How prelinlinary

 

(57) Abstract:

The inventive product is vinylphosphonate acid Branstad. Purity 99% Reagent 1: vinylphosphonate acid Bronsted selected from the group of vinyl esters of saturated or unsaturated carboxylic acid. Reagent 2: another acid Branstad. Reaction conditions: in the presence of compounds of ruthenium as a catalyst when its concentration from 30,000 to 0.23 h/million by weight of the liquid-phase reaction mixture at a molar ratio of acid Brenster and ruthenium 0,5/1 at a temperature of 75-259°C and a pressure of from 10 to 2644,8 mm RT.article 11 C. p. F.-ly, 4 PL.

The invention relates to a method of prelinlinary vinylphosphonic acid Bronsted other acid Bronsted selected from the group of vinyl esters of saturated or unsaturated carboxylic acid, which receive liquid-phase mixture containing a specified derivative the vinyl and the specified acid Branstad, in the presence of compounds of ruthenium at a temperature at which there is prevenlion with selection as the target product vinylphosphonic.

Methodology prelinlinary or vinyl interchange exists in several desacyl the active hydrogen-containing compound in the following form:

RX+RCH= CH RCH=CH2+R-X, where R represents carboxy, amido, araxi, alkoxy, etc., X represents hydrogen, hydroxyl, alkyl, aryl, etc., and R' denotes carboxyl, amido, alkyl, substituted alkyl, aryl or substituted aryl.

Prevenlion called the "reaction of the vinyl interchange" to distinguish it from the typical reactions of transesterification and the ether-acid metabolism [1] are the following advantages of this reaction. Very mild conditions of the reaction and low outputs of by-products lead to high outputs monomers with higher purity and activity than those obtained by the interaction of acetylene with acids. In addition, complex vinyl esters of dibasic acids are much more easier by vinyl exchange, rather than through acetylene path, and recent developments in this laboratory have shown that the reaction of vinyl acetate catalyzed by salts of mercury, is not limited to carboxylic acids, and can and will occur with other compounds containing active hydrogen, such as acetoacetic ester and glycol ethers [1]

Known reaction of vinyl exchange between simple vinyl ether and alcohol using PAL and carboxylic acid.

Literary sources suggest that the preferred catalysts of reactions prelinlinary compounds mercury and palladium. Known for catalysis of reactions of PT (II) and Rh (III) [3] it is Known the use of supported catalysts on the basis of salts of Nd, PD, PT, Ir, Rh, Ru, or OS in a vapor-phase process prelinlinary [4] Experimental part of this patent discloses the use of only palladium on coal, copper, coal, iron, coal, palladium/copper coal palladium/copper/iron on silica, acetate of mercury in coal and chloride of mercury in coal. Nd and Pd are mentioned as preferred metals. In this patent there is no consideration of the question of the special advantages of the use of ruthenium compounds as catalysts for reactions prelinlinary and implementation of reactions in liquid-phase reaction medium with the use of ruthenium compounds as the catalyst.

Known techniques have the following disadvantages.

The catalyst based on mercury is toxic, undesirable volatile and, as a rule, activated with sulfuric acid, promotiom reaction, then deactivated by neutralization of the extension of the free acid, gr> Catalysts based on palladium not sufficiently thermally stable to allow you to delete the product by distillation at elevated temperatures, the catalyst is often deactivated by formation of metallic PD.

Know the use of catalysts based on ruthenium for promotion of addition of carboxylic acids to alkynes and production of alkenylboronic. In particular, facilitated the interaction of carboxylic acids with substituted alkynes. It is also possible reaction of carboxylic acids with acetylene (ventiliruemye) with a vinyl ester, however, in a smaller degree. Explore the various precursors of catalysts, which include ruthenium-carbonyl, bis/this 5-cyclooctadiene/ruthenium (II)/three-n-butylphosphine and bis/this 5-cyclooctadiene/ruthenium (II)/trialkylphosphine/maleic anhydride. (Company M and other ORGANOMETALLIC Compounds, 1983, 2, S. 1689-1691; Mitsudo T. and others the Journal of Organic Chemistry, 1985, 50, S. 1566-1568; Mitsudo T. and others the Journal of Organic Chemistry, 1987, 52, S. 2230-2239.

The use of these and similar compounds of ruthenium as catalysts prelinlinary, apparently, until the present invention was not recognized. Vigorou solves some of the above disadvantages of the known catalysts, also was not evaluated to the present invention. Therefore, in the field of prelinlinary there is a need for a catalyst having high catalytic activity at elevated temperatures, which would facilitate the separation of the desired reaction product, without affecting the other components present in the mixture of the reaction products.

The invention relates to a method of prelinlinary vinyl derivative of the acid of another Breasted acid Bronsted, which receive liquid-phase mixture containing a specified vinyl derivative and the above acid Branstad in the presence of a ruthenium compound, at a temperature at which there is prevenlion, and extracted as a product prelinlinary vinyl derivative of another acid Branstad. In a preferred embodiment, the method ruthenium soluble in the reaction mixture in a catalytically effective amount.

Prelinlinary are equilibrium reactions. Reaction efficiency is measured by the degree to which the desired reaction product of prelinlinary present in the products of the equilibrium reaction. In other words, the reaction generates more than m the reaction products of prelinlinary.

The reaction of the present invention includes a combination of a vinyl derivative of the acid of Branstad, another acid Bronsted with which the exchange occurs, the compounds of ruthenium and conditions of the liquid-phase reaction.

Vinyl derivative is any connection in which the vinyl group is linked to acid Branstad. They can be characterized as vinnilirunnu acid Branstad. Vinyl covers a group of the formula

RoR1C= CH where Roand R1each separately represents hydrogen, alkyl containing from 1 to about 12 carbon atoms, cycloalkyl, aryl, alkalemia esters, etc., Acid Bronsted is any species that can act as a source of protons.

