Concentrated storage-stable aqueous optical brightening solutions

FIELD: chemistry.

SUBSTANCE: invention relates to a concentrated storage-stable aqueous solution (S) comprising components (a), (b) and (c), wherein component (a) is at least one optical brightening agent of formula (1), in which the anionic charge on the brightener is balanced by a cationic charge composed of one or more cations selected from a group consisting of hydrogen, alkali metal cation, alkali-earth metal cation, ammonium, ammonium which is mono-, di- or trisubstituted by a C1-4 linear or branched alkyl radical and ammonium which is mono-, di- or trisubstituted by a C1-4 linear or branched hydroxyalkyl radical, and the concentration of component (a) is 0.08-0.3 mol/kg, based on the total weight of the concentrated storage-stable aqueous solution (S); component (b) is at least one inorganic salt (SA), in a concentration of 2-15 wt %, based on the total weight of the concentrated storage-stable aqueous solution (S), where the salts (SA) are preferably by-products of the production process and component (c) is water, in a concentration of 10-88 wt %, based on the total weight of the concentrated storage-stable aqueous solution (S).

EFFECT: invention relates to a method of producing a concentrated storage-stable aqueous solution (S), a method for use thereof as an optical brightening agent for bleaching cellulose substrates, fabrics or nonwoven materials, a sizing solution or suspension when processing paper and a pigmented coating composition containing the solution (S).

23 cl, 1 dwg, 7 tbl, 14 ex

 

The technical field to which the invention relates

The present invention relates to concentrated aqueous solutions of specific optical brighteners based trainerstation with high stability in storage without the use solubilizing excipients, processes of extraction, or membrane filtration. The above-mentioned bleaching solutions provide an excellent effect of fluorescent whitening when applied to the surface of paper or in a size press or in a pigmented coating composition and show a reduced anionic charge.

The level of technology

Paper industry prefers to use optical brightening agents (OBA) in the form of concentrated aqueous solutions that can be easily and accurately dosed. However, it is well known that in typical cases OVA have low solubility in water at ambient temperatures due to the presence of inorganic salts, which are formed as by-products of the production process.

To eliminate this disadvantage, Japanese patent Kokai 62-106965 offers vysokodetalnye OVA based trainerstation derived from the following compounds of formula (1),

where: M is typically an alkali metal atom,

R - ,1, or 2 and

R - amino acid residue from which is removed the hydrogen atom of the amino group.

However, the high anionic charge generated by amino acid residues, may create difficulties for manufacturers of paper, wishing to begin recycling paper marriage (i.e. the transformation into a fibrous mass of any paper waste generated in the paper manufacturing process), in which the optical Brightener can be extracted in the process of dissolution of waste paper, leading to the appearance of the anionic charge in the system, which is used together with cationic chemicals may preclude, for example, processes of sizing or retention and dehydration.

US 4 900 466 describes a method for preparing stable in storage of aqueous solutions containing having a reduced anionic charge of a compound of formula (1) where: M is typically an alkali metal atom,

R-2 and

R - (along with others) diethylaminoethyl according to example 1

which is characterized by passing the reaction mixture through a semipermeable membrane to remove inorganic salts. Because of this additional time-consuming and laborious stage of the described method is economically disadvantageous.

CH-686 532 describes the preparation and isolation of having a reduced anionic charge of the compounds of formula (1), where:

p> M is typically an alkali metal atom,

R-2 and

R is selected from dialkylaminoalkyl (table 1 mentioned di-n-Propylamine), which is characterized by precipitation from the reaction mixture. The thus obtained solid compound of formula (1) are used directly for bleaching of paper or in a size press or in a coating composition. However, this patent is silent as to the preparation of concentrated stable in storage of aqueous solutions.

WO 2006/000573 A1 discloses stable in storage of concentrated solutions of optical brighteners derived from aliphatic alkylamine branched alkyl chain. Formula (10) describes hexachlorophane OVA obtained from a secondary amine - methylisobutylketone.

Thus, there is a need for optical brighteners having a reduced anionic charge from which it is possible to prepare concentrated stable in storage aqueous bleaching solutions without additional time-consuming and laborious stages, such as membrane filtration, separation or the addition of auxiliary substances.

Disclosure of the invention

Unexpectedly it was found that the compounds of formula (1), being prepared in the form of concentrated aqueous solutions without the need for �additional stages or the use of solubilization, combine a reduced anionic charge with a high stability in storage and at the same time provide an excellent effect of fluorescent whitening when applied to the surface of paper or in a size press or in a pigmented coating composition.

The present invention provides stable concentrated in storing the aqueous solution (S) comprising components (a), (b) and (C), in which

component (a) is at least one optical whitening agent of formula (1),

in which the anionic charge on the Brightener is balanced by a cationic charge generated by one or more cations selected from the group consisting of hydrogen, alkali metal cation, alkaline earth metal cation, ammonium, ammonium which is one, two or trehzameshchenny in C1-4linear or branched alkyl radical, ammonium which is one, two or trehzameshchenny in C1-4linear or branched hydroxyalkyl radical; the concentration of component (a) is from 0.08 to 0.3 mol/kg in recalculation on total weight of the concentrated stable in storage of the aqueous solution (S);

component (b) is at least one inorganic salt (SA) and its concentration is from 2% to 15% wt., in terms of�transfer the total weight of the concentrated stable in storage of the aqueous solution (S); and

component (C) is water, and its concentration ranges from 10% to 88% of the mass.[% wt., in terms of the total weight of the concentrated stable in storage of the aqueous solution (S)].

Not necessarily concentrated stable in storing the aqueous solution (S) can contain polyethylene glycol in an amount of from 2% to 40% of the mass.[% wt., in terms of the total weight of the concentrated stable in storage of the aqueous solution (S)], which functions as a so-called media to enhance the effectiveness of the component (a).

Not necessarily concentrated stable in storing the aqueous solution (S) may contain polyvinyl alcohol in an amount of from 0.01% to 10 wt%.[% wt., in terms of the total weight of the concentrated stable in storage of the aqueous solution (S)], which functions as a so-called media to enhance the effectiveness of the component (a).

Preferred compounds of formula (1) are compounds in which the anionic charge on the Brightener is balanced by a cationic charge generated by one or more cations selected from the group consisting of Li+, Na+To+CA+, Mg+and ammonium, which is one-, two - or trehzameshchenny in C1-4linear or branched hydroxyalkyl radical.

More preferably�mi compounds of formula (1) are compounds, in which the anionic charge on the Brightener is balanced by a cationic charge generated by one or more cations selected from the group consisting of Na+To+CA+, Mg+and ammonium, which is one-, two - or trehzameshchenny in C1-4linear or branched hydroxyalkyl radical.

Especially preferred compounds of formula (1) are compounds in which the anionic charge on the Brightener is balanced by a cationic charge generated by one or more cations selected from the group consisting of Na+and+.

Preferably, if the anionic charge on the Brightener is balanced by a cationic charge created more than one cation, the mixture of different cations contains 2, 3, 4 or 5, more preferably 2, 3 or 4, most preferably 2 or 3 different cation.

In one preferred aspect of the invention a concentrated stable in storing the aqueous solution (S) contains from 0.08 to 0.2 mol of the component (a) per kg of concentrated stable in storage of the aqueous solution (S), more preferably from 0.09 to 0.18 mol of the component (a) per kg of concentrated stable in storage of the aqueous solution (S).

