Production of substituted phenylene aromatic diesters

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

 

PRIORITY CLAIMS

According to this application claims priority under provisional application U.S. No. 61/141902, filed December 31, 2008, and provisional application No. 61/141959, filed December 31, 2008, the contents of each of these applications is fully incorporated into the present application by reference.

Background of the INVENTION

The present invention relates to the preparation of phenylene aromatic complex diapirov.

The substituted phenylene aromatic complex dietary are used as internal electron donor in obtaining pronatalistic compositions for the synthesis of polymers based on olefins. In particular, the Ziegler-Natta catalysts containing 5-tert-butyl-3-methyl-1,2-phenylene, dibenzoate as an internal electron donor, show high catalytic activity and high selectivity in the polymerization. In addition, these catalysts allow to obtain polymers based on olefins (for example, polymers based on propylene) with high isotacticity and wide distribution of molecular weights.

In the technique recognizes the need for polymers based on olefins and polymers based on propylene with improved properties. Need to search multiple and/or alternative ways of synthesis of substituted phenylene aromatic complex diapirov for both�biscuit inexpensive and reliable method of obtaining these compounds.

Summary of the INVENTION

The present invention is directed to obtaining a substituted phenylene aromatic complex diapirov and, in particular, 5-tert-butyl-3-methyl-1,2-phenylene of dibenzoate. The invention discloses ways of obtaining synthetic precursor 5-tert-butyl-3-methyl-1,2-phenylene of dibenzoate, namely 5-tert-butyl-3-methylcatechol. The receipt of this precursor, as shown in the present invention greatly simplifies the synthesis of 5-tert-butyl-3-methyl-1,2-phenylene of dibenzoate and gives you the opportunity to get it on a large scale, based on common inexpensive starting compounds.

In one aspect of the present invention relates to methods of synthesis. In one of the embodiments proposed in the invention method, which includes the interaction in suitable reaction conditions, 5-tert-butyl-3-methylcatechol (BMC) with an aromatic carboxylic acid or derivative of an aromatic carboxylic acid with the formation of 5-tert-butyl-3-methyl-1,2-phenylene of dibenzoate (BMPD).

In addition, the invention relates to another method. In one of the embodiments proposed in the invention method, which involves the alkylation of 3-methylcatechol tert-butanol or isobutylene in the suitable reaction conditions with the formation of 5-tert-butyl-3-methylcatechol.

Further, the invention relates to trail�usamu method. In one of the embodiments proposed in the invention method, comprising the oxidation of 5-tert-butyl-3-methyl-2-hydroxybenzaldehyde in the suitable reaction conditions with the formation of 5-tert-butyl-3-methylcatechol.

In addition, the invention relates to another method. In one of the embodiments proposed in the invention method, which involves the oxidation of 4-tert-butyl-2-METHYLPHENOL in the suitable reaction conditions with the formation of 5-tert-butyl-3-methylcatechol.

The invention further relates to the next method. In one of the embodiments proposed in the invention method, which involves the hydrolysis of 2-halo-4-tert-butyl-6-METHYLPHENOL in the suitable reaction conditions with the formation of 5-tert-butyl-3-methylcatechol.

In addition, the invention relates to another method. In one of the embodiments proposed in the invention method, comprising the hydrogenolysis of 5-tert-butyl-3-aminomethylpyridine in the suitable reaction conditions with the formation of 5-tert-butyl-3-methylcatechol.

An advantage of the present invention is an improved method of obtaining substituted phenylene aromatic reaction diapirov, for example, 5-tert-butyl-3-methyl-1,2-phenylene of dibenzoate.

An advantage of the present invention is to provide a synthetic precursor 5-tert-butyl-3-methyl-1,2-Hairdryer�of flax dibenzoate, namely 5-tert-butyl-3-methylcatechol.

An advantage of the present invention is to provide several ways of synthesis of 5-tert-butyl-3-methylcatechol.

An advantage of the present invention is to provide 5-tert-butyl-3-methyl-1,2-phenylene of dibenzoate using inexpensive starting materials.

An advantage of the present invention is to provide several ways of synthesis of substituted phenylene aromatic complex diapirov, for example, 5-tert-butyl-3-methyl-1,2-phenylene of dibenzoate that guarantees reliable acquisition of these connections intended for the synthesis of polymers based on propylene.

An advantage of the present invention is a method for producing the substituted phenylene aromatic complex diapirov in significant quantities.

An advantage of the present invention is environmentally safe, non-toxic method of obtaining substituted phenylene aromatic complex diapirov.

An advantage of the present invention to provide a substituted phenylene aromatic complex diapirov in significant quantities.

An advantage of the present invention is simple, economical in time and/or cost-effective method of purification of substituted phenylene aromatic complex diapirov.

BRIEF DESCRIPTION of ILLUSTRATIVE MATERIAL

Fig.1 is a block diagram showing the method of producing a substituted phenylene aromatic diester complex according to one of embodiments of the present invention.

Fig.2 is a block diagram showing the method of cleaning the substituted phenylene aromatic diester complex according to one of embodiments of the present invention.

DETAILED description of the INVENTION

The present invention is directed to obtaining a substituted phenylene aromatic complex diapirov. It was found that 5-tert-butyl-3-methylcatechol (or "BMC") is an effective synthetic precursor in obtaining the substituted phenylene aromatic diester complex, namely 5-tert-butyl-3-methyl-1,2-phenylene of dibenzoate (or "BMPD"). BMPD an effective internal electron donor in the Ziegler-Natta catalysts. The method disclosed in the present description, is able to provide economical (from the point of view of saving both time and money), a simple, scalable from the point of view of increasing the number of ways of synthesis of BMC, with outputs that are acceptable for commercial/industrial applications. The opportunity to obtain economical BMC, respectively, facilitates the economical production of 5-tert-butyl-3-methyl-1,2-phenylene of dibenzoate.