Illustration of suitable vinyl derivatives acid Bronsted for the practice of the present invention are vinyl acetate, vinylbilt, vinylbenzoate, vinylmethyl, vinylacetat, devicelistener, divinitatem, divinerecipes, finalproject, ministart, vinylacetat, vinilinum, vinyl 2-ethylhexanoate, vinylcyclohexane, N-vinylpyrrolidone, N-vinylamine, finalfantasy ether, vinylmations ether, Vinitaly ether, N-vinyl-2-oxazolidinone, acrylate, the vinyl chloride, vinylsulfonate etc.

Preferred vinyl derivatives are complex, vinyl esters of carboxylic acids and mineralquelle or akrilovye esters because they are more available commercially.

Illustration of suitable acids Branstad for the practice of the present invention are carboxylic acids such as monocarboxylic and polycarboxylic acids, in particular acetic acid, propionic acid, butyric acid, pavlikova acid and other neocolony, stearic acid and other complex vinyl esters of fatty acids, benzoic acid, terephtalate acid, isophthalic acid, phthalic acid, adipic acid, succinic acid, malic acid, maleic acid, polyacrylic acid, crotonic acid, acrylic acid, methacrylic acid, salicylic acid, cinnamic acid, 2-atelophobia and cyklokapronbuy acid; amides, such as 2-pyrrolidone, 2-pyrrolidinone, E-caprolactam, 2-oxazolidone, etilenmocevina, N-acetyltyrosine and succinimide; alcohols such as methanol, ethanol, n-propanol, isobutyl alcohol, fluorinated alkanols, such as 1,1,1,3,3,3-hexamer-2-propanol, monoethanolamine, diethanolamine and triethanolamine; feelin the e are essentially acid, such as secondary aromatic amines, azoles, protected amines and imini, silazane, etc. esters of oxyacids, such as hydroxyalkyl-acrylates (namely, 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate) and hydroxyalkyl-alkanoate (namely, 2-hydroxyethylated, 2-gidroksietilmetilts); sulfonamides such as diethylsulfate and toluensulfonate; silanes such as phenylsilane, diphenylsilanediol, triphenylsilanol-ol, dimethylsilanol, trimethylsilane-ol, dimethylsilanol, trimethylsilane - ol, etc.

The preferred acid Bronsted are carboxylic acids, alcohols, imine, amides, imides, phenolic compounds, etc.

Illustration of the reactions prelinlinary, which can be carried out using the proposed method, are the following:

Vinyl derivatives of Acid Bronsted Product

The vinyl acetate + pavlikova acid vinylbilt

Vinylbenzoate + pavlikova acid vinylbilt

The vinyl acetate + methacrylic acid vanillacream

The vinyl acetate + acrylic acid vinylacetat

The vinyl acetate + isophthalic acid divinitatem

The vinyl acetate + terephthalic acid divinitatem

The vinyl acetate + propionic acid finalproject

Vinylbilt + stearic acid ministart

The vinyl acetate + salicylic acid, fenilsalicilat

The vinyl acetate + cinnamic acid vinilinum

Finalproject + 2-atelophobia

acid vinyl 2-ethyl-hexanal

The vinyl acetate + cyklokapronbuy

acid vinylcyclohexane

The vinyl acetate + 2-pyrrolidinone N-vinyl 2-pyrrolidinone

Vinylbilt + 2 pyrrolidinone N-vinyl-2-pyrrolidinone

Vinylbilt + succinamic N-vinylamine

Vinylmations + phenol finalfantasy ether

Ether

The vinyl chloride + methanol vinylmations ether

Vinylmations + ethanol unilateraly ether

Ether

The vinyl acetate + 2-oxazolidinone, N-vinyl-2-oxazolidinone

The vinyl acetate + etilenmocevina N-vinyl etilenmocevina

The vinyl acetate + etilenmocevina N-vinyl etilenmocevina

The vinyl acetate + N-acetyl ethylene-

urea N-vinyl N-acetylamino-

Cavina

The vinyl acetate + 2-hydroxyethylated 2-vinylacetylene

Vinylbilt + 2-gidroksietilmetilts 2-vinyloxyethyl

Vinylbilt + 2-hydroxyethylacrylate 2-vinyloxyethyl

The proposed method provides an excellent way of getting the vinyl compounds vsledstvii the reaction. Ruthenium catalysts are easily available as soluble and can be used in the form of non-volatile compounds with high thermal resistance and having a high catalytic activity only at elevated temperatures. In contrast, the palladium catalyst based on ruthenium does not lead to the observed deposition of the metal, even when the reaction is carried out at temperatures above 150aboutC. From a practical point of view, physical and chemical properties of ruthenium catalyst (soluble, Neleus and has high thermal stability) allow the extraction of the product by distillation. These properties suggest that the system ruthenium catalyst is much better known techniques prelinlinary using palladium and mercury.

The selection of suitable compounds of ruthenium to provide catalytic activity for the reaction of prelinlinary is not crucial. Any connection of ruthenium can be used effectively to implement the response prelinlinary. However, I believe that the invention includes new catalysts based on ruthenium, which promotirovat vinyl exchange (re the tori and the desired catalytic activity is the precursor for ruthenium catalyst, which can be converted to [Ru(CO)2R2] or similar connection, even if the predecessor during the reaction should not be turned into such structures. [Ru(CO)2RCO2] or similar compounds may or may not be a catalyst for prelinlinary of the present invention, however, it should be noted that the use of such compounds to guarantee the efficiency of the catalytic reaction and good results. The proposed method can be implemented using a wide range of compounds of ruthenium. Even in those cases when the connection ruthenium is very resistant to catalyze the reaction, catalysis can be carried out by including a compound that has no detrimental effects on the reaction prelinlinary and stimulates the conversion of compounds of ruthenium in appearance, having catalytic activity. For example, ruthenium chloride in an inert catalyst, however, it becomes quite active when adding alkali such as an alkali metal salt of carboxylic acid, namely sodium acetate. Do not assume that a simple connection salts of ruthenium catalyst are or that many of the compounds used here ruthenium for osenia, who are the catalyst of the present invention, is not installed, but found exactly what many ruthenium containing compounds can be used in situ generation of the catalyst. The variety of selection of ruthenium compounds used as precursors of catalysts in the proposed method, really wide; it is noteworthy that compound precursors can vary from ruthenium on a carrier, such as ruthenium on charcoal, alumina, etc. to ruthenocene, bis/this 5-cyclooctadiene/ruthenium (II) tri-n-butylphosphine and bis/this 5-cyclooctadiene/ruthenium (II) trialkyl-phosphine/maleic anhydride.