In the following preferred aspect of the invention a concentrated stable in storing the aqueous solution (S) contains from 2.5 d� 14 wt.%, more preferably from 2.5 to 12 wt.%, inorganic salts (SA) [% wt., in terms of the total weight of the concentrated aqueous solution (S)]. Preferably salt (SA) are by-products of the production process.

Preferred inorganic salts (SA) are salts of alkali metals and salts of alkaline earth metals, preferably salts of lithium, sodium, potassium, calcium or magnesium or a mixture of these compounds.

More preferably, inorganic salts (SA) are a lithium halide, sodium halide or potassium halide or a mixture of these compounds.

Even more preferably, inorganic salts (SA) are sodium chloride, potassium chloride or a mixture of these compounds.

The next subject of invention is a method of producing the above-mentioned concentrated stable in storage of the aqueous solution (S), also in all its preferred embodiments, the step response of cianurchloride

(a) an amine of the formula (2)

in the form of the free acid, partial-or full salt,

(b) a diamine of formula (3)

in the form of the free acid, partial-or full salt and

(C) with di-n-Propylamine of the formula (4)

in the presence of water and with the use of the basis�ia (In).

Preferably, the solution obtained during the production process, is used directly for the preparation of stable storage of the aqueous solution (S), if necessary by dilution to the desired final concentration. Preferably for the preparation of concentrated stable in storage of the aqueous solution (S) additional method steps, such as membrane filtration, drying, etc., are not conducted.

As cianurchloride can be fluoride, chloride or bromide. It is preferred to cyanuramide.

Each reaction can be carried out in an aqueous medium, wherein cyanogenetic-suspended in water or in an aqueous-organic medium, wherein cyanogenetic dissolved in a solvent, such as acetone. Each amine may be administered without dilution or aqueous solution or suspension. Amines can react with cyanoglucosides in any order, although it is preferred that the first introduced in the reaction with aromatic amines. The stoichiometric amount of amine means half of the molar amount of cianurchloride in the case of a diamine of formula (3) and equivalent means a molar amount of cianurchloride in the case of an amine of the formula (2) and di-n-Propylamine of the formula (4). Each amine may be introduced into the reaction in a stoichiometric amount or in �SByte against cianurchloride. In typical cases, aromatic amines react in stoichiometric amounts or in slight excess; di-n-Propylamine of the formula (4) in most cases is used in excess of about 0.1% to 30% compared with the stoichiometric quantity.

For the substitution of the first halogen of cianurchloride it is preferable to work at temperatures from 0°C to 20°C and under conditions of pH from acid to neutral, more preferably in the range of pH from 2 to 7. For the substitution of the second halogen of cianurchloride it is preferable to work at temperatures from 20°C to 60°C and under conditions of pH from slightly acidic to slightly alkaline, more preferably at a pH in the range from 4 to 8. For substitution of the third halogen of cianurchloride it is preferable to work at temperatures from 60°C to 102°C and under conditions of pH from slightly acidic to alkaline, more preferably at a pH in the range from 7 to 10.

The duration of the substitution reaction of the first, second and third halogen of cianurchloride, for example, an aromatic amine of the formula (2) and formula (3) and di-n-Propylamine of the formula (4) is from 10 minutes to 24 hours, preferably from 30 minutes to 10 hours, more preferably from 1 to 5 hours.

the pH of each reaction in most cases be adjusted by the addition of a suitable base (At), and the choice of the base (B) is dictated desirable �of course the concentrated composition is stable in storage of the aqueous solution (S). Preferred bases (b) are, for example, hydroxides of alkali metals or alkaline earth metals (e.g. lithium, sodium, potassium, calcium, magnesium, carbonates or bicarbonates or tertiary aliphatic amines, e.g., triethanolamine or triisopropanolamine any combination of these. If the base (B) is a combination of two or more different bases, these bases may be added in any order or simultaneously.

Preferably salt (SA) are formed during the production process, for example, in the neutralization of halogenated appropriate base (B), for example, according to equation 1, in which the base (B) is sodium hydroxide

NaOH+Hcl- > NaCl+H2O (equation 1).

Preferably, halogenated released in the process of the three substitutions of cianurchloride, for example, an aromatic amine of the formula (2) and formula (3) and di-n-Propylamine of the formula (4).

If necessary, regulate the pH of the reaction may be acid, examples of which include hydrochloric acid, sulfuric acid, formic acid and acetic acid.

Thus, as the subject of the invention is the use of the above-described concentrated stable in storage of aqueous solutions (S), also in all its preferred embodiments, as the opt�ical bleaching agents, preferably for optical bleaching of cellulosic substrates, for example, tissues, nonwoven materials, or more preferably of paper.

Perhaps the use of other optical brighteners, structurally different from formula (1) in addition to the component (a).

For optical bleaching of fabrics and nonwovens concentrated stable in storing aqueous solutions (S) may be used, for example, in the processes of priming, in which the concentration of bleach in the bath for treatment can be maintained almost constant. In the finishing of textile materials (fabrics or preferably non-woven materials) binding agents, preferably synthetic resins, concentrated stable in storing aqueous solutions (S) may be added to a synthetic resin or in the bath for treatment, or before treatment. Optical Brightener can be fixed, and a finishing agent - cross to sew during the process of cold exposure or heat treatment, optionally after intermediate drying. Due to its resistance to acids and salts, such as magnesium chloride and zinc chloride, the compounds of formula (1) in the form of concentrated stable in storage of aqueous solutions (S) suitable for optical simultaneous bleaching and finishing of cotton with imparting wrinkle resistance. Concentrated stable in storing water� solutions (S) may be used in an amount of from 0.01 to 2.5 wt.%, preferably from 0.02 to 2.0 wt%.[% wt., in recalculation on weight of dry cellulosic substrate].

More preferably the concentrated stable in storing aqueous solutions (S) are suitable as optical bleaching agents for bleaching of paper and nonwoven materials, even more preferably for optical bleaching of paper after the formation of the paper ceiling or nonwoven materials after the formation of the roll.

Particularly preferably concentrated stable in storing aqueous solutions (S) are suitable for the bleaching of paper after the formation of the paper web. This can be achieved by the addition of concentrated stable in storage of the aqueous solution (S) to the pigmented coating composition or a solution or suspension for sizing. The paper may be fine or coarse in nature and from bleached or unbleached pulp.

For the treatment of paper in the size press can be used solutions or suspensions for sizing containing a concentrated stable in storing the aqueous solution (S) in an amount of from 0.5 to 125 grams per liter of solution or suspension for gluing, preferably from 2 to 100 grams/liter. Solution or suspension for the sizing may also contain one or more binding agents in a concentration of from 1 to 30 wt.%, preferably from 2 to 20 wt.%, most preferably from 5 to 15 wt%.[% wt., in recalculation on weight of a solution for the sizing]. the pH of a solution or suspension for gluing in typical cases is 5 to 9, preferably from 6 to 8.

The binding agent is selected from the group consisting of native starch, enzymatically modified starch, chemically modified starch and mixtures thereof. Modified starches preferably represent oxidized starch, hydroxyethyl starch or acetylated starch. Native starch preferably is an anionic starch, cationic starch or amphoteric starch. Although the source of the starch may be any source, but preferably sources of starch are corn, wheat, potato, rice, tapioca or sago.

Solution or suspension for the sizing may not necessarily contain a divalent metal salt or mixture of salts of divalent metals, different from inorganic salts (SA) contained in a concentrated stable in storing the aqueous solution (S), in a concentration of from 1 to 100 g/l, preferably from 2 to 80 g/l, most preferably from 5 to 70 g/l solution for sizing.