5-tert-butyl-3-metelka�Ehin (BMC) has the following structure (I)

In one of the embodiments of a method for producing a BMC. This method involves the alkylation of 3-methylcatechol tert-butanol or isobutylene in the suitable reaction conditions with the formation of 5-tert-butyl-3-methylcatechol (BMC) (reaction 1 or Rx 1). The term "alkylation" or "alkylation reaction" means the introduction of an alkyl substituent in an organic compound. "Organic compound" is a chemical compound that contains carbon atoms. In the present description, the term "suitable conditions the reaction" refers to temperature, pressure, concentration of reactants, concentration of solvents, the parameters of the mixing/addition of reagents and/or other conditions in the reaction vessel, which contribute to the interaction between the reagents and the formation of the final product. In one embodiment, the implementation of the alkylation occurs when adding an inorganic acid (e.g. sulfuric acid) to a mixture of 3-methylcatechol and tert-butanol in heptane.

In one variation of the above method includes obtaining 3-methylcytidine. To do this, perform the oxidation of 2-hydroxy-3-methylbenzaldehyde in the suitable reaction conditions with the formation of 3-methylcatechol (Rx 2). In another embodiment of the oxidizer is a feather�led, for example hydrogen peroxide, which was added to 2-hydroxy-3-methaldehyde in an aqueous solution of the base.

In one variation of the above method includes obtaining 2-hydroxy-3-methylbenzaldehyde (Rx 3). To do this, carry out the formylation of o-cresol with paraformaldehyde in a suitable reaction conditions to obtain 2-hydroxy-3-methylbenzaldehyde. The terms "formylation" or "formylation reaction" refers to a chemical reaction in which an organic compound is introduced formyl group (-CH=O). Then 2-hydroxy-3-methylbenzaldehyde is oxidized to obtain 3-methylcytidine.

The formylation reaction can be carried out by formylation of o-cresol with paraformaldehyde in the presence of magnesium chloride (MgCl2) and triethylamine (Et3N) in boiling tetrahydrofuran (THF). The result of this reaction is ortho-formylation of o-cresol. Other suitable formylation reaction is the reaction of Rimera-Timan (i.e. ortho-formylation of o-cresol in a mixture of chloroform/sodium hydroxide).

In one embodiment, the implementation of the 3-methylcatechol produced directly from o-cresol. This method involves the oxidation of o-cresol in the suitable reaction conditions and obtaining 3-methylcytidine (Rx-4). In yet another embodiment of the oxidizing agent is a peroxide, such as peroxide of odor�Yes. At later stages this process involves the alkylation of 3-methylcatechol and the formation of BMC, as described above.

Non-limiting display of reactions 1, 2 and 3 are shown below in scheme (II).

Non-limiting display of reaction 4 is shown below in scheme (III).

In one embodiment, the implementation of the developed another way of getting the BMC. This method involves the oxidation of 5-tert-butyl-3-methyl-2-hydroxybenzaldehyde in the suitable reaction conditions with the formation of 5-tert-butyl-3-methylcatechol (Rx 5). In an additional embodiment of the oxidant is a peroxide, e.g. hydrogen peroxide.

In one embodiment, the implementation of this method involves the synthesis of 5-tert-butyl-3-methyl-2-hydroxybenzaldehyde. To do this, carry out the formylation in suitable conditions, 4-tert-butyl-2-METHYLPHENOL by paraformaldehyde with the formation of 5-tert-butyl-3-methyl-2-hydroxybenzaldehyde (Rx 6). Formirovanie can be carried out using any suitable formylation reaction disclosed in the present description.

In one variation of the above method includes the synthesis of 4-tert-butyl-2-METHYLPHENOL. For this purpose, in suitable reaction conditions carry out the alkylation of o-cresol with isobutylene or t-butanol with the formation of 4-t�et-butyl-2-METHYLPHENOL (Rx 7). The alkylation can be carried out using any suitable alkylation reaction disclosed in the present application. Unexpectedly, this compound, i.e., o-cresol, is a good starting material for obtaining the BMC.

o-Cresol is an inexpensive compound, and methyl group is in the immediate vicinity of the group-OH aromatic cycle. Group-OH o-cresol contributes significantly to the reaction of electrophilic substitution at the para-position that makes it easy to alkylating o-cresol with obtaining 4-tert-butyl-2-METHYLPHENOL. Then 4-tert-butyl-2-METHYLPHENOL formuliruut at suitable reaction conditions to obtain 5-tert-butyl-3-methyl-2-hydroxybenzaldehyde.

Non-limiting display of reactions 5, 6 and 7 is shown below in scheme (IV).

In the present invention developed another way of obtaining the BMC. In one embodiment, the implementation of a method that includes oxidation in suitable conditions, 4-tert-butyl-2-METHYLPHENOL with the formation of 5-tert-butyl-3-methylcatechol (Rx 8). The oxidation can be done by adding peroxide to 4-tert-butyl-2-metalcraze in an aqueous solution of the base.

In one embodiment, the implementation of this method involves the synthesis of 4-tert-butyl-2-METHYLPHENOL. To do this, hold al�iliriana o-cresol tert-butanol or isobutylene in the suitable reaction conditions with the formation of 4-tert-butyl-2-METHYLPHENOL (Rx 9). The alkylation can be carried out using any patcheada alkylation reaction disclosed in the present description. Then 4-tert-butyl-2-metalcraze oxidize with getting the BMC.

Non-limiting display of reactions 8 and 9 is shown below in scheme (V).

In the present invention developed another way of obtaining the BMC. In one embodiment, the implementation of the developed method, which involves the hydrolysis of 2-halo-4-tert-butyl-6-METHYLPHENOL in the suitable reaction conditions with the formation of 5-tert-butyl-3-methylcatechol (Rx 10). In this application, the terms "hydrolysis" or "hydrolysis reaction" refers to a chemical reaction in which water splits into ions (H+and OH-and ion of OH-replaces functional group. The term "halogen" refers to the halogen atoms F, Cl, Br, I. In one of the embodiments of the halogen atom is bromine, i.e. the compound is a 2-bromo-4-tert-butyl-6-METHYLPHENOL. In another embodiment of the halogen atom is chlorine, i.e. the compound is a 2-chloro-4-tert-butyl-6-METHYLPHENOL. In one embodiment, the implementation of the hydrolysis reaction catalyze base and/or salt, such as copper sulfate (II).