The most preferred catalysts form of carboxylates ruthenium-carbonyl or predecessors, who can turn into these kinds of. Based on the analysis of literature data we can make certain assumptions about the likely structure of the catalyst. On the basis that routinearbeit interacts with carboxylic acids to produce soluble orange-yellow complexes having the empirical formula [Ru(CO)2RCO2]nand the fact that these complexes are sufficiently labile to contribute what roximately, I believe that these structures are involved in the catalysis process prelinlinary. It is known that in the presence of carbon monoxide [Ru(CO)2RCO2] n is easily converted into dimer EN2(CO)6/RCO2)2. Similarly, the substitution of other ligands, such as phosphines, results in complexes Ru2(CO)4(L)2(RCO2)2. A similar tool for the coordination proposed for vinyl esters. Addition of one equivalent of triphenylphosphine (ruthenium) to the catalyst based on ruthenium-carbonyl reduces the speed prelinlinary approximately ten times, indicating that the complex formed EN2(CO)4(L)2(RCO2)2is a less active precursor. Similarly, the addition of one equivalent of phosphonium-ilide, 2-/triphenylphosphane-anilide/succinic anhydride results in low reaction rate. The complex hydride/acetate/Tris/triphenyl-phosphine/ruthenium (II) demonstrates a lack of activity, which indicates that a higher ratio of phosphorus to the ruthenium lead to more serious inhibition of the reaction rate. Dodecanoyl tetrahydrocarboline H4EN4(CO)12may be this is the uranyl chloride and Ruthenian show only very low catalytic activity, which further proves that the level of catalytic activity directly depends on the form of the ruthenium precursor.

Found that the alleged catalyst precursor [Ru(CO)2RCO2]ncan be obtained in several ways. For example, trinuclear complex [Ru3O(OAc)6(H2O)3OAc results in good catalyst prelinlinary. Infrared analysis shows that [Ru3O(OAc)6(H2O)3]OAc, you will notice in [Ru(CO)2RCO2]nunder the reaction conditions of prelinlinary. This is observed even when the reaction is carried out in a nitrogen atmosphere, and no carbon monoxide. Often there is a sufficient number of additional carbon monoxide to in situ turn all of EN in the carbonyl form. As indicated above, the predecessors on the basis of trihalogen ruthenium such as ruthenium (III) chloride and ruthenium (III) iodide, show only marginal activity of the catalyst. However, a very active and more selective catalyst can be obtained in situ from rotaryglobe and sodium acetate. This leads to the generation of a precursor [Ru3O(OAc)6(H2O)3]oAc and not soluble chloride salt NAT is I or mixture of reagents, which can lead to precursor ruthenium carboxylate. Dichlorocarbanilide (II) dimer [RuCl2(CO)3]2also provides an active, but non-selective catalyst, which produces significant quantities of heavier products, which are believed hypothetically, are complex diesters of ethylidene and glycol. Postulate that after the conversion in the catalyst [RuCl2(CO)3]2also produces trace amounts of hydrochloric acid, which are mainly responsible for the formation of by-products. There is a basis to prove these assumptions. In a similar reaction conditions but in the absence of ruthenium hydrochloric acid, as shown, easily promotiom the formation of heavy by-products. The typical conclusion is that the predecessors of ruthenium halide can be used in the practice of the present invention, however, they are best used in combination with the carboxylates of alkali metal (usually sodium acetate) in order to facilitate the deposition of a halide of an alkali metal (usually sodium chloride). Decarbonnel and decarboxylating is Oh, conducted in an atmosphere of carbon monoxide, ruthenium (III) acetyl-acetonate, ruthenium (IV) oxide, ruthenium coal and ruthenium on alumina showed catalytic activity. Under such conditions, the powder of ruthenium shows minor activity. Method for producing catalysts prelinlinary from halides of ruthenium includes, as described above, displacement of halide from a ruthenium precursor. It is also likely that other metal salts, precipitating the halide (Ag+, Cu+Hg+), would also be effective in combination with halides of ruthenium to obtain a catalyst precursor.

The amount of ruthenium catalyst suitable for implementation of the response prelinlinary, is not critical. The usual amount is a catalytically effective amount, i.e., sufficient to implement the desired vinyl exchange. For example, it was found that the concentration of ruthenium catalyst ranging, from about 30,000 parts to 0.5 parts per million (ppm) of ruthenium based on the weight of liquid reaction medium, can be used to implement the response. For the implementation of the reaction can be used for higher and lower is placed on the same basis.

Preferably, the reaction prelinlinary was carried out in the absence of a quantity of water in the reaction medium, which inhibits obtain the desired product of the vinyl exchange. However, as shown in the examples 60-63 below, the reaction can be performed in the presence of significant quantities of water. Inhibiting effects of water depend on the reactants. Increasing the concentration of the ruthenium catalyst in the reaction medium is an easy method to overcome the inhibition of water in many, if not most, cases. There is a correlation between the amount of ruthenium catalyst and the amount of water used in the method. More than ruthenium is present, the greater the amount of water may be present in the reaction without adversely affecting the reaction. It is desirable to use a system that essentially does not contain water. The smaller the amount of water present, the better reaction takes place and the greater the yield of the desired reaction product. Preferred essentially anhydrous reaction system described here. It is desirable that the amount of water in the reaction medium was approximately less than 10 wt. by weight of a mixture of the art, more preferably, if it is approximately less than 2.5 wt. by weight of the mixture, most preferably approximately less than 1 wt. by weight of the mixture. The water concentration in the reaction mixture can be adjusted by traditional methods, such as drying agents, azeotropic distillation of water from the reaction mixture when formed azeotrope, and the addition of desiccant molecular sieve.