Preferred salts of divalent metals are selected from the group consisting of calcium chloride, magnesium chloride, calcium bromide, bromide, mA�tion, of calcium iodide, magnesium iodide, calcium nitrate, magnesium nitrate, calcium formate, magnesium formate, calcium acetate, magnesium acetate, calcium citrate, magnesium citrate, calcium gluconate, magnesium gluconate, calcium ascorbate, magnesium ascorbate, calcium sulfite, magnesium sulfite, calcium bisulphite, bisulphite magnesium, dithionite calcium, dithionite magnesium, calcium sulfate, magnesium sulfate, calcium thiosulfate, magnesium thiosulfate, and mixtures of these compounds.

More preferred salts of divalent metals are selected from the group consisting of calcium chloride, magnesium chloride, calcium bromide, magnesium bromide, calcium sulfate, magnesium sulfate, calcium thiosulfate, magnesium thiosulfate, and mixtures of these compounds.

Especially preferred salts of divalent metals are selected from the group consisting of calcium chloride, magnesium chloride, magnesium sulfate and mixtures of these compounds.

If the divalent metal salt is a mixture of one or more calcium salts and one or more magnesium salts, the amount of calcium salts may be from 0.1 to 99.9 wt.%, in terms of the total mass of the added salts of bivalent metals.

In addition to stable in concentrated aqueous solution storage (S), solution or suspension for the sizing may also contain one or more� binder water and optional optical brighteners, which are structurally different from formula (1), and optionally one or more salts of bivalent metals. Solution or suspension for the sizing may contain by-products formed during the preparation of the component (a), and other additives commonly used for the treatment of cellulosic substrates, such as fabrics, nonwovens or paper.

Examples of additives to the paper are secondary binders, antifreeze, biocides, defoamers, wax emulsions, dyes, inorganic salts, preservatives, chelating agents, thickeners, surface sizing agents, crosslinking agents, pigments, special resins etc.

Composition for sizing preferably prepared by adding the concentrated stable in storage of the aqueous solution (S) and optionally divalent metal salts and/or any other components to the aqueous binder solution, preferably at a temperature from 20°C to 90°C.

Composition for sizing can be applied to the surface of a paper substrate by any method of surface treatment known in the prior art. Examples of methods of applying the composition for sizing include the application of the sizing press, the application using the calender, coating by dipping into a solution for procla�and, the application in the form of coating and the application of irrigation. The preferred method of applying the composition for sizing is the application of the sizing press, such as Sizer press with watering roller. The preformed fabric paper is passed through a two-roll clamp, flooded composition for sizing. The paper absorbs some amount of the composition, the rest is removed in the roll gap.

The paper substrate contains a grid-matrix of cellulose fibers, which can be obtained from any fibrous plant. Preferably the source of cellulose fibers is solid wood and/or soft wood. The fibers may be either natural (primary) or recycled (secondary), or any combination of natural and regenerated fibers.

Pigmented coating compositions are largely aqueous compositions that contain at least one binder and a white pigment, in particular an opaque white pigment, and may additionally contain other additives such as dispersing agents and defoamers.

Although there is the possibility of producing a coating compositions that do not contain white pigments, the best white substrates for printing are obtained by using an opaque coating compositions which ODS�rat 10% to 80% of the mass.[% wt., in terms of the total weight of the opaque coating composition] the white pigment. Such white pigments in most cases, are inorganic pigments, for example, aluminum silicates (such as kaolin, otherwise known as China clay), calcium carbonate (e.g. chalk), titanium dioxide, aluminum hydroxide, barium carbonate, barium sulfate or calcium sulfate (e.g., gypsum) or mixtures of these.

Binder in pigmented coating compositions can be any of the binders traditionally used in the paper industry for the production of coating compositions, and may consist of a single binder or a mixture of primary and secondary binders. The main or primary binder is preferably a synthetic latex, in typical cases, styrene - butadiene, vinyl acetate, styrene-acrylic, vinyl-acrylic or ethylene vinyl acetate polymer. The secondary binder may be, for example, starch, carboxymethylcellulose, casein, soy polymers or polyvinyl alcohol.

The main or primary binder is used in typical cases in an amount of from 5 to 25 wt%.[wt%. in terms of the total weight of the white pigment]. The secondary binder is used usually in an amount of from 0.1 to 10 wt%.[wt%. in terms of the total weight of the white pigment] however, starch is used in typical cases in an amount of from 3 to 10 wt%.[wt%. in terms of the total weight of the white pigment].

Concentrated stable in storing aqueous solutions (S) may be used in quantities determined by the amount of the component (a), namely from 0.01 to 3 wt.%, preferably from 0.05 to 2 wt%.[% wt., in terms of the mass of the white pigment].

Concentrated stable in storing aqueous solutions (S) containing optical brightening agents of formula (1), have the advantage that they are lower anionic charge compared with similar compounds of the above-mentioned application of Japan Kokai 62-106965.

Unexpectedly, it was found that optical brightening agents of formula (1) also have higher water solubility than the analogous compounds in which di-n-propylaminoethyl compounds of formula (1) substituted by di-n-ethylamino-or di-n-butylaminoethyl, as evidenced by the examples in the patent CH 686 532 and US 4 900 466.

Unexpectedly, it was found that stable concentrated in the storage of aqueous solutions (S) show a better ability to coating the substrate compared to the same compounds mentioned above, application Japan Kokai 62-106965.

The following examples will explain in more detail the present invention. If not indicated otherwise, " % " and "parts" mean wt.%, and parts by mass.

The implementation of Fig�plants

Examples

Example of preparation 1

520,2 parts of the monosodium salt of aniline-2,5-disulfonic acid are added to 900 parts of water and dissolved with about 295,1 parts of aqueous sodium hydroxide solution [30% (wt./mass.)] at approximately 25°C and a pH of about 8 to 9. Thus obtained solution is added within about 30 minutes to 331,9 parts of cyanuramide dispersed in 405 parts of water and 630 parts of ice. The temperature is kept below 5°C using ice/water bath, and the pH is maintained at approximately 4 to 5 with about 504,1 parts of an aqueous solution of sodium carbonate [20% wt./mass.]. After adding the pH rises to approximately 6 approximately 35.1 parts of an aqueous solution of sodium carbonate [20% wt./mass.], and the stirring is continued at a temperature of from about 0°C to 5°C until then, until the reaction ends. Then to the reaction mixture are added 151,2 parts of sodium bicarbonate. After that the reaction mixture is introduced dropwise an aqueous solution obtained by dissolving under nitrogen 333,4 parts of 4,4'-diaminostilbene-2,2'-disulfonic acid in 1240 parts of water with approximately amounting to 235.8 parts of an aqueous solution of sodium hydroxide [30% wt./mass.] at a temperature of from about 45°C to 50°C and a pH of from about 8 to 9. The total mixture is made at a temperature of about �t 45°C to 50°C to complete the reaction. The resulting aqueous mixture contains a compound of the formula (5) in a concentration 0,161 mol/kg of the mixture.