In one variation of the above method includes the synthesis of 2-halogen-4-tert-butyl-6-METHYLPHENOL. This �the Intesa includes halogenoalkane in suitable conditions, 4-tert-butyl-2-METHYLPHENOL with the formation of 2-halogen-4-tert-butyl-6-METHYLPHENOL (Rx 11). The terms "halogenoalkane" or "halogenation reaction" refers to the introduction of the halogen atom in an organic compound. Halogenoalkane is carried out by interaction of 4-tert-butyl-2-METHYLPHENOL with halogenous agent, such as brainwashin agent or a chlorinating agent. Non-limiting examples of suitable galogenidami agents include N-bromosuccinimide (NBS), which is brainwashin agent, and/or N-chlorosuccinimide (NCS), which is a chlorinating agent. Halogenoalkane can also occur in the interaction of 4-tert-butyl-2-METHYLPHENOL with elemental Halogens. The symbol "X2"the diagram below (VI) means interacting with elemental halogen. This elemental halogen may be Cl2or Br2.

In one variation of the above method includes the synthesis of 4-tert-butyl-2-METHYLPHENOL. 4-Tert-butyl-2-METHYLPHENOL obtained when the alkylation of o-cresol with isobutylene or t-butanol in suitable conditions as described above (Rx 12). Then the resulting 4-tert-butyl-2-METHYLPHENOL halogenous, getting a 2-halogen-4-tert-butyl-6-METHYLPHENOL.

Non-limiting display of reactions 10, 11 and 12 below in scheme (IV).

In the present invention developed another way of obtaining the BMC. In one embodiment, the implementation�ing this method involves hydrogenolysis in a suitable reaction conditions, 5-tert-butyl-3-aminomethylpyridine with the formation of 5-tert-butyl-3-methylcatechol (Rx 13). The term "hydrogenolysis" or "reaction the experimental data showed" refers to a chemical reaction in which simple bond carbon-carbon or carbon-heteroatom undergoes cleavage by the action of hydrogen. Non-limiting examples of suitable agents to include experimental data showed catalytic agents for the experimental data showed (for example, palladium catalysts), as well as borhydride, such as cyanoborohydride sodium.

In one variation of the above method includes the synthesis of 5-tert-butyl-3-aminoadenine. For this exercise to aminoalkylsilane in suitable conditions, 4-tert-butylcatechol with the formation of 5-tert-butyl-3-aminomethylpyridine (Rx 14). Then 5-tert-butyl-3-aminomethylation subjected to hydrogenolysis with the formation of 5-tert-butyl-3-methylcatechol. Aminoalkylsilane performed using the Mannich reaction. "The Mannich reaction is an organic reaction in which aminoalkylated containing an acidic proton located next to the carbonyl group, interact with formaldehyde and ammonia or primary or secondary amine.

Non-limiting display of reactions 13 and 14 below in scheme (VII).

In one of the embodiments of the invention a method of producing 5-tert-butyl-3-methyl-1,2-phenylene of dibenzoate (BMPD). This method includes radio frequency interference�of BMC in the suitable reaction conditions with a compound, selected from aromatic carboxylic acids and/or derivatives of aromatic carboxylic acids, with subsequent formation of 5-tert-butyl-3-methyl-1,2-phenylendiamine (BMPD). BMC receive any of the methods of synthesis described above in the text of the application.

In the present description, the term "aromatic carboxylic acid" means a compound containing at least one benzene cycle and at least one carboxyl group directly associated with the benzene ring cycle. Have in mind that this aromatic carboxylic acid may be a monocyclic structure or polycyclic structure. Aromatic carboxylic acid may be mono - or polycarboxylic acid. Non-limiting examples of suitable aromatic carboxylic acids include benzoic acid, 1-natoinal acid, 2-natoinal acid, 6H-phenylene-2-carboxylic acid, anthracene-2-carboxylic acid, phenanthrene-2-carboxylic acid and phenanthrene-3-carboxylic acid.

The term "derivative of the aromatic carboxylic acid" in the present description means an aromatic allalone, aromatic anhydride, salt of the aromatic carboxylic acids or any combination of them. Have in mind that the derivative of the aromatic carboxylic acid may be a monocyclic structure or polycyclic structure. Not limited�iausia examples of suitable aromatic allelochemical include any of the halides disclosed above aromatic carboxylic acids (i.e. halides of one or more of the following acids: benzoic acid, 1-natoinal acid, 2-natoinal acid, 6H-phenylene-2-carboxylic acid, anthracene-2-carboxylic acid, phenanthrene-2-carboxylic acid and/or phenanthrene-3-carboxylic acid). Additional non-limiting examples of suitable aromatic allelochemical include benzoyl chloride, benzoylchloride, benzylbromide and benzoinated, aftercare, naphtholphthalein, afterbrain, nahcolite, as well as any combination of the above aromatic allelochemical.

Non-limiting examples of suitable anhydrides of aromatic carboxylic acids include anhydrides of the above-listed aromatic carboxylic acids (e.g., anhydrides of one or more of the following acids: benzoic acid, 1-natoinal acid, 2-natoinal acid, 6H-phenylene-2-carboxylic acid, anthracene-2-carboxylic acid, phenanthrene-2-carboxylic acid and/or phenanthrene-3-carboxylic acid). Additional non-limiting examples of suitable aromatic anhydrides include benzoic anhydride, and any combination of the above aromatic anhydrides.

Non-limiting examples of suitable salts of aromatic carboxylic acids include potassium, sodium or lithium salts of the above-listed aromatic carboxylic acid�t (i.e. salt is one or more of the following acids: benzoic acid, 1-natoinal acid, 2-natoinal acid, 6H-phenylene-2-carboxylic acid, anthracene-2-carboxylic acid, phenanthrene-2-carboxylic acid and/or phenanthrene-3-carboxylic acid). Additional non-limiting examples of salts of aromatic carboxylic acids include potassium benzoate, sodium benzoate, lithium benzoate, 2-aftout potassium 2-aftout sodium and any combination of the previously salts of aromatic carboxylic acids.