The temperature at which it is possible to carry out the reaction also is not critical. The reaction rate varies with the identity of the acid Bronsted be prevenlion. More acidic acid are prone to reactivity at lower temperatures. It is also desirable to conduct the reaction at a temperature at which the acid reagent is dissolved or liquid. How beneficial exercise, maintaining a reaction temperature below the boiling point of the most high-boiling reagent or under sufficient pressure to maintain a liquid state. Liquid-phase state can be maintained by carrying out the reaction at temperatures above the melting point of the acid. However terephthalic acid (melting point above 300aboutC), which is insoluble in most rest the order of ester aromatic series at elevated temperatures (approximately 150aboutC). These conditions presumably facilitate prevenlion through what is achieved slight solubility of terephthalic acid. The temperature at which it is possible to carry out the reaction varies from about 75 to 250aboutC.

The optimal conditions of the reaction depend mainly on acid Bronsted, such as carboxylic acid, be prevenlion. If the acid is soluble at the reaction temperature, the latter should be performed without solvent. It is also preferable to carry out the reaction at temperatures above the melting point of the acid, if possible.

Prevenlion is better without solvents or non-polar solvents. Acceptable results were achieved in solvents such as toluene, heptane, silicone oil, mineral oil, phenylbenzoate, exporter and dioctylphthalate. More highly polar solvents, such as alcohols, water, sulfolan, carbowax and N-methylpyrrolidinone, tend to inhibit the reaction rate. Oxidized aromatics, such as diphenyl ether, methylbenzoate, exporter and dioctylphthalate, are desirable solvents in the synthesis of delimiter is islote Branstad (such as carboxylic acid) to the vinyl derivative. The preferred ratio depends mainly on the envisaged transformation.

The molar ratio of acid Bronsted (namely, carboxylic acid or carboxylate) ruthenium should be at least 0.5 to 1. The concentration of ruthenium in the reaction mixture is catalytically effective amount and is usually in the range of parts per million, and the acid is, as a rule, the main component of the reaction mixture. Most preferably the molar ratio of acid Branstad to ruthenium in the range of from about 50/1 to 1000000/1.

Several reaction media, such as carbon monoxide, air, nitrogen and ethylene, compatible with catalyst prelinlinary. Nitrogen and ethylene are suitable in most situations. Carbon monoxide increases the selectivity of the catalyst. The air used in combination with phenothiazines (inhibitor of liberizatsii) for the synthesis of vinylacetate. In some cases, the catalytic reaction leads to the production of small amounts of methane, carbon monoxide and carbon dioxide, and these side products increase initially installed the reaction atmosphere.

- cluster. In some situations, the reaction can also be carried out in a vacuum, for example in a distillation apparatus. The desired pressure of the reaction is approximately 10-6to 2644,8 mm RT.article.

As indicated above, the reaction is carried out at a time when all the reactants are in the liquid phase. It does not require the reaction medium was completely in the liquid phase. This simply means that in the liquid phase should be a sufficient amount of reagents and catalyst so that the reaction could occur in the liquid phase. For example, solid ruthenium on solid media can be used as a catalyst precursor. In the presence of the reagent, solvent and/or carbon monoxide sufficient amount of ruthenium can be converted into a compound soluble in the liquid to happen catalytic reaction. In another case, the reagent may be placed in a supercritical liquid state, which is enough liquid in order to maintain liquid-phase conditions of the present invention. A large part of the reaction system may be in the gas or solid phase, and this is acceptable up until a sufficient portion of the reaction system is in the liquid phase in order to maintain the reaction is about how is the shift in the equilibrium of the reaction towards the desired product with the in order to obtain a higher concentration of the product based on the quantity of the source material. This can be done by continuous extraction of one of the reaction products in order to shift the balance in a favorable direction, without detrimental effects on the values of the catalyst and/or ruthenium.

P R I m e R 1. In the bottle Fisher-porter download ruthenium-carbonyl 0,316 g benzoic acid 183 g, 1.50 mol and a vinyl acetate 258 g, 3.00 mol. The bottle attached to the reactor apparatus, rinsed and increase the pressure to 25 psig (1,758 kg/cm2) with carbon monoxide, then heated to a temperature of 150aboutC for 3 hours, the Reaction mixture was cooled to room temperature, transferred to a one litre flask and distilled in a rotary evaporator under reduced pressure. The fraction taken under pressure of about 15 mm RT. Art. and a temperature of 85about(187,8 g) and re-distilled through a 15 cm column in the Game. Vinylbenzoate (100,4 g, more than 99% purity by gas chromatography) is collected in fractions, boiling at a temperature 90-101aboutWith under a pressure of 15 mm RT.article.

P R I m m e R 2. In the bottle Fisher-porter load Tris/akvo/-hexa/--Aceto-3-exocrine the actor apparatus, purge and increase the pressure to 25 psig (1,758 kg/cm2) with carbon monoxide, then heated to a temperature of 150aboutC for 3 hours the Reaction mixture is freed from volatile constituents in a rotary evaporator and the residue is distilled through a 15 cm column in the Game. The fraction collected at the temperature of the 49aboutC and a pressure of 5 mm RT.article is a vinyl-2-ethylhexanoate (9.0 g, more than 99% purity as determined by gas chromatography).

P R I m e R 3. In the bottle Fisher-porter download ruthenium-carbonyl amount of 0.118 g, Pavlinov acid 68,43 g, 0.67 mol and vinylbenzoate 48,87 g, 0.33 mol. The bottle attached to the reactor apparatus, the purge and the pressure is increased to 25 psig (1,758 kg/cm2) with carbon monoxide, then heated to a temperature of 150aboutC for 2 h the Cooled reaction mixture is loaded into a 250 ml flask and subjected to vacuum distillation through a 15 cm column in the Game. The fraction collected at the temperature of 60.5-65aboutC and a pressure of 150 mm RT.article (31.7 g), re-distilled at atmospheric pressure (boiling point 114aboutWith 24.2 g). It contains vinylbilt.

P R I m e R 4. In the bottle Fisher-porter download ruthenium-carbonyl 0,211 g adipic acid and 7.3 g, 0.05 mol and vinylic is. inch (1,758 kg/cm2) nitrogen, then heated to a temperature of 130aboutWith over 4.5 hours the Reaction mixture is freed from volatile constituents in a rotary evaporator and the residue is distilled through a 15 cm column in the Game. The fraction collected at the temperature 72-79aboutC and a pressure of 0.75 mm RT.article is divinerecipes (1.5 g, 98% purity as determined by gas chromatography).