Example of preparation 2A

To 1234,5 parts of an aqueous mixture comprising compound of the formula (5) obtained according to example of preparation 1, are added to 42.5 parts of di-n-Propylamine. The mixture was stirred in the reverse flow for 2 hours while maintaining the pH at 8 to 9 by addition of aqueous sodium hydroxide solution [30% wt./mass.]. Thus obtained aqueous solution is cooled to a temperature from 60°C to 65°C and filtered. Water is added to the filtrate or is removed by distillation to obtain a concentrated stable in storage of an aqueous solution of 2A containing the compound of the formula (6) in concentration is 0.150 mol/kg of finished concentrated stable in storing the aqueous solution for optical bleaching 2A (20,4% of the mass. in recalculation on total weight of finished concentrated stable in storing the aqueous solution for optical bleaching 2A) and about 5.3% of the mass.(% wt. in recalculation on total weight of finished concentrated stable in storing the aqueous solution for optical bleaching 2A) of sodium chloride. The resulting concentrated stable in storing the aqueous solution for optical bleaching 2A has a pH from 8 to 9 and shows no signs of deposition SPU�thee 2 weeks of storage at 5°C.

Example of preparation 2b

Concentrated stable in storing the aqueous solution for optical bleaching 2b was prepared by mixing together

- concentrated aqueous solution for optical bleaching comprising compound of the formula (6) and prepared according to example of preparation 2A, and

- of polyethylene glycol having an average molecular mass (SMM), 1500,

in the conditions of heating to a temperature of from 90 to 95°C. the Number of parts of each component is selected so as to obtain the finished concentrated stable in storing the aqueous solution for optical bleaching 2b containing the compound of the formula (6) in concentration is 0.150 mol/kg of finished concentrated stable in storing the aqueous solution for optical bleaching 2b and 6% wt., of polyethylene glycol with SMM 1500 [wt%. in recalculation on total weight of finished concentrated stable in storing the aqueous solution for optical bleaching 2b]. To provide the desired concentration of each component in the finished concentrated stable in storing the aqueous solution for optical bleaching 2b water is either added or removed by distillation. Concentrated stable in storing the aqueous solution for optical bleaching 2b has a pH from 8 to 9 and contains p�around 5.3% of the mass.[% wt., in recalculation on total weight of finished concentrated stable in storing the aqueous solution for optical bleaching 2b] sodium chloride. Concentrated stable in storing the aqueous solution for optical bleaching 2b, obtained by the procedure described above, shows no signs of precipitation after 2 weeks of storage at 5°C.

Comparative example 2C

The compound of formula (6A) was obtained as a powder by the same procedure which is described in example 6 from SN 532686, wherein the anionic charges on the optical Brightener is balanced by cations Na+and/or+.

Along with the compound of formula (6A), the powder contains about 1.9% wt., cation sodium and 7.5% wt., cation potassium of 5.1 wt.%, anion chloride and 1.3 wt.%, water [wt%. in terms of the total weight of the ready-obtained powder].

The aqueous mixture containing the compound of formula (6A) in concentration is 0.150 mol/kg, is prepared by adding a powder containing the compound of formula (6A) and obtained as described in example 6 from SN 532686, in water and stirring for 1 hour.

(Photo 1, see Annex).

Comparative example 3

Aqueous solution for optical bleaching 3 containing the compound of the formula (7) in concentration is 0.150 mol/kg aqueous solution for optical bleaching 3 (19,6% wt., in terms of overall �Assou prepared aqueous solution for optical bleaching 3) and about 5.3% of the mass.[% wt., in terms of the total weight of the prepared aqueous solution for optical bleaching 3] sodium chloride, receive the same methodology, which is described in example of preparation 2A, with the only difference that instead of 42.5 parts of di-n-Propylamine is used to 30.7 parts of diethylamine. Thus obtained aqueous solution for optical bleaching 3 has a pH of 8 to 9 and shows signs of precipitation during 0 to 4 days of storage at 5°C.

Comparative example 4

Aqueous solution for optical whitening 4 containing the compound of formula (8) in concentration is 0.150 mol/kg aqueous solution for optical bleaching 4 (21,3% wt., in terms of the total weight of the final aqueous optical whitening 4) and about 5.3% of the mass.[% wt., in terms of the total weight of the final aqueous optical whitening 4] sodium chloride, receive the same methodology, which is described in example of preparation 2A, with the only difference that instead of 42.5 parts of di-n-Propylamine is used to 54.3 parts of di-n-butylamine. Thus obtained aqueous solution for optical whitening 4 has a pH of 8 to 9 and shows signs of precipitation during 0 to 4 days of storage at 5°C.

Comparative example 5a

Aqueous solution for optical bleaching 5a, containing�th compound of formula (9) in concentration is 0.150 mol/kg aqueous solution for optical bleaching 5a (22,7% of the mass. in terms of the total weight of the prepared aqueous solution for optical bleaching 5a) and about 5.3% of the mass.[wt%. in terms of the total weight of the prepared aqueous solution for optical bleaching 5a] sodium chloride, receive the same methodology, which is described in example of preparation 2A, with the only difference that instead of 42.5 parts of di-n-Propylamine is used to 55.9 parts of L-aspartic acid. Thus obtained aqueous solution for optical bleaching 5A has a pH from 8 to 9 and shows signs of precipitation after 2 weeks of storage at 5°C.

Comparative example 5b

Aqueous solution for optical bleaching 5b was prepared by mixing together

- aqueous solution containing a compound of the formula (9) and prepared according to example of preparation 5 a, and

- of polyethylene glycol having an average molecular mass (SMM), 1500,

in the conditions of heating to a temperature from 90°C to 95°C. the Number of parts of each component is selected so as to obtain the prepared aqueous solution for optical bleaching 5b containing the compound of the formula (9) in concentration is 0.150 mol/kg aqueous solution for optical bleaching 5b, and 6% wt., of polyethylene glycol with SMM 1500 [% wt., in terms of the total weight of the prepared aqueous solution for optical bleaching 5b]. For about�of especiany the desired concentration of each component in the finished water solution for optical bleaching 5b water is either added or is removed by distillation. Aqueous solution for optical bleaching 5b has a pH from 8 to 9 and contains about 5.3% of the mass.[% wt., in terms of the total weight of the prepared aqueous solution for optical bleaching 5b] sodium chloride. Aqueous solution for optical bleaching 5b, obtained by the above procedure, shows no signs of precipitation after 2 weeks of storage at 5°C.

Comparative example 6A

Aqueous solution for optical bleaching 6A containing the compound of formula (10) described in WO 2006/000573 A1, the concentration is 0.150 mol/kg aqueous solution for optical bleaching 6A (19,6% wt., in terms of the total weight of the prepared aqueous solution for optical bleaching 6A) and about 5.3% of the mass.[wt%. in terms of the total weight of the prepared aqueous solution for optical bleaching 6A] sodium chloride, receive the same methodology, which is described in example of preparation 2A, with the only difference that instead of 42.5 parts of di-n-Propylamine is used 30.7 parts of N-methyl-N-Isopropylamine. Thus obtained aqueous solution for optical bleaching 6A has a pH from 8 to 9 and shows signs of deposition within 1 to 5 days of storage at 5°C.

Comparative example 6b

Aqueous solution for optical bleaching 6b was prepared by mixing together

in�tion of the solution containing the compound of formula (10) and prepared according to comparative example 6A, and

- of polyethylene glycol having an average molecular mass (SMM), 1500,

in the conditions of heating to a temperature from 90°C to 95°C. the Number of parts of each component is selected so as to obtain the prepared aqueous solution for optical bleaching 6b containing the compound of formula (10) in concentration is 0.150 mol/kg aqueous solution for optical bleaching 6b, and 6% of the mass. of polyethylene glycol with SMM 1500 [wt%. in terms of the total weight of the prepared aqueous solution for optical bleaching 6b]. To provide the desired concentration of each component in the finished water solution for optical bleaching 6b water is either added or removed by distillation. Aqueous solution for optical bleaching 6b has a pH from 8 to 9 and contains about 5.3% of the mass.[wt%. in terms of the total weight of the prepared aqueous solution for optical bleaching 6b] sodium chloride. Aqueous solution for optical bleaching 6b, obtained by the procedure described above, shows signs of precipitation during 1 week of storage at 5°C.