Aromatic carboxylic acids or their derivatives may be substituted. The term "substituted aromatic carboxylic acid or its derivative" in the present application means an aromatic carboxylic acid or its derivative in which at least one of the substituents in the benzene ring (different from the carboxyl group) is a substituted gidrolabilna group comprising from 1 to 20 carbon atoms, unsubstituted hydrocarbonous group comprising from 1 to 20 carbon atoms, alkoxygroup comprising from 1 to 20 carbon atoms, heteroatom, or a combination. Thus, the term "substituted aromatic carboxylic acid or its derivative" includes substituted aromatic carboxylic acid, substituted aromatic allalone, substituted aromatic anhydride and/or salt for�esenkoy aromatic carboxylic acid.

In the present description, the terms "substituted hydrocarbyl" and "hydrocarbon" refer to substituents containing only hydrogen atoms and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic, condensed or acyclic structure, and combinations thereof. Non-limiting examples hydrocarbonrich groups include alkyl, cycloalkyl, alkenyl, akadeemiline, cycloalkenyl, cycloalkenyl, aryl, kalkilya, alkylaryl and alkyline group.

In the present description, the terms "substituted substituted hydrocarbyl" and "substituted hydrocarbon" refers to gidrolabilna group, which is substituted by one or more not gidrolabilna replacement groups. Non-limiting examples not hydrocarbonrich substituents are heteroatoms. In the present description, the term "heteroatom" refers to an atom different from carbon or hydrogen. This heteroatom may be a carbon atom from groups IV, V, VI and VII of the periodic system of elements. Non-limiting examples of heteroatoms include: Halogens (F, Cl, Br, I), N, O, P, B, S, and Si. Substituted gidrolabilna groups also include galogenirovannyie groups and/or silicon-containing gidrolabilna group. In the present description, the term "halogenecarbonate group" refers to hydrocar�ilen group, which is substituted by one or more halogen atoms. In the present description, the term "silicon-containing gidrolabilna group" refers to gidrolabilna group, which is substituted by one or more silicon atoms. Atom(s) of silicon may or may not be included in the chain of carbon atoms.

In one embodiment, the implementation BMPD prepared by reacting, in suitable conditions, BMC derived from aromatic carboxylic acids, namely benzoyl chloride. This method includes the interaction of the BMC with benzoyl chloride in the presence of base in suitable reaction conditions with the formation BMPD (Rx 15). Non-limiting examples of bases include pyridine, triethylamine, trimethylamine and/or molecular sieves. Non-limiting display of the reaction below 15 in scheme (VIII).

5-Tert-butyl-3-methyl-1,2-phenylendiamin (BMPD) shown above as formula (IX). BMC depicted in the diagram above formula (I) receive any of the above methods/ways of synthesis. In other words, the method of obtaining BMPD may also include any of the above-described methods of obtaining the BMC.

In one embodiment, the implementation of this reaction involves the addition of benzoyl chloride to a mixture of BMC, pyridine and dichloromethane. The pyridine binds HCl is a byproduct of the reaction.

In one of �of aryanto the implementation of the method includes obtaining BMPD adding benzoyl chloride to the reaction mixture, comprised of BMC, acetonitrile and triethylamine. Triethylamine binds HCl is a byproduct of the reaction. The use of acetonitrile, and triethylamine is preferable to provide an environmentally safe method of producing BMPD low health risk (not toxic), and in particular, to obtain BMPD at a significant scale (i.e., greater than 10 g or more than 1 kg).

In one variation of the above method includes adding water to the reaction mixture (containing BMPD, acetonitrile, triethylamine, benzoyl chloride and BMC) and deposition BMPD. The solvent, i.e., acetonitrile, soluble in water. Not limited to any particular theory, the addition of water to terminate the reaction and changes the solvent capacity of the solvent, which leads to precipitation from solution BMPD ("sediment BMPD"). The presence of a solvent system containing acetonitrile, allows us to offer a simple, economical and effective way of obtaining BMPD suitable for commercial and industrial applications. Fig.1 shows a non-limiting block diagram of a receiving BMPD.

In one of the embodiments the method includes cleaning and education BMPD composition BMPD that contains more than 98 wt.% or more than 99 wt.% BMPD. Cleaning BMPD includes the implementation of one or more transactions with sediment BMPD: the process of recrystallization, extraction, concentration, washing, distillation and �ubuy the combination of the above operations.

In one embodiment, the cleaning implement comprises dissolving the precipitate in BMPD non-aqueous solvent (e.g., ethyl acetate and extraction with water. Not limited to a specific theory, it is believed that the extraction with water to remove ionic impurities and/or ionic by-products from non-aqueous phase, whereby it is cleaned BMPD. The nonaqueous phase was dried (over MgSO4) and concentrated by evaporation on a rotary evaporator ("concentrate") in combination with flushing hydrocarbons (heptane) to remove organic by-products/impurities. Recrystallization yields a composition purified BMPD that contains more than 98 wt.% BMPD or more than 99 wt.% BMPD.

In one embodiment, the cleaning implement includes a distillation of the concentrate in combination with flushing hydrocarbon (heptane). Filtration and drying yields a composition purified BMPD that contains more than 98 wt.% or more than 99 wt.% BMPD. Fig.2 shows a non-limiting block diagram of the purification sludge BMPD.

BMPD mainly used as an internal electron donor in precatalytic/catalyst composition for polymers based on olefins (particularly propylene polymers), as disclosed in the provisional application U.S. No. 61/141902, filed December 31, 2008, and provisional application U.S. No. 61/141959, filed December 31, 2008 �., the content of each of these applications is fully incorporated into the present application by reference.

DEFINITIONS

All references to the periodic table of elements in this application shall refer to the periodic table of the elements, published by CRC Press, Inc., 2003, and are protected by copyright. In addition, all references to the group or groups should be attributed to the group or groups reflected in this periodic table of elements using the numbering system of IUPAC groups. Unless otherwise defined herein, is not implied by the context or is not generally accepted in the art, all of the shares and percentages are given on a mass basis. For the purposes of patent practices of the United States the contents of any patent, patent application or publication referenced in this application are incorporated in this application in its entirety using links (or the American equivalent versions of these documents are also incorporated by reference), especially with regard to the disclosure of synthesis techniques, definitions (to the extent in which they are not inconsistent with any definitions provided in the present application) and General knowledge in the art.