P R I m e R 5. In the bottle Fisher-porter load Tris/akvo/-hexa-Aceto-3-oxo-triruthenium 0.9 g, 150 g of dioctylphthalate, terephthalic acid (75 g, 0.45 mol and 150 g of vinyl acetate, 1,74 mol. The bottle attached to the reactor apparatus, the purge and the pressure is increased to 25 psig (1,758 kg/cm2) with carbon monoxide and heated to a temperature of 175aboutWith over 4.5 hours the Reaction mixture is freed from volatile constituents in a rotary evaporator. Distillation through a column with a short path allows you to obtain a fraction boiling at a temperature of 111aboutC at a pressure of 0.7 mm RT.article (7,1 g), which cures after condensation (the melting temperature of 76.5-80,5aboutC). It contains divinitatem.

P R I m e R 6. Using a technique similar to example 5, isophthalic acid 75 g turn in divine is the PMC with a short path leads to the production of fractions, boiling at a temperature 117-145aboutC and a pressure of 1.2 mm RT.article (7,1 g), which cures after condensation (the melting temperature of 53.5-56,5aboutC). It contains divinitatem.

P R I m e R 7-12. The data in the table. 1 shows a number of prelinlinary catalyzed by ruthenium, which carry between vinyl acetate and a variety of carboxylic acids, where the products of ester instead of highlighting characterized by either gas chromatography, infrared or mass spectroscopy, or the retention time in gas chromatography by comparison with authentic sample. In table. 1 shows the conditions of the reaction.

P R I m e p 13. In three portions, which are later combined to a ruthenium-carbonyl 44.4 g (total of three servings), Pavlinov acid 510 g (total of three portions) and vinyl acetate 432 g (total of three portions) are loaded into the bottle Fisher-porter, washed and the pressure is increased to 25 psig (1,758 kg/cm2) with carbon monoxide, then heated to a temperature 145-160aboutC for 2 h resulting in a highly concentrated solution of the catalyst based on ruthenium (2,15% ruthenium or 21500 ppm ruthenium), in which the reaction is dissolved in ur is she a volume of 30 gallons (approximately 113 l) with 10 gallons each of vinyl acetate and pavlinovoi acid with getting vinylbilt get 300 ppm concentration of the ruthenium catalyst.

Vinylbilt (91 lb, i.e., about 41 kg) receive two 20-gallon (75 l) servings per 30-gallon (113 l) reactor made of stainless steel. In two portions Pavlinov acid (75.5 lbs, 34,3 kg) 10 gallon (37,8 l) and vinyl acetate (77.9 lb 35 kg) 10 gallon (37,8 l) prevenalert in the presence of 300 ppm of ruthenium catalyst described above, at a temperature of 145aboutWith using the reactionary atmosphere of carbon monoxide at 50 psi (3,515 kg/cm2within 5 hours the Reaction product removed from the reactor by vacuum distillation (60-130aboutWith 240 mm RT.CT.) of the ruthenium catalyst. Based on gas chromatographic analysis to 94.7 90.4 and vinylbilt, respectively formed in the two reaction portions, can be taken into consideration after distillation. This shows that re-balancing vinylbilt (and acetic acid) in vinyl acetate (and Pavlinov acid) successfully controlled during the distillation in the range of 9.6% (batch I) and 5.3% (batch 2), respectively. The mass balance for each component is over 98%

P R I m e R s 14-32. The catalytic activity of numerous compounds of the ruthenium precursor is evaluated according to the following method. The mixture Ruthenian the definition of analysis) is loaded into the bottle Fisher-porter, seal, rinsed three times with carbon monoxide and increase the pressure to 25 psig (1,758 kg/cm2). Mixed using a magnetic stirrer, the reaction mixture was heated in an oil bath to the desired reaction temperature for a set period of time (both values are given in table. 2). Gas chromatographic analysis on a capillary column of fused silica DB-1 (F) shows the number of vinylbenzoate formed by parafinirovannaya (shown in the table. 2).

P R I m e R s 33-46. In table. 3 shows prevenlion without isolating the product. In the examples presented in table. 3, prelinlinary catalyzed by ruthenium (300 ppm ruthenium), various acidic compounds or vinyl acetate (VA), or vinylphenol (EAP), carried out in such a way that the products of vinylaromatic instead of highlighting characterized by gas chromatography (IR), mass spectroscopy or retention time in gas chromatography by comparison with an authentic way. In table. 3 shows the conditions of the reaction.

P R I m e R s 47-55. Using the methods of examples 33-46 vinyl products described in the examples 47-55, to obtain using 300 ppm of ruthenium, probablecause the logical time of retention for these products. The data are given in table. 4.

P R I m e R 57. In the bottle Fisher-porter download cyclohexanecarbonyl acid 100.0 g, 0.78 mol, vinyl acetate 134,3 g, 1.56 mol and carbonyl ruthenium 0,056, Bottle seal, rinsed four times with carbon monoxide and the pressure raised to 25 psig (1,758 kg/cm2). The bottle was placed in an oil bath with a temperature of 150aboutAnd the contents stirred for 4.5 hours the resulting solution, after cooling to room temperature, concentrated by rotary evaporation. The residue is distilled through a column in the Game to obtain the fraction of cases (53.2 g, 54-64aboutWith 4/3 mm RT. Art.), which is a carboxylate of vinylcyclohexane.