Application example 2A and comparative application example 5A Solutions for sizing are prepared by adding one from aqueous solutions for optical bleaching containing

- connected�e of the formula (6) and prepared according to example of preparation 2A, and

- the compound of formula (9) and prepared according to comparative example 5 and, respectively, in the concentration range from 0 to 80 g/l (from 0 to about 20 g/l in terms of dry optical Brightener), to a mixed aqueous solution containing calcium chloride (30 g/l) and anionic potato starch (50 g/l) [Perfectamyl A from AVEBE B. A.] at 60°C. the Solution sizing give time for cooling, and then pour it between the rotating rollers of a laboratory size press and put on sheet traded pasted with glue AKD (alkylbetaine), bleached base paper weighing 75 g/m2. The treated paper is dried for 5 minutes at 70°C in a tablet the dryer. Dried paper give time for conditioning, and then measure its whiteness (CIE) and the values of a* and b* on a calibrated spectrophotometer Auto Elrepho. The results are presented in table 1 and table 2, respectively, and demonstrate a high degree of whiteness and improved distribution of shade provided by the present invention.

Table 1
Whiteness CIE
The OVA solution [g/l]Examples
2A5A
0104,3104,3
20135,2134,3
40139,9138,6
60141,2137,8
80Of 143.1135,2

Table 2
The values a* and b* in the CIELAB system
The OVA solution [g/l]Examples
2A5A
a*b*a*b*
01,19-3,591,19-3,59
202,36-9,95 2,30-9,89
402,65-10,182,01-10,73
602,55-11,401,53-10,49
802,61-11,820,92-9,77

Application example 2b and comparative application example 5b

Solutions are prepared for gluing by adding one of the aqueous solutions for optical bleaching containing

- the compound of formula (6) and prepared according to example 2b and cooking

- the compound of formula (9) and prepared according to comparative example 5b, respectively, in the concentration range from 0 to 80 g/l (from 0 to about 20 g/l in terms of dry optical Brightener), to a mixed aqueous solution containing calcium chloride (30 g/l) and anionic potato starch (50 g/l) [Perfectamyl A from AVEBE B. A.] at 60°C. the Solution sizing give time for cooling, and then pour it between the rotating rollers of a laboratory size press and put on sheet traded pasted with glue AKD (alkylating�measures), bleached base paper weighing 75 g/m2. The treated paper is dried for 5 minutes at 70°C in a tablet the dryer. Dried paper give time for conditioning, and then measure its whiteness (CIE) and the values of a* and b* on a calibrated spectrophotometer Auto Elrepho. The results are presented in table 3 and table 4, respectively, and demonstrate a high degree of whiteness and improved distribution of shade provided by the present invention.

Table 3
Whiteness CIE
The OVA solution [g/l]Examples
2b5b
0104,3104,3
20137,3136,1
40141,5139,9
60143,5138,2
80144,5136,8

Table 4
The values a* and b* in the CIELAB system
The OVA solution [g/l]Examples
2b5b
a*b*a*b*
01,19-3,591,19-3,59
202,83-10,67Of 2.35-10,29
402,87-11,112,03-11,01
603,03-11,991,53-10,51
802,93-12,151,11-10,13

Application example 3

Prepare porownywania, containing 70 parts chalk (marketed under the trade name Hydrocarb 90 from OMYA), 30 parts of clay (marketed under the trade name Kaolin SPS from IMERYS), 42.8 parts of water, 0.6 parts of a dispersant (sodium salt of polyacrylic acid, sold in the market under the trade name Polysalz S from BASF), 20 parts of 50% latex (copolymer of styrene-butadiene sold under the trade name DL 921 from Dow) and 8 parts of 10 wt%. aqueous solution of polyvinyl alcohol (of 0.8 part of dry polyvinyl alcohol) and having a degree of hydrolysis of 98% to 99% and a viscosity according to Brookfield from 4.0 to 5.0 MPa·s (4% aqueous solution at 20°C). The dry solids content of the coating composition regulate to about 65% by adding water and set at pH 8 to 9 with sodium hydroxide.

Aqueous solutions for optical bleaching 2A, 2b, 5A and 5b, prepared as described respectively in examples of preparation 2A and 2b and comparative examples 5A and 5b, it is added in the concentration range from 0.8% to 2.0% wt., dry matter to the mixed coating composition. Then put this coating composition on a sheet traded white base paper with a neutral sizing (weight 75 g/m) with automatic wire fixture for coating, adjusted to a standard speed and standard load featu�obline. The paper with the coating was dried for 2 minutes in a stream of hot air. Dried paper give time for conditioning, and then measure its whiteness (CIE) and the values of a* and b* in the CIELAB system on a calibrated spectrophotometer Auto Elrepho. The results are presented in table 5 and table 6, respectively, and demonstrate a high degree of whiteness and improved distribution of shade provided by the present invention.

Table 5
Whiteness CIE
The concentration of solutions of OVA in recalculation on weight of dry matter (%)ExamplesComparative examples
2A2b5A5b
088,788,788,788,7
0,8116,1Area of 116.3116,0Area of 116.3
1,2 Of 120.7Of 118.4To 120.4
1,6121,5123,0118,2121,5
2,0122,1To 124.2116,6122,5

Table 6
The values a* and b* in the CIELAB system
The concentration of solutions of OVA in recalculation on weight of dry matter (%)ExamplesComparative examples
2A2b5A5b
a*b*a*b*a*b*a*b*
0 0,230,200,230,200,230,200,230,20
0,81,83-5,611,85-5,751,57-5,611,68-5,73
1,21,98-6,372,07-6,691,41-6,051,68-6,52
1,62,00-6,832,16-7,170,91-5,901,47-6,70
2,01,90-6,922,15-7,400,42-5,471,13-6,64

p> Application example 4

Solutions are prepared for gluing by adding one of our water mixtures for optical bleaching containing

- the compound of formula (6A) and prepared according to comparative example 2

and

- the compound of formula (6) and prepared according to example of preparation 2A, respectively, in the concentration range from 0 to 60 g/l (from 0 to about 20 g/l in terms of dry optical Brightener), to a mixed aqueous solution containing anionic potato starch (50 g/l) [Perfectamyl A from AVEBE B. A.] at 60°C. the Solution for the sizing given time to cool, and then pour it between the rotating rollers of a laboratory size press and put on sheet traded pasted with glue AKD (alkylether)bleached base paper weighing 75 g/m2. The treated paper is dried for 5 minutes at 70°C in a tablet the dryer.

Dried paper give time for conditioning, and then measure its whiteness (CIE) on a calibrated spectrophotometer Auto Elrepho. The results are presented in table 7 and demonstrate the achievement of high degree of whiteness provided by the present invention.