The term "comprising" and its derivatives does not imply the exclusion of the presence of any additional component, stage techniques, regardless of whether they are opened in �asteady the application. To avoid any doubt, all compositions claimed in the text using the words "comprising" may include any additional additive, adjuvant or polymeric compounds or of other nature, if not opposite directions. In contrast, the term "essentially consisting of" excludes any further mention of any other components, the stages of the methodology, except for those that are not essential for the applicability of the invention. The term "consisting of" excludes any component, phase or techniques that are not specified or not specifically listed. The term "or", unless otherwise indicated, refers to the above components separately and in any combination.

Any numerical range defined in the present application, includes all values from smallest to largest, with an increment of one unit, provided that the difference between the smallest and largest value is at least 2 units. As an example, if it is determined that the number of the component or the value relating to the composition or physical property, such as the number of components of the mixture, softening temperature, melt index, etc., is in the range from 1 to 100, meaning that this definition explicitly specified all individual values, such as 1, 2, 3, etc., and all subranges, such as up to 20, from 55 to 70, from 97 to 100, etc. For values smaller than one, the increment shall be equal to 0,0001, 0,001, 0,01 or 0.1 for each case. The above is only an example of what exactly is meant by the definitions of numerical values, and we must assume that all possible combinations of numerical values between the lowest and highest values explicitly specified in this application. In other words, any given in the application form numerical range includes any value or subrange within a specified range. In the present application is specified numeric ranges that belong to the melt index, the melt flow rate of and other properties.

The terms "blend" or "polymer mixture" in the present description refers to a mixture of two or more polymers. Such a mixture may have or not have the ability to mix (there is no separation of the phases at the molecular level). Such a mixture can include or not include a separate phase. Such a mixture may contain or may not contain one or more domain configurations, as determined according to transmission electron spectroscopy, scattering of light rays, x-ray scattering and other methods known in the art.

The term "composition" in the present description includes a mixture of materials that are not included in the composition, as well as reaction products and decomposition products formed from the materials of the composition.

The term "polymer" refers to a macromolecular compound obtained by polymerization of monomers of the same or different type. "Polymer" includes homopolymers, copolymers, terpolymers, interpolymer, etc. the Term "interpolymer" means a polymer obtained by polymerizing at least two types of monomers or comonomers. It includes, but is not limited to, copolymers (the term usually refers to polymers derived from two different types of monomers or comonomers), terpolymers (this term usually refers to polymers derived from three different types of monomers or comonomers), terpolymer (this term usually refers to polymers derived from four different types of monomers or comonomers), etc.

The term "polymer-based olefin" refers to a polymer main mass, the content of which in relation to the total weight of the polymer is an olefin in polymerized form, for example ethylene or propylene. Non-limiting examples of polymers based on olefins include polymers of ethylene and polymers of propylene-based.

The term "polymer based on propylene" in the present description refers to the polymer main mass, the content of which (from General Koli�society of monomers, capable of curing) is polymerized propylene monomer, and it can optionally include at least one polimerizovannye of comonomer.

The term "alkyl" in the present description refers to a branched or unbranched, saturated or unsaturated acyclic hydrocarbon radical. Non-limiting examples of suitable alkyl radicals include, for example, methyl, ethyl, n-propyl, isopropyl, 2-propenyl (or allyl), vinyl, n-butyl, t-butyl, isobutyl (or 2-methylpropyl"), etc alkili include from 1 to 20 carbon atoms.

The term "substituted alkyl" in the present description refers to the above alkyl in which one or more hydrogen atoms associated with any carbon atom of alkyl, substituted with another group, for example halogen, aryl, substituted aryl, cycloalkyl, heteroseksualci, substituted heteroseksualci, halogen, halogenation, hydroxy, amino, phosphido, alkoxy, amino, thio, nitro, and combinations. Suitable substituted alkali include, for example, benzyl, trifluoromethyl, etc.

The term "aryl" in the present description refers to an aromatic substituent which can be a single aromatic cycle or a structure of several aromatic cycles that are condensed, connected by a covalent bond or are linked by some groups�, for example methylene or ethylene fragment. Aromatic cycle(s) may include, among others, phenyl, naphthyl, anthracene and biphenyl. These arily include from 6 to 20 carbon atoms.

The term "substituted phenylene aromatic diester complex" includes substituted 1,2-phenylene aromatic complex dietary substituted 1,3-phenylene aromatic complex dietary and substituted 1,4-phenylene aromatic complex dietary. In one of the embodiments of substituted phenylenediamine complex is a diester of 1,2-phenylenediamine complex aromatic diester having the following structure (A):

where the substituents R1-R14are the same or different from each other. Each of the substituents R1-R14selected from hydrogen, substituted gidrolabilna the group including 1 to 20 carbon atoms, unsubstituted hidrocarburos the group including 1 to 20 carbon atoms, alkoxygroup comprising from 1 to 20 carbon atoms, a heteroatom, and combinations thereof. At least one of the substituents R1-R14is not hydrogen.

Research methods

Data1H nuclear magnetic resonance (NMR) were recorded on a Bruker 400 MHz in CDCl3(M. D.).

As an example, and not limitation, the following are examples for us�oasea the invention.

EXAMPLES

Example 1: Conversion of 3-methylcytidine 5-tert-butyl-3-methylcatechol (reaction 1)

In a 1000 ml three-neck flask equipped with a stirrer, reflux condenser and thermometer, was placed 3-methylcatechol (25,0 g, 0.20 mol), tert-butanol (38,0 ml of 0.40 mol) and 500 ml of heptane, and then slowly added sulfuric acid (98%, 20 g). This mixture was heated to 80°C for 6 hours until gas chromatography (GC) showed completion of the reaction. The solvent was removed in vacuo, the residue was dissolved in CH2Cl2and washed with water, NaHCO3(water.), saturated brine, and dried (Na2SO4). After filtration and concentration was obtained 5-tert-butyl-3-methylcatechol (36 g, 84%).1H NMR: of 6.79 (s, 1H), 6.75 in (s, 1H), 5,01 (user., 1H), to 2.29 (s, 1H), 1,29 (s, 9H).