P R I m e R 58. In the bottle Fisher-porter download salicylic acid, 13.8 g, 100 mmol, vinyl acetate 34.4 g, 400 mmol and carbonyl ruthenium 0,03304, Bottle seal, rinsed four times with carbon monoxide and the pressure is increased to 25 psig (1,758 kg/cm2). The bottle was placed in an oil bath and the contents stirred for 2 hours at a temperature of 130-140aboutC. the resulting solution after cooling to room temperature, concentrated in a rotary evaporator. The residue is distilled through a column in the Game with obtaining fractions (3,81 the a-porter download transcoding acid, 148 g, 1 mole, a vinyl acetate 172 g, 2 mol and ruthenium-carbonyl 0,201, Bottle seal, rinsed three times with carbon monoxide and the pressure raised to 25 psig (1,758 kg/cm2). The bottle was placed in an oil bath and stirred for 3 hours at a temperature of 145aboutC. the resulting solution after cooling to room temperature, concentrated in a rotary evaporator. The residue is distilled through a column in the Game with obtaining fractions (57 g, 112-130aboutC, 1.0 mm RT.cent.), which is vinilinum.

P R I m e R 60. A mixture consisting of propionic acid and 12.2 g of vinyl acetate and 17.2 g of distilled water 0,5011 g nonane (internal standard), 0,864 g and ruthenium-carbonyl 0,211 g (calculated concentration of ruthenium 3340 ppm), loaded into the reactor Fischer-porter, purge and pressure up to 25 psi (1,758 kg/cm2) nitrogen, followed by heating to a temperature of 130aboutWith over 15 p.m analysis of the cooled reaction mixture by gas chromatography shows that there is the following composition of products, g: vinyl Acetate 9,893 Acetic acid 5,032 Finalproject 7,398 Propionic acid 7,488

P R I m e R 61. A mixture consisting of propionic acid and 12.2 g of vinyl acetate and 17.2 g, the Ute in the reactor Fischer-porter, purge and pressure up to 25 psi (1,758 kg/cm2) nitrogen, followed by heating to a temperature of 150aboutC for 2 hours Analysis of the reaction mixture by gas chromatography shows that there is the following composition of products, g: vinyl Acetate 9,759 Acetic acid 2,811 Finalproject 8,232 Propionic acid 5,897

P R I m e R 62. Prevenlion untreated exhaust stream of vinyl acetate with industrial enterprises, contaminated with ethyl acetate, fenilpropionata and about 2% of the water used for transformation contained vinyl acetate in miniproject. The crude wet vinyl acetate 5.0 g, propionic acid 25,0 g, nonun-standard 0,4225 g and ruthenium-carbonyl 0,019 g (300 ppm Ru) is loaded into the bottle Fisher-porter, purge and pressure up to 25 psi (1,758 kg/cm2) carbon monoxide, after which the heating is carried out until a temperature of 160aboutC for 3 h, and then take samples. Contains the following products g: there were 1,227 vinyl Acetate Acetic acid 0,654 Finalproject 1,684

P R I m e R 63.

The vinyl acetate of example 62 is subjected to azeotropic drying before use. The crude vinyl acetate is dried by azeotropic reflux distilled in USTR,0 g, nonan-standard 0,4398 g and ruthenium-carbonyl 0,019 g (300 ppm Ru) is loaded into the vessel Fischer-porter, purge and pressure up to 25 psi (1,758 kg/cm2) with carbon monoxide, then heated at a temperature of 140aboutC for 3 h and take samples. The following products, g: vinyl Acetate 1,290 Acetic acid 0,468 Finalproject 3,249

1. HOW PRELINLINARY vinylphosphonic acid Bronsted selected from the group of vinyl esters of saturated or unsaturated carboxylic acid, another acid Branstad in the presence of compounds of ruthenium as a catalyst, at elevated temperature, wherein the process is conducted in the liquid phase, in which a soluble compound of ruthenium at a concentration of ruthenium 30,000 0,23 including 1 million by weight liquid-phase reaction mixture and the molar ratio of acid Branstad to ruthenium of 0.5/1 at a temperature of 75 250oC and a pressure of 10-62644,8 mm RT.article (3,48 at) emitting in the quality of the target product vinylphosphonic other acid Branstad.

2. The method according to p. 1, characterized in that the vinyl ester karbonovoi acid is a vinyl acetate.

3. The method according to p. 1, characterized in that the vinyl OIC acid vinylbenzoate.

5. The method according to p. 1, characterized in that the vinyl ester of carboxylic acid vinylacetat.

6. The method according to p. 1, characterized in that the vinyl ester of carboxylic acid vanillacream.

7. The method according to p. 1, characterized in that the liquid-phase reaction mixture is practically anhydrous.

8. The method according to p. 8, characterized in that the amount of water in the reaction mixture is less than 10% by weight of the mixture.

9. The method according to p. 1, characterized in that the acid Bronsted is a nitrogen-containing compound.

10. The method according to p. 9, characterized in that the nitrogen-containing compound is aminecontaining compound.

11. The method according to p. 1, wherein the process is conducted in the presence of carbon monoxide.

12. The method according to p. 1, characterized in that the solvent is present, directionspanel in relation to at least one of the reagents.

 

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The invention relates to a have a weed-killing activity of new (S)- and (RS)-1'-alkoxycarbonylmethyl-2-chloro-5-(2-chloro-4-triptoreline) benzoate General formula (I)

F3CO(I) in which R denotes methyl or ethyl

The invention relates to servicenational (S)-1'-ethoxycarbonylethyl 2-bromo-5-(2-chloro-4-triptoreline) benzoate and (S)-1'-ethoxycarbonylethyl 2-bromo-5-(2-chloro-4-triptoreline) benzoate

The invention relates to a derivative of acrylic acid, useful in agriculture and, in particular, suitable for use as fungicides, insecticides or plant growth regulators

The invention relates to organic chemistry, in particular to a method of producing butylbenzylphthalate, which is used as a plasticizer in polymer materials, additives for paint compositions

The invention relates to organic chemistry, in particular to a method of obtaining dimethacrylate esters oxyalkylene diphenylolpropane used as a Monomeric basis of filling materials

The invention relates to the use of chemical compounds, in particular of the lower esters of 2-methyl-6-alkyl-4-oxocyclohexa-2-inkarbaeva acids of General formula (I)

< / BR>
(I) where R=ISO-C3H7THE H5H11when R'=CH3and R=ISO-C3H7when R'=C2H5as components of perfume compositions

FIELD: chemistry.