Table 7
Whiteness CIE
The OVA solution [g/l]Examples
2A2C
0101,2101,2
10121,7121,7
20130,4128,9
30135,0133,3
40137,8135,6
60141,2139,0

1. Concentrated stable in storing the aqueous solution (S) comprising components (a), (b) and (C), where
component (a) is at least one optical whitening agent of formula (1)

in which the anionic charge on the Brightener is balanced by a cationic charge generated by one or more cations selected from the group consisting of hydrogen, alkali metal cation, alkaline earth metal cation, ammonium, ammonium which is one, two or trehzameshchenny1-4linear or branched alkyl radical, and am�onium, which is one, two or trehzameshchenny1-4linear or branched hydroxyalkyl radical, and the concentration of the component (a) is from 0.08 to 0.3 mol/kg in recalculation on total weight of the concentrated stable in storage of the aqueous solution (S);
component (b) is at least one inorganic salt (SA) and its concentration is from 2 to 15 wt%. in terms of the total weight of the concentrated stable in storage of the aqueous solution (S), preferably where salt (SA) are by-products of the production process and
component (C) is water, and its concentration is from 10 to 88% by weight. in terms of the total weight of the concentrated stable in storage of the aqueous solution (S).

2. Concentrated stable in storing the aqueous solution (S) according to claim 1, characterized in that it further comprises polyethylene glycol in an amount of from 2 to 40 wt%. in terms of the total weight of the concentrated stable in storage of the aqueous solution (S).

3. Concentrated stable in storing the aqueous solution (S) according to claim 1, characterized in that it additionally contains polyvinyl alcohol in an amount of from 0.01 to 10 wt%. in terms of the total weight of the concentrated stable in storage of the aqueous solution (S).

4. Concentrated stable in storing water� solution (S) according to claim 1, characterized in that the anionic charge on the Brightener of the formula (1) is balanced by a cationic charge generated by one or more cations selected from the group consisting of Li+, Na+To+CA+, Mg+and ammonium, which is one-, two - or trehzameshchenny1-4linear or branched hydroxyalkyl radical.

5. Concentrated stable in storing the aqueous solution (S) according to claim 1, characterized in that the concentration of the component (a) is from 0.08 to 0.2 mol/kg of concentrated stable in storage of the aqueous solution (S), more preferably from 0.09 to 0.18 mol/kg.

6. Concentrated stable in storing the aqueous solution (S) according to claim 1, characterized by the fact that the concentration of inorganic salts (SA)/component (b) is from 2.5% to 14% wt., more preferably from 2.5 to 12 wt.%, in terms of the total weight of the concentrated aqueous solution (S) and salt (SA) are by-products of the production process.

7. Concentrated stable in storing the aqueous solution (S) according to any one of the preceding paragraphs, characterized in that the inorganic salt (SA) are the salts of alkali metals and salts of alkaline earth metals, preferably salts of lithium, sodium, potassium, calcium or magnesium, or a mixture of these compounds.

8. Ability� produce a concentrated stable in storage of the aqueous solution (S) according to claim 1 the step response of cianurchloride
(a) an amine of the formula (2)

in the form of the free acid, partial-or full salt
b) a diamine of formula (3)

in the form of the free acid, partial-or full salt
and
b) di-n-Propylamine of the formula (4)

in the presence of water and base (B).

9. A method according to claim 8, wherein the quality of cianurchloride use fluoride, chloride or bromide.

10. A method according to claim 8, in which cyanogenetic suspended in water or in an aqueous-organic medium.

11. A method according to claim 8, in which aromatic amines (2) and (3) react in stoichiometric amounts or in slight excess, and di-n-Propylamine (4) is used in excess of about 0.1% to 30% compared with the stoichiometric quantity.

12. A method according to claim 8, in which the first reaction stage is carried out at a temperature from 0°C to 20°C, the second reaction stage is carried out at a temperature from 20°C to 60°C and the third reaction stage is carried out at a temperature from 60°C to 102°C.

13. A method according to claim 8, in which the first reaction stage is carried out in conditions from acid to neutral, the second reaction stage is carried out under conditions of from slightly acidic to slightly alkaline and the third reaction stage is carried out under conditions of from weakly acid to alkaline.

14. A method according to any one of the preceding claims. 8-13, in Kotor�m base (B) is an alkali metal hydroxide or alkaline earth metal hydroxide, carbonate or bicarbonate, or a tertiary aliphatic amine, or a combination of the above.

15. Method of application of the concentrated stable in storage of the aqueous solution (S) according to any one of the preceding claims. 1-7 as optical bleaching agent for the bleaching of cellulosic substrates, textiles or nonwovens.

16. A method according to claim 15, in which the solution (S) is used in an amount of from 0.01 to 2.5 wt%. in terms of the mass of cellulosic material in the case of its use for optical bleaching of fabrics and nonwovens.

17. A method according to claim 15 or 16, in which the solution (S) used for the treatment of paper in the size press, solutions or suspensions for gluing in a concentration of from 0.5 to 125 grams/liter of solution or suspension for sizing.

18. Solution or suspension for sizing in the processing of paper containing a concentrated stable in storage solution (S) according to any one of the preceding claims. 1-7.

19. Solution or suspension for sizing according to claim 18, in which the solution (S) contained in a concentration of from 0.5 to 125 grams/liter of solution or suspension for sizing.

20. The glue solution according to claim 18, which further comprises one or more binding agents selected from the following group: native starch, enzymatically modified starch, chemically modified cu�hmal or mixtures thereof.

21. The glue solution according to claim 18, further comprising the divalent metal salt or mixture of salts of divalent metals, which differ from the salt (SA).

22. The glue solution according to any one of the preceding claims. 18-21, further comprising one or more binders, water and optionally other optical brighteners, which are structurally different from formula (1).

23. Pigmented coating composition comprising a concentrated stable in storage solution (S) according to any one of the preceding claims. 1-7.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to the field of organic chemistry, namely, to novel heterocyclic compounds of the general formula or to their pharmaceutically acceptable salts, where R1 stands for cyano, nitro, amino, -NHCOOR4 or -NHCOR4; R2 stands for a halogen, C1-alkyl, halogenC1-alkyl or C1-alkoxy; R3 stands for C1-alkyl; or both radicals R3 form a cycloalkyl, containing 3 members, together with carbon atom, which they are bound to; X stands for either an alkylene chain of 4-7 carbon atoms, linear or branched, and the said chain can contain one or several similar or different additional units, selected from -O-, -N(R5)-; either a group where n1 and p1 stand for two integer numbers, the sum of which n1+p1 is an integer number, selected from 2; R6 and R7 together form a covalent bond or R6 and R7 together with carbon atoms, which they are bound to, form a cycle or a cycloalkyl, containing 3 members; R4 stands for C1-alkyl; R5 stands for C1-alkyl. The invention also relates to particular compounds, a pharmaceutical composition based on formula (I), application of the formula (I) compound.

EFFECT: obtained are the novel heterocyclic compounds, useful in treating cancer.