Example 2: Transformation of 2-hydroxy-3-methylbenzaldehyde 3-methylcatechol (reaction 2)

In a 100-ml three-neck round bottom flask equipped with a stirrer, reflux condenser, thermometer and addition funnel, was placed 6.8 g of 2-hydroxy-3-methaldehyde and 25 ml of 2n. aqueous solution of NaOH. With stirring in portions of 10 ml was added dilute H2O2by maintaining an internal temperature of 40 to 50°C. After adding the first portion of hydrogen peroxide, the temperature was increased to 45°C, and the dark solution formed. The temperature was allowed to drop to 40°C, after chodorowski second portion of hydrogen peroxide. After addition of hydrogen peroxide the reaction mixture was allowed to cool to room temperature, saturated with sodium chloride and was extracted with ether (3×50 ml). The combined extracts were dried over sodium sulfate, ether was removed, and distilled, yielding the product.1H NMR: 6,73 (m, 3H), 2,89 (s, 3H).

Example 3: Conversion of o-cresol 2-hydroxy-3-methylbenzaldehyde (reaction 3)

A 1-liter chetyrehosnuju round bottom flask equipped with a stirrer, reflux condenser, thermometer, input and nitrogen bubbler, was placed 20,64 ml of o-cresol and 14.0 g of paraformaldehyde. With a pipette THF was injected and then using a dropping funnel was added triethylamine. After stirring for another 10 min slowly with a pipette was added o-cresol, which led to the formation of opaque light pink mixture, which was boiled to reflux for 4 hours. The obtained reaction mixture was cooled and diluted with 200 ml of ether, washed with 1N. HCl, water and dried over Na2SO4. After removal of the solvent in vacuo the residue was purified by distillation, yielding 15.6 g (57%) of product.1H NMR: of 11.3 (s, 1H), of 9.89 (s, 1H), 7,41 (d, J=7,44 Hz, 2H), 6,95 (t, J=7.5 Hz, 1H), 2,30 (s, 3H).

Example 4: Conversion of 5-tert-butyl-3-methylcytidine 5-tert-butyl-3-methyl-1,2-phenylene, dibenzoate (reaction 15)

In a 250-ml round-bottom flask was placed 5-tert-BU�Il-3-methylcatechol (BMC) (0,025 mol), pyridine (0.05 mol, 1.0 EQ.) and dichloro methane (50 ml). The flask was cooled in an ice-water bath and dropwise added benzoyl chloride (0.1 mol, 1.0 EQ.). Upon completion of the addition the temperature of the reaction mixture was raised to room temperature and stirred over night. The mixture was diluted with an additional portion of dichloromethane and then washed with a mixture of a saturated solution of NH4Cl/1H. HCl, water, saturated sodium bicarbonate solution and concentrated solution of salt. The organic layer was separated and dried over magnesium sulfate. After filtration the filtrate was concentrated and the residue was dried under vacuum. A large portion of the crude product was sufficiently pure and was further purified by recrystallization from ethanol (solid product) or by distillation under vacuum to obtain product in the form of solids/liquids from white to yellow. Crude yield 98%.1H NMR (500 MHz, CDCl3, M. D.): 8,08 (DD, 2H), 8,03 (DD, 2H), 7,53 (TT, 1H), 7,50 (TT, 1H), 7,38 (t, 2H), 7,34 (t, 2H), 7,21 (d, 1H), of 7.19 (d, 1H), 2,28 (s, 3H), of 1.34 (s, 9H).

Example 5: Conversion of 5-tert-butyl-3-methylcytidine 5-tert-butyl-3-methyl-1,2-phenylene, dibenzoate (reaction 15)

500-ml three-neck round bottom flask with a channel for insertion of thermocouple supplied drip funnel/input for N2, mechanical stirrer, and stopper. After purging�Oia system of N 2the flask was placed 5-tert-butyl-3-methylcatechol (20.0 g, 0.11 mole) and CH3CN (100 ml). The mixture was stirred at room temperature until complete dissolution of solids. Into the flask was added triethylamine (26,8 g, 0.27 mole) and brought the internal temperature up to 10°C using a bath of ice water. Dropwise added benzoyl chloride (34,4 g, 0,24 mol), maintaining the temperature between 10-20°C. the addition took about 30 minutes Removed the bath with ice and the obtained thick suspension was allowed to stir at room temperature for 1 hour.

1-liter three-neck round bottom flask with a channel for insertion of thermocouple supplied input to N2, mechanical stirrer, and stopper. Into the flask was added water (400 ml). The previously obtained suspension was added in eight portions over about 20 min. the resulting suspension was stirred at room temperature for 30 min and then separated solid substance by filtration.

The crude solid was dissolved in EtOAc (150 ml) and was extracted with water (75 ml). The aqueous phase was discarded and the EtOAc phase was dried over MgSO4. MgSO4separated by filtration, receiving 175 g light brown solution. The solution was concentrated on a rotary evaporator (temperature of the bath to 45-50°C, a pressure of 150-200 mm Hg), driving 96 g of solvent. Added heptane (150 ml) and continued concentrating, p�of contracts 55 g of distilled solvent. Removed the flask from the rotary evaporator and placed in a rotor magnetic stirrer. Has introduced a number of for the seed crystals and the mixture was stirred at room temperature. Crystallization began almost immediately. The suspension was stirred at room temperature for about 1 hour and then the product was separated by filtration. Cake filtrate was washed with heptane (40 ml) and then dried to constant weight (5 mm Hg/40°C), yielding the product as an off-white crystals (35 g, 81%).

Example 6: Conversion of 5-tert-butyl-3-methylcytidine 5-tert-butyl-3-methyl-1,2-phenylene, dibenzoate (reaction 15)

A 5-liter three-neck round bottom flask with a channel for insertion of thermocouple supplied drip funnel/input for N2, mechanical stirrer, and stopper. After you purge the system of N2in a container put the original 5-tert-butyl-3-methylcatechol (314,3 g, 1.75 mole) and CH3CN (1570 ml). The mixture was stirred at room temperature until complete dissolution of solids. Into the flask was added triethylamine (423 g of 4.17 mmol) and the internal temperature of the reaction mixture was adjusted to 10°C using a bath of ice/water. Dropwise added benzoyl chloride (543 g, 3,84 mol), maintaining the temperature between 10-20°C. Initially in the dropping funnel was added only half of the benzoyl chloride, to prevent the addition of all substances for Odie� time. In total, the addition took about 2 hours. Cleaned the bath with ice and left a thick residue to stir at room temperature over night.