SUBSTANCE: invention concerns organic compound synthesis, particularly method of obtaining 4-biphenylmetacrylate of the formula . Obtained compound is applied in production of heat and weather resistant polymer materials. Claimed method involves dissolution of 4-phenylphenol in 10 wt % aqueous solution of caustic soda, further dosage of acylating agent in the form of metacrylic acid anhydride agent in reaction mix preliminarily cooled to 0-(+5°)C at such rate so as to keep the mix temperature below +10°C at molar ratio of 4-phenylphenol and metacrylic acid anhydride of 1:(1.1-1.5), reaction mix maturing at room temperature with stirring, organic layer extraction, flushing by alkali solution, and drying.

EFFECT: enhanced output of 4-biphenylmetacrylate, admixture content of non-reacted 4-phenylphenol reduced to 0,003-0,005 wt %.

3 cl, 1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method for synthesis of alkyl(meth)acrylates which are used in synthesis of polymers and copolymers with other polymerisable compounds, involving a step for re-esterification of alkyl ester of α-hydroxycarboxylic acid with (meth)acrylic acid, accompanied by formation of alkyl(meth)acrylates and α-hydroxycarboxylic acid, and a step for dehydration of α-hydroxycarboxylic acid, accompanied by formation of (meth)acrylic acid.

EFFECT: method enables to obtain a product with high selectivity.

22 cl, 2 tbl, 2 dwg, 38 ex

FIELD: chemistry.

SUBSTANCE: apparatus for re-esterification of organic acid with ester has a fixed-bed catalytic reactor and a distillation column, where the pipe between the reactor and the distillation column is fitted with pressure increasing apparatus, and the head of the distillation column is connected to a phase separator which is in turn connected to said reactor, and flow to the reactor passes through a heat exchanger for regulating reaction temperature. The re-esterification method involves the following steps: A) mixing organic acid a) with ester b) and B) transfer of the alcohol residue of the ester b) to the acid a), accompanied by formation of an ester of acid a) and an acid of ester b), where the transfer of the alcohol residue of the ester b) to the acid a) at step B) is carried out in the apparatus described in claim 1. Reactants are fed into the distillation column to carry out re-esterification in the fixed-bed catalytic reactor lying outside the column; a portion of the liquid phase flowing downwards inside the distillation column is trapped and output from the column in form of a separate stream whose pressure is raised using the pressure increasing apparatus and its temperature is controlled in the heat exchanger before being fed into the reactor; the stream coming out of the reactor is fed into the distillation column where the mixture of reaction products is separated and the stream coming out of the top of the column is separated in the phase separator.

EFFECT: reduced expenses.

11 cl, 1 dwg, 2 tbl, 38 ex

FIELD: chemistry.

SUBSTANCE: invention relates to improved methods of producing alkyl esters of methacrylic acid as a reaction product, particularly to a method in which a) a reaction mixture which contains an amide of methacrylic acid, water, sulphuric acid and at least one alkanol undergoes esterification in one or more reaction spaces, b) the crude reaction product, in at least one fractionation column, is subjected to a separation process to obtain a reaction product which contains water, alkyl methacrylate and alkanol, c) the reaction product obtained at step b) is condensed in one or more heat-exchangers, d) the condensate is separated in at least one separation device into an organic phase and an aqueous phase, e) the organic phase is washed with water to obtain a washed organic phased and flush water and f) the separated aqueous phase, along with the flush water, is returned to at least one reaction space. The invention also relates to an apparatus for producing alkyl esters of methacrylic acid, at least having i) one or more reaction spaces in which a reaction mixture, which contains an amide of methacrylic acid, water, sulphuric acid and alkanol, undergoes esterification, ii) at least one fractionation column in which the reaction product is subjected to separation, iii) one or more heat-exchangers in which the reaction product subjected to separation is condensed, iv) at least one separation device in which the condensate is separated into an organic phase and an aqueous phase, v) at least one washing column in which the organic phase is washed with water, vi) at least one liquid-conducting connection between the separation device and at least one reaction space, through which the separated aqueous phase, optionally along with flush water, is returned to at least one reaction space.

EFFECT: high efficiency.

18 cl, 11 dwg

FIELD: organic chemistry, chemical technology.

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EFFECT: improved preparing method.

11 cl, 2 sch, 1 tbl, 12 ex

FIELD: organic chemistry, biochemistry, pharmacy.

SUBSTANCE: invention relates to a method for preparing statin sodium salts that relate to enzyme inhibitors that inhibit biosynthesis of plasma cholesterol of different species of mammals and can be used in preparing medicinal preparations. Method involves preparing statin sodium salts of the general formula: , wherein R represents hydrogen atom (H), CH3 or OH. Method involves interaction of statins as an oxyacid with the stoichiometric amount of 2-ethylhexanoate sodium to obtain suspension. Statin sodium salts are prepared from this suspension by filtration and drying a precipitate in the form of dry powder. Invention provides preparing such statin sodium salts as compactin, lovastatin and pravastatin sodium salts.

EFFECT: improved preparing method.

11 cl, 5 ex

FIELD: organic chemistry, biochemistry, pharmacy.

SUBSTANCE: invention relates to a method for preparing statin sodium salts that relate to enzyme inhibitors that inhibit biosynthesis of plasma cholesterol of different species of mammals and can be used in preparing medicinal preparations. Method involves preparing statin sodium salts of the general formula: , wherein R represents hydrogen atom (H), CH3 or OH. Method involves interaction of statins as an oxyacid with the stoichiometric amount of 2-ethylhexanoate sodium to obtain suspension. Statin sodium salts are prepared from this suspension by filtration and drying a precipitate in the form of dry powder. Invention provides preparing such statin sodium salts as compactin, lovastatin and pravastatin sodium salts.

EFFECT: improved preparing method.

11 cl, 5 ex

FIELD: vinyl acetate production by ethane catalytic acetoxylation with acetic acid obtained as intermediate.