23 cl, 10 dwg, 23 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds of formula

,

possessing properties of binding with delta opioid receptors. In formula I R1 is selected from the group, consisting of phenyl, pyridinyl and thiazolyl, with R1 being optionally substituted with one or two substituents, independently selected from the group, consisting of C1-4alkoxy, fluorine atom, chlorine atom, bromine atom and cyanogroup; in addition, R1 is optionally substituted with di(C1-4alkyl)aminocarbonyl; Y represents O, S, H3, vinyl, ethinyl or S(O); R2 represents a substituent, selected from the group, consisting of hydrogen, C1-4alkyl, C1-4alkoxy, C1-4alkylthio, fluorine atom, chlorine atom, bromine atom and hydroxy; Ra represents hydrogen or methyl; R3 is selected from the group, consisting of pyrrolidin-2-ylmethyl; pyrrolidin-3-ylmethyl; piperidin-2-ylmethyl, piperidin-3-ylmethyl, piperidin-4-ylmethyl, piperidin-2-ylethyl, piperidin-3-ylethyl, piperidin-4-ylethyl, pyridine-4-yl-(C1-2)alkyl, azetidin-3-ylmethyl; morpholin-2-ylmethyl, morpholin-3-ylmethyl, imidazolylmethyl, thiazolylmethyl, (amino)-C3-6cycloalkyl, 3-hydroxy-2-aminopropyl, 8-azabicyclo[3.2.1]octanyl, 1-azabicyclo[2.2.2]octanyl, guanidinylethyl, 4-(imidazol-1-yl)phenylmethyl, 2-(methylamino)ethyl, 2-diethylaminoethyl, 4-diethylaminobut-2-yl, piperidin-3-yl, piperidin-4-yl and pyrrolidin-3-yl; with piperidin-3-yl being optionally substituted on a carbon atom with phenyl; with pyrrolidin-2-yl in pyrrolidin-2-yl-methyl, pyrrolidin-3-yl, piperidin-3-yl and piperidin-4-yl being optionally substituted on a nitrogen atom with methyl, phenylmethyl, phenethyl or methylcarbonyl.

EFFECT: compounds can be used in the treatment of pain, induced by diseases or conditions, such as osteoarthritis, rheumatoid arthritis, migraine, burn, fibromyalgia, cystitis, rhinitis, neuropathic pain, idiopathic neuralgia, toothache, etc.

24 cl, 3 tbl, 19 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing pyrazoline carboxamidine derivatives of formula . Said compounds are known as powerful 5-HT6 antagonists. The disclosed method comprises reacting a corresponding substituted 4,5-dihydro-(1H)-pyrazole or an isomer thereof with isothiocyanate R6-N=C=S to obtain an amide of substituted 4,5-dihydro-(1H)-pyrazole-1-carbothioic acid or tautomeric substituted 4,5-dihydro-(1H)-pyrazole-1-carboxymidothioic acid . The obtained intermediate compounds are reacted with a corresponding alkylating agent to obtain an intermediate S-alkylated compound . Said intermediate compound is reacted with a sulphonamide derivative R7SO2NH2 and the target compound of formula (I) is separated from the reaction mixture. The invention also relates to novel intermediate products (IIIa), (IIIb) and (IV). Symbols given in the formulae have values given in the description.

EFFECT: providing an alternative method which improves atom efficiency of synthesis of desired compounds with higher output compared to existing methods for synthesis of said compounds.

8 cl, 1 tbl, 3 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to organic chemistry, namely to compounds of formula (I), wherein R1 and R2 independently represent C6-C10 aryl optionally substituted by -OH, halogen, -OC1-C3 alkyl, -NO2, -CF3 or C1-C3 alkyl, or 5- or 6-merous heteroaryl containing one heteroatom specified in N, S and O; A and M independently represent a methylene group or a single bond; an adjacent aromatic cycle is attached directly to an amide group; the group Y=Z represents together and irregularly oxygen atom (-O-), cis-vinylidene group (-CH=CH-), iminogroup (-N=CH- or -CH=N-) or methylene group with sp2-hybridised carbon atom (=CH-); X irregularly represents methine group (=CH-), cis-vinylidene group (-CH=CH-) or carbon atom (=N-), and W represents hydroxyl group (-OH), C1-C6 alkyl optionally substituted by -SH, 5- or 6-merous heteroaryl containing 1 to 2 nitrogen heteroatoms, or C6-C10 aryl, optionally substituted by -SH, -NH2, and their pharmaceutically acceptable salts.

EFFECT: described are the methods for preparing the compounds, using as a drug for treating cancer and the based pharmaceutical composition.

14 cl, 6 tbl, 49 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to a compound of formula , wherein Y and Z are independently specified in a group of a) or b) so that one of Y or Z is specified in the group a), and another one - in the group b); the group a) represents i) substituted C6-10aryl; ii) C3-8cycloalkyl; iii) trifluoromethyl or iv) heteroaryl specified in a group consisting of thienyl, furanyl, thiazolyl, isothiazolyl, oxazolyl, pyrrolyl, pyridinyl, isoxazolyl, imidazolyl, furasan-3-yl, benzothienyl, thieno[3,2-b]thiophen-2-yl, pyrazolyl, triazolyl, tetrazolyl and [1,2,3]thiadiazolyl; the group b) represents i) C6-10aryl; ii) heteroaryl specified in a group consisting of thiazolyl, pyridinyl, indolyl, pyrrolyl, benzoxazolyl, benzothiazolyl, benzothienyl, benzofuranyl, imidazo[1,2-a]pyridin-2-yl, furo[2,3-b]pyridinyl, pyrrolo[2,3-b]pyridinyl, pyrrolo[3,2-b]pyridinyl, thieno[2,3-b]pyridinyl, quinolinyl, quinazolinyl, thienyl and benzimidazolyl; iii) benzofused heterocyclyl attached through a carbon atom, and when a heterocyclyl component contains a nitrogen atom, the carbon atom is optionally substituted by one substitute specified in a group consisting of C3-7cycloalkylcarbonyl; C3-7cycloalkylsulphonyl; phenyl; phenylcarbonyl; pyrrolylcarbonyl; phenylsulphonyl; phenyl(C1-4)alkyl; C1-6alkylcarbonyl; C1-6alkylsulphonyl; pyrimidinyl and pyridinyl; C3-7cycloalkylcarbonyl, phenyl, phenylcarbonyl, phenyl(C1-4)alkyl and phenylsulphonyl are optionally substituted by trifluoromethyl, or by one or two fluor-substitutes; iv) phenoxatiynyl; vi) fluoren-9-on-2-yl; vii) 9,9-dimethyl-9H-fluorenyl; viii) 1-chlornaphtho[2,1-b]thiophen-2-yl; ix) xanthen-9-on-3-yl; x) 9-methyl-9H-carbazol-3-yl; xi) 6,7,8,9-tetrahydro-5H-carbazol-3-yl; xiii) 3-methyl-2-phenyl-4-oxochromen-8-yl; or xiv) 1,3-dihydrobenzimidazol-2-on-5-yl optionally substituted by 1-phenyl, 1-(2,2,2-trifluoroethyl), 1-(3,3,3-trifluoropropyl) or 1-(4,4-difluorocyclohexyl); 1-phenyl is optionally substituted by one or more fluor-substitutes or trifluoromethyl; or xv) 4-(3-chlorophenyl)-3a,4,5,9b-tetrahydro-3H-cyclopenta[c]quinolin-8-yl; R1 represents C6-10aryl, C1-3alkyl, benzyloxymethyl, hydroxy(C1-3)alkyl, aminocarbonyl, carboxy, trifluoromethyl, spirofused cyclopropyl, 3-oxo or aryl(C1-3)alkyl; or when s is equal to 2 and R1 represents C1-3alkyl, the substitutes C1-3akyl is taken with a piperazine ring to form 3,8-diazabicyclo[3.2.1]octanyl or 2,5-diazabicyclo[2.2.2]octanyl ring system, and its pharmaceutical compositions.

EFFECT: preparing the new pharmaceutical compositions.