12-liter three-neck round bottom flask with an outlet provided at the bottom of the channel for thermocouple input N2, mechanical stirrer, and stopper. Into the flask was added water (6.3 l). Into the flask for 15 min portions was added the slurry obtained in the above synthesis, washing away her from the walls of the reaction vessel with water (100 ml) and CH3CN (50 ml). The resulting suspension was stirred at room temperature for 2 hours and then separated solid substance by filtration. The solid is placed in a container for storage until the completion of the synthesis of the second portion of the substance. These two portions were treated jointly.

A second portion received in a similar way.

Treatment:

2 servings of crude solids obtained by the method of example 6 (a total of 1968, with the moisture content), was dissolved in EtOAc (4,8 l), was extracted with water (2400 ml) and was allowed to stir at room temperature over night. The aqueous phase was discarded and the light brown solution in EtOAc (5529 g) were divided into two portions for distilling off the solvent.

The Stripping solvent No. 1

Concentrated the resulting solution (2824,9 g), by distillation of the solvent skorodin by the motion of the distillate (the temperature of the distillate 40-45°C, 250-300 mm Hg) and getting 1718 g of distilled solvent. Added heptane (2.4 l) and continued to concentrate the mixture is getting 926 g of distilled solvent. The mixture was allowed to cool to room temperature and stirred over night. Product was collected by filtration, sludge cake was washed with heptane (620 ml) and then dried to constant weight (5 mm Hg/25°C), yielding the product as an off-white crystals (to $ 636.6 g).

The Stripping solvent No. 2

Concentrated the resulting solution (2692,4 g), by distillation of the solvent with the short path of movement of the distillate (the temperature of the distillate 40-45°C, 250-300 mm Hg) and getting 1545 g of distilled solvent. Added heptane (2.4 l) and continued to concentrate the mixture is getting 864 g of distilled solvent. The mixture was allowed to cool to room temperature and stirred over night. Product was collected by filtration, sludge cake was washed with heptane (620 ml) and then dried to constant weight (5 mm Hg/25°C), yielding the product as an off-white crystals (606,8 g).

In total, received 1243,4 g of product with a melting point of 110-112°C, which corresponds to a yield of 92%. The purity of the product exceeded 99 wt.%.

There is a specific intention that the present invention is not limited contained in the application versions of the implementation and illustrations, but included adultery�nnye forms of these variants of implementation, including separate parts of the embodiments and combinations of elements of different embodiments that fall within the scope described hereinafter in the claims.

1. A method of producing 5-tert-butyl-3-methyl-1,2-phenylene of dibenzoate, including:
the interaction in the reaction conditions, 5-tert-butyl-3-methylcatechol (CPA) with triethylamine and a compound selected from the group consisting of aromatic carboxylic acid and a derivative of the aromatic carboxylic acids, where the derivative of the aromatic carboxylic acid is an aromatic allalone, aromatic anhydride, salt of the aromatic carboxylic acids or any combination of them; and where the aromatic carboxylic acid is a benzoic acid; and
the formation of compositions containing 5-tert-butyl-3-methyl-1,2-phenylene, dibenzoate (BMPD).

2. A method according to claim 1, including cleaning and education BMPD composition BMPD containing more than 98% of the BMPD.

3. A method according to claim 1, comprising adding benzoyl chloride to the reaction mixture containing IUD, acetonitrile and triethylamine and education BMPD.

4. A method according to claim 1, comprising adding water to the reaction mixture and precipitation BMPD.

5. A method according to claim 1, including dissolution of precipitated BMPD and extraction of the water.

6. A method according to claim 5, comprising the formation of the composition BMPD that contains more than 98 wt.% BPD.

7. A method according to claim 1, including:
alkylation in the reaction conditions, 3-methylcytidine compound selected from the group consisting of tert-butanol and isobutylene; and
the formation of 5-tert-butyl-3-methylcatechol.

8. A method according to claim 1, including:
oxidation reaction conditions, 5-tert-butyl-3-methyl-2-hydroxybenzaldehyde; and
the formation of 5-tert-butyl-3-methylcatechol.

9. A method according to claim 1, including:
oxidation reaction conditions, 4-tert-butyl-2-METHYLPHENOL; and
the formation of 5-tert-butyl-3-methylcatechol.

10. A method according to claim 1, including:
the hydrolysis in the reaction conditions of 2-halogen-4-tert-butyl-6-METHYLPHENOL; and
the formation of 5-tert-butyl-3-methylcatechol.



 

Same patents:

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

Multicore bisazide // 2067572
The invention relates to new compounds of General formula I

< / BR>
Z=-SO2-, -X--Y--X-

X=O,S

Y=0, S, SO2; CO.,

which can be used as light-sensitive components of photoresists

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 0-5°C.

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

3 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 (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 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 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

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to new idebenone derivatives substituted by carboxylic acid with general formula I wherein R1 represents C2-C22 saccharic acid with a direct or branched chain, while two or more hydroxy groups are independently substituted by C1-C22 carboxylic acid, wherein the term 'branched' refers to one or more groups of a lower alkyl. The invention also refers to a formulation for skin treatment containing the above idebenone derivatives, a method of treating the skin changes by local applications with these idebenone derivatives, as well as to methods of synthesis thereof. When adding the idebenone derivatives according to the present invention into the formulations for local application, they possess the antioxidant action effective in treating the skin changes.

EFFECT: above idebenone derivatives have unexpectedly occurred to be effective in skin treatment, especially in relation to skin tolerance.