SUBSTANCE: claimed method includes: a) bringing gaseous raw material, containing ethane as a main component, into contact in the first reaction zone with molecular oxygen-containing gas in presence of catalyst to obtain the first product stream including acetic acid and ethylene; b) bringing the said first product stream in second reaction zone with molecular oxygen-containing gas in presence of catalyst to obtain the second product stream including vinyl acetate; c) separation the second product stream from stage b) to recovery of vinyl acetate. In the first reaction zone catalyst of general formula MOaPdbXcYd is used, wherein X is at least one element selected from Ti, V, and W; Y is at least one element selected from Al, Bi, Cu, Ag, Au, K, Rb, Cs, Mg, Ca, Sr, Ba, Nb, Sb, Si, and Sn; a, b, c, and d are gram-atom ratio, and a = 1; b = 0.0001-0.01, preferably 0.0001-0.005; c = 0.4-1, preferably 0.5-0.8; and d = 0.005-1, preferably 0.01-0.3. Gaseous raw material from step a) preferably includes ethane and molecular oxygen-containing gas in volume ratio of ethane/oxygen between 1:1 and 10:1, and 0-50 % of vapor as calculated to total volume of starting raw material. Ratio of selectivity to ethylene and selectivity to acetic acid in the first product stream is 0:95-95:0.

EFFECT: integrated technological cycle with controllable product yield while changing technological parameters of the process.

6 cl, 11 ex, 2 tbl, 1 dwg

FIELD: organic synthesis.

SUBSTANCE: invention relates to A-ring precursors of vitamin D having formula I:

in which A represents -CH2OH, -CH2-OCOR', -COR", or ethynyl; R represents hydrogen or C1-C6-alkyl; R1 hydrogen, C1-C6-alkyl, or (CH2)nOP; R2 hydrogen or -OP; R' is phenyl; R" hydrogen, hydroxyl, C1-C6-alkoxy; P hydrogen or group -Si(R3)3, wherein each R3 independently represents C1-C6-alkyl or phenyl; n = 0 or 1, provided that, when compound I has configuration 2S,3aS,4aS, A is formyl, hydroxymethyl, ethynyl, or methoxycarbonyl, and R and R2 are both hydrogen atoms, then R1 is not -OSi(R3)3.Preparation of compounds I comprises: (i) interaction of compounds having general formula 1:

,

in which A represents C1-C6-alkoxycarbonyl or C1-C3-alkylaminocarbonyl, with lipase in vinyl alkanoate or acid anhydride and (ii) conversion of resulting compound of formula 2: (2) or 2': (2'), where Z represents alkyl, preferably C1-C3-alkyl, into corresponding compound I via formation of a leaving group and cyclization caused by treatment with a base to form desired bicyclo[3.1.0]hexane, said conversion comprising: protection of hydroxy groups, hydrolysis of ester, inversion of 3- or 5-hydroxy group, and converting carboalkoxy or carbamoyl group into desired substituent A.

EFFECT: optimized synthesis conditions allowing more effective larger-scale preparation of precursors.

8 cl, 4 dwg, 45 ex

FIELD: pharmaceutical chemistry, in particular crystal form of pravastatine sodium salt.

SUBSTANCE: invention relates to new crystal form of pravastatine sodium salt known under chemical name of 1,2,6,7,8,8a-hexahydro-b,d,6-trihydroxy-2-methyl-8-(2-methyl-1-oxobubutoxy)-haphtaleneheptane acid monosodium salt, obtained by a) preparation of solution containing pravastatine and sodium cations in lower aliphatic C1-C4-alcohol; b) addition ethylacetate to said solution; c) cooling of obtained alcohol/ethylacetate mixture; and d) crystallization. Characteristics of new crystal form of pravastatine sodium salt such as crystallogram and melting point (170-1740C) also are disclosed. The subject invention also pertains to method for pravastatine production as well as pharmaceutical composition containing the same. Pravastatine, its derivatives and analogs are well-known HMG-CoA reductase inhibitors and are useful as anticholesterenemic agents in treatment of hypercholesterenemia and hyperlypemia.

EFFECT: crystal form of pravastatine sodium salt and pharmaceutical composition with improved therapeutic action.

29 cl, 5 ex, 4 dwg

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides improved process for production of a fluorine-containing compound useful as starting material for manufacture of a variety of fluoropolymers with high output when performing short process and using inexpensive and easily accessible chemicals. Process comprises: (i) interaction of indicated below compound 1 with indicated below compound 2 to form indicated below desired compound 3, which is a compound, wherein content of fluorine is at least 30 wt % and which has hydrogen atom or multiple bond capable of being fluorinated; and (ii) liquid-phase fluorination of compound 3 to give indicated below compound 4 followed by (iii) cleaving group EF in compound 4 to produce compound 5 and compound 6: E1-RA-E1 (1), E2-RB (2), RB-E-RA-E-RB (3),

RBF-EF-RAF-EF-RBF (4), EF1-RAF-EF1 (5),

and RBF-EF2 (6), where RAF represents fluorine-containing bivalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether oxygen atoms; RA represents group, which is the same as group RAF or bivalent organic group capable of being converted into group RAF using fluorination reaction; RBF represents fluorine-containing polyvalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether or carbonyl oxygen atoms; RB represents group, which is the same as group RBF or polyvalent organic group capable of being converted into group RBF using fluorination reaction; E1 and E2 are such that, when group E1 is -CH2OH or Q1-CH2OH group, then group E2 is -COX or -SO2X group and, when group E2 is -CH2OH or -Q2-CH2OH group, then group E1 is -COX or -SO2X group, where X is halogen atom and Q1 and Q2 may be identical or different and represent -CH(CH3)- or -CH2CH2- group; E represents group -CH2OCO-, -CH2OSO2-, -Q1-CH2OCO-, -Q2-CH2OCO-, -Q1-CH2OSO2-, or -Q2-CH2OSO2-; EF represents group, which is the same as group E or group obtained by fluorination if group E on conditions that at least one group RAF, RBF, or EF is a group formed by fluorination reaction and groups EF1 and EF2 are groups formed by cleaving group EF. Invention also relates to novel fluorine-containing compounds of formulas 3-12, 3-13, 3-14, 3-15, 3-16, 4-12, 4-13, 4-14, 4-15, 4-16, 5-16, which are indicated in description.

EFFECT: increased resource of raw materials for production of fluoropolymers.

8 cl, 23 ex

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