20 cl, 7 tbl, 72 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a novel crystalline form of N-[-2[[(2,3-difluorophenyl)methyl]thio]-6-{[(1R,2S)-2,3-dihydroxy-1-methylpropyl]oxy}-4-pyrimidinyl]-1-azatidine-sulphonamide, which has an X-ray powder diffractogram, measured with the application of a wavelength of X-rays of 1.5418 E and containing, at least, one crystalline peak with a value 2-theta (in degrees) 21.0, 28.8 and/or 29.1; or containing, at least, 2 crystalline peaks with a value 2-theta (in degrees) 21.0, 28.8 and/or 29.1; or containing, at least, 3 crystalline peaks with a value 2-theta (in degrees) 21.0, 28.8 and/or 29.1. The said crystalline form can contain additional crystalline peaks with a value 2-theta (in degrees), selected from 12.9 and 18.0, obtained under the said conditions.

EFFECT: crystalline form has the X-ray powder diffractogram, measured with the application of a wavelength of X-rays of 1,5418 E, with the crystalline peaks with a value 2-theta (in degrees) 12,9, 13,1, 18,0, 21,0, 22,5, 25,1, 25,3, 28,8, 29,1 and 30,4, and has melting point (beginning) 152,7°C.

6 cl, 3 dwg, 2 tbl, 5 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to new aminotetraline derivatives of formula (I) and their physiologically tolerable salts. In formula

,

A means a benzene ring or a ring specified in a group consisting of a 5-merous ring

,

R means the group R1-W-A1-Q-Y-A2-X1-; R1 means hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, halogenated C1-C6-alkyl, tri-(C1-C4-alkyl)-silyl-C1-C4-alkyl, C1-C6-alkoxy-C1-C4-alkyl, amino-C1-C4-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, an optionally substituted phenyl, C1-C6-alkoxy, di-C1-C6-alkylamino, an optionally substituted 5 or 6-merous heterocyclyl containing 1-3 heteroatoms specified in nitrogen and/or oxygen or sulphur; W means a bond; A1 means a bond; Q means -S(O)2- or -C(O)-; Y means -NR9- or a bond; A2 means C1-C4-alkylene, or a bond; X1 means -O-, C1-C4-alkylene, C2-C4-alkynylene; R2 means hydrogen, halogen, or two radicals R2 together with the ring atom to which they are attached form a benzene ring; R3 means hydrogen. The other radical values are specified in the patent claim. The invention also refers to intermediate products for preparing the compounds of formula (I).

EFFECT: compounds possess the properties of glycine transporter inhibitors, particularly GlyT1 and can find application in treating neurological and psychiatric disorders, such as dementia, bipolar disorder, schizophrenia, etc or for managing pain related to glycerinergic or glutamatergic neurotransmission dysfunction.

20 cl, 2 tbl, 326 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to organic chemistry, namely to pyrazine derivatives of formula I, as well as to their enanthiomers, diastereomers and pharmaceutically acceptable salts, wherein R1 is specified in a group consisting of ii) pyridinyl optionally having one substitute specified in a group consisting of C1-4alkoxy and cyano; and iii) pyrimidin-5-yl; or R1 optionally represents methoxymethyl, when Y represents ethinyl; Y represents ethinyl or a bond; R2 represents phenyl, benzofuranyl, 2,3-dihydrobenzofuranyl, benzo[1,3]dioxol-5-yl, indolyl or pyridinyl substituted by methyl, phenyl has one to two substitutes independently specified in a group consisting of C1-4alkyl, C1-4alkoxy, fluorine, chlorine, cyano, cyanomethyl, difluoromethyl, trifluoromethyl and hydroxy; or R2 represents phenyl having one C1-4alkylcarbonylamino or 1H-imidazol-1-yl substitute; X represents O or CH2; L is absent, and R3 represents 4-aminocyclohexyl, or L represents methylene, while R3 is specified in a group consisting of i) pyrrolidin-2-yl; ii) 1-aminoeth-1-yl; and iii) 1-aminocyclopent-1-yl; or R3 is combined into one cycle with L nitrogen atom to which L is attached to form piperazinyl. Besides, the invention refers to specific compounds, a pharmaceutical compound based on a compound of formula I, a method of treating pain and some neurodegenerative diseases.

EFFECT: there are produced new pyrazine derivative effective in treating pain and some neurodegenerative diseases.

21 cl, 3 tbl, 13 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: present invention refers to specific compounds or to their therapeutically acceptable salt presented in the patent claim and representing sulphonyl benzamide derivatives. The invention also refers to a pharmaceutical composition inhibiting the activity of anti-apoptotic proteins of the family Bcl-2, containing an excipient and an effective amount of a specific sulphonyl benzamide derivative.

EFFECT: sulphonyl benzamide derivatives inhibiting the activity of anti-apoptotic Bcl-2 proteins.

2 cl, 3 tbl, 558 ex

Antiviral compounds // 2541571

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to new compounds of formula I, such as below, or its pharmaceutically acceptable salts. What is described is a method for preparing them.

,

wherein: A independently from B means phenyl,

, or ,

and B independently from A means phenyl,

, or ,

and the values Z, Y, D, L1, L2, L3, Z1, Z2 are presented in the patent claim.

EFFECT: compounds are effective for hepatitis C virus (HCV) replication inhibition.

17 cl, 3 tbl, 8 dwg, 177 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel compounds of general formula (1), which possess an affinity to the µ-opiod receptor and the ORL1-receptor. The invention also relates to the application of the said compounds for obtaining medications, which can be used in treatment of fear, stress and associated with stress syndromes, depressions, epilepsy, Alzheimer's disease, senile dementia, general cognitive dysfunctions, learning and memory disorders (as nootropic), withdrawal syndromes, alcohol and/or drug abuse and/or abuse of medications and/or alcohol, narcotic and medication addiction, etc. In general formula (1) (1) Y1, Y1', Y2, Y2', Y3, Y3', Y4 and Y4' in each case stand for -H; Q stands for -R0, -C(=O)-R0, -C(=O)OR0, -C(=O)NHR0, -C(=O)N(R0)2 or-C(=NH)-R0; R0 in each case stands for -C1-8-aliphate, -C3-12-cycloaliphate, -aryl, -heteroaryl, -C1-8-aliphate-C3-12-cycloaliphate, -C1-8-aliphate-aryl, -C1-8-aliphate-heteroaryl, -C3-8-cycloaliphate-C1-8-aliphate, -C3-8-cycloaliphate-aryl or -C3-8-cycloaliphate-heteroaryl; R1 and R2 independently on each other stand for -C-1-8-aliphate; R3 stands for -C1-8-aliphate, -aryl, -heteroaryl or -C1-8-aliphate-C3-12-cycloaliphate; n stands for 0; X stands for -NRA-;RA stands for -C1-8-aliphate; RB stands for -C1-8-aliphate; on condition that R1, R2, RA and RB simultaneously do not stand for the non-substituted-C1-8-aliphate.

EFFECT: increased efficiency of the application of the compounds.

9 cl, 11 tbl, 164 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to novel compounds of general formula (1), which possess affinity for µ-opioid receptor and ORL1-receptor, to medications, containing said compounds, and to application of said compounds for obtaining medications, suitable for treating pain, fear, stress and other diseases or conditions. In general formula (1) Y1, Y1', Y2, Y2', Y3, Y3', Y4 and Y4' stand for -H; R1 and R2 independently on each other stand for -H or -CH3; on condition that R1 and R2 both simultaneously do not stand for -H; Q stands for: -C6-16-aryl, non-substituted or mono- or poly-substituted with -F, -Cl, -Br or -I; or heteroaryl; R3 stands for: -C1-8-alkyl, non-substituted or mono- or poly-substituted -