-boron-containing methacrylate that can be used as inhibitor of combustion of polyvinyl alcohol-base film materials. Invention describes phosphorus-boron-containing methacrylate of the following formula: wherein n = 4-8. Polyvinyl alcohol films modified with indicated phosphorus-boron-containing methacrylate shows the enhanced refractoriness, rupture strength up to 206 kgf/cm2, water absorption up to 240% and relative elongation up to 12%.

EFFECT: valuable properties of substance.

1 tbl, 2 ex

FIELD: chemical engineering.

SUBSTANCE: task of invention resides in prevention of monomeric methyl methacrylate from polymerization via inhibition of inner surface of the process equipment and thereby prevention of polymeric scale formation thereon, which would lead to heavy cleaning operation involving dismounting of equipment to fragments and burning out of polymeric scale. To that end, inner surface of equipment is treated with inhibitory solution containing sodium liquid glass solution, sodium silicofluoride as hardened in amount 25% of the weight of liquid glass, and water-soluble nigrozin at concentration in hardened liquid glass layer not exceeding 1% of the weight of liquid glass. Method may be used in production of other ethylenically-unsaturated monomers.

EFFECT: eliminated scale cleaning operation.

2 ex

FIELD: organic chemistry, chemical technology, microbiology.

SUBSTANCE: invention relates to a method for preparing esters of acrylic acid and (C2-C8)-aliphatic alcohols. Method involves hydrolysis of acrylonitrile to acrylic acid ammonium salt by using the strain of bacterium Alcaligenes denitrificans C-32 VKM 2243 D. Then ammonium salt is converted to acrylic acid by acidification with sulfuric acid (the mole ratio = 1:0.5), extraction of acrylic acid with the corresponding alcohol, esterification of acrylic acid in the presence of sulfuric acid and the polymerization inhibitor followed by isolation of the ready product by the known procedure. Method provides reducing consumption of sulfuric acid and the polymerization inhibitor, to reduce energy consumption and, therefore, formation of by-side product and equipment corrosion.

EFFECT: improved preparing method.

5 ex

FIELD: industrial production of methacrylic acids at reduced amount of industrial wastes.

SUBSTANCE: proposed method is performed by catalytic oxidation of propane, propylene or isobutylene in vapor phase at separation of final product and forming of high-boiling mixture as by-product which contains (according to Michaels addition) water, alcohol or methacrylic acid added to methacrylic group. By-product is decomposed in thermal decomposition reactor at simultaneous distillation of decomposition products in distilling column from which methacrylic acid is taken in form of distillate. Flow of liquid decomposition residue is forced for peripheral direction by means of mixing blades before withdrawal from reactor. Peripheral direction is obtained with the aid of liquid fed from the outside of decomposition reactor; to this end use is made of initial high-boiling material or flow of liquid discharged from decomposition reactor. If necessary, etherification stage is performed through interaction with alcohol for obtaining methecrylic ester. Decomposition of by-product formed at obtaining methacrylic acid by oxidation of propylene or isobutylene or at obtaining methacrylic acid by interaction of acid with alcohol by alcohol through introduction of by-product into thermal decomposition reactor provided with distilling column which has plates made in form of disks and toroids for simultaneous decomposition and distillation. Plant proposed for realization of this method includes thermal decomposition reactor and distilling column, level meters and lines for discharge of liquid containing easily polymerized compounds. Level indicator mounted at area of accumulation of liquid shows pressure differential. Line for detecting the side of high pressure of this level meter is connected with accumulated liquid discharge line.

EFFECT: updated technology; increased yield of target products.

38 cl, 14 dwg, 2 tbl, ex

FIELD: organic synthesis.

SUBSTANCE: claimed method includes reaction of maleic acid C1-C4-alcohol esters with ethylene in presence of metathesis catalyst at 20-140°C ethylene pressure of 101325-506625 Pa.

EFFECT: method of high selectivity, mild conditions without uses of toxic reagents.

7 cl, 28 ex, 8 tbl

FIELD: organic chemistry, chemical technology, polymers.

SUBSTANCE: invention relates to novel polyalkoxylated trimethylolpropane (meth)acrylic esters. Invention proposes polyesters of the following formulas (Ib) and (Ic) wherein EO means O-CH2-CH2-; PO means independently of one another O-CH2-CH(CH3)- or O-CH(CH3)-CH2-; n1 + n2 + n3 = 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 54, 55, 56, 57, 58, 59 or 60; m1 + m2 + m3 = 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13; R1, R2 and R3 mean independently of one another hydrogen atom (H) or -CH3. Proposed esters can be used in preparing polymers absorbing aqueous liquids and forming hydrogel. Invention provides development of compounds that can be used as radical cross-linking agent, in particular, for superabsorbers.

EFFECT: valuable properties of esters.

12 cl, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: catalytic composition contains the catalyst of olefin metathesis as one component, and phenol derivatives as another component, at proportion: 1 mol equivalent of catalyst to 200-1500 mol equivalents of phenol derivatives. In another modification, the catalytic composition contains as the second component the alcohol derivates which do not contain the C-H fragments at α-position to hydroxyl function, at proportion: 1 mol equivalent of catalyst to 200-1500 mol equivalents of alcohol derivatives. Another one modification of the invention has quinine or its derivatives as the second component of the catalytic composition. Particularly, the ruthenium complex with formula can be used as a catalyst of olefin metathesis.

EFFECT: number of catalyst turnover and life-time of catalyst in metathesis reaction of dialkylmaleate with ethylene are increased.

10 cl, 12 ex, 6 tbl

Up!