20 cl, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of obtaining esters of amyl alcohols and simplest carboxylic acids C1-C4. Alcohol-containing wastes of caprolactam production are used as raw material. Method includes etherification of alcohol-containing wastes of caprolactam wastes with simplest carboxylic acids C1-C4 in presence of acidic catalyst. Process of etherification is carried out with continuous azeotropic distillation of water with reaction mixture components, as catalyst, sulfuric or orthophosphoric acid is used, catalyst is loaded in amount 0.1-2.5% of the total weight of initial substances, reaction mixture is cooled to 20-30°C and neutralised with water-alkaline solution with mixing to water layer pH 7-8, water phase is separated, organic phase is washed one-two times with water, final purification of esters is carried out by fractional distillation of organic phase. Obtained products are suitable for application as solvents for paints and varnishes, raw material for organic synthesis, as component of complex fuel additives.

EFFECT: obtaining esters of amyl alcohols and simplest carboxylic acids C1-C4, characterised by high purity without catalyst admixtures, low water content - not more than 0,1%, and residual organic acids - not more than 0,01 without application of secondary rectification, as absence of acid facilitates purification of esters.

9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining benzophenone (meth)acrylates, in which contact of hydroxybenzophenones and (meth)acrylic acid is realised in the presence of catalytic quantities of concentrated sulphuric acid, alkyl- or arylsulphonic acid with the following neutralisation of the catalyst and further purification of the raw monomer.

EFFECT: method makes it possible to achieve high degrees of conversion, which leads to the considerable reduction of quantity of byproducts.

5 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of processing ammonium lactate into lactic acid and esters thereof. The disclosed method is carried out by bringing aqueous ammonium lactate solution into contact with a hydroxyl-containing compound in a vertical mass-exchange apparatus at high temperature and pressure, removing reaction by-products, primarily with a stream of steam and end products, primarily with a liquid stream. The process is carried out in adiabatic conditions in one or more mass-exchange apparatus.

EFFECT: method simplifies the process of converting ammonium lactate and reduces power consumption, prevents salt deposits on heated surfaces, reduces the amount of alcohol fed into the reaction, while maintaining a high degree of conversion of ammonium lactate and short duration of the process.

5 cl, 4 dwg, 5 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: claimed invention relates to compounds of the following formula , in which n equals integer number from 1 to 15, m equals 0, 1, 2 or 3, and R represents hydrocarbon chain of polyunsaturated fatty acid, selected from omega-3 and omega-6 polyunsaturated fatty acids, and to method of obtaining them.

EFFECT: development of pharmaceutical or cosmetic composition based on said compounds and to method of acne or seborrheic dermatitis treatment for cosmetic purposes.

16 cl, 4 dwg, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing an acrylic ester of formula CH2=CH-COO-R, in which R denotes an alky radical, straight or branched, containing 1-18 carbon atoms and optionally a nitrogen heteratom, wherein at the first step glycerine CH2OH-CHOH-CH2OH is dehydrated in the presence of an acid catalyst to obtain acrolein of formula CH2=CH-CHO, then a second step where the obtained acrolein is converted via catalytic oxidation to acrylic acid CH2=CH-COOH, a third step where the acid obtained at the second step is either esterified with an alcohol R0OH, wherein R0 is CH3, C2H5, C3H7 or C4H9, followed by re-esterification of the obtained ester with an alcohol ROH, wherein R assumes the value given above, or esterified with an alcohol ROH, wherein R assumes said value, where content of furfural in the acrylic ester is less than 3 ppm.

EFFECT: high efficiency of the method.

15 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing pure methacrylic acid, which involves: a) gas-phase oxidation of a C4 compound to obtain a methacrylic acid-containing gas phase, b) condensing the methacrylic acid-containing gas phase to obtain an aqueous methacrylic acid solution, c) separating at least a portion of the methacrylic acid from the aqueous methacrylic acid solution to obtain at least one methacrylic acid-containing raw product, d) separating at least a portion of methacrylic acid from the at least one methacrylic acid-containing raw product by thermal separation to obtain pure methacrylic acid, wherein at step (d), methacrylic acid is separated from at least a portion of at least one methacrylic acid-containing raw product by fractionation, and wherein the pure methacrylic acid is collected through a side outlet used for the fractionation column, and the amount of pure methacrylic acid collected over a certain time interval ranges from 40% to 80% of the amount of the methacrylic acid-containing raw product fed into the fractionation column over the same time interval. The invention also relates to an apparatus for producing methacrylic acid using said method, the apparatus comprising: a1) a gas-phase oxidation unit, b1) an absorption unit, c1) a separation unit, and d1) a purification unit, wherein the purification unit has at least one distillation column, wherein the at least one distillation column has at least one side outlet for pure methacrylic acid. The invention also relates to a method of producing methacrylic esters, polymethacrylate, polymethacrylic esters, which includes a step for said production of pure methacrylic acid.

EFFECT: obtaining an end product with fewer by-products while simplifying the process.

32 cl, 3 tbl, 4 dwg, 6 ex

FIELD: machine building.

SUBSTANCE: invention refers to a method for obtaining an ether additive, which involves mixing of dicarboxylic acid with ether so that water, ether and excess alcohol is obtained with further separation of water and alcohol from ether by rectification; at that, as an acid there used is oxalic acid, and as alcohol - n-butanol or 2-ethylhexanol. Cyclohexane used as a solvent is supplied for mixing of oxalic acid with alcohol, and rectification is performed in two columns so that cyclohexane (solvent) is obtained in the first column, which is returned to the stage of mixing with oxalic acid and alcohol and supply of residue of the first column to the second one so that alcohol and target product (ether additive) are obtained in it.

EFFECT: method allows simplifying the process and making it more economic by excluding the use of a catalyser, processing stages of reaction mass with an agent decomposing the catalyser, and reaction mass sorption and filtration stages.

2 cl, 2 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to chemical engineering and specifically to processing fusel oil, which is a large-tonnage waste in the alcohol industry. Fusel oil from production of ethyl alcohol is processed by esterification with glacial acetic acid in the presence of a sulphuric acid catalyst, and neutralisation, wherein esterification is carried out while boiling the reaction mixture and continuously separating water using a separating flask. The obtained product is separated from the catalyst under a vacuum at temperature not higher than 110°C. The obtained product and the catalyst are separately neutralised and the obtained product is additionally dried.

EFFECT: method enables to process fusel oil into a highly efficient component of mixed solvents of high quality with low cost of production and high output of the product.

4 cl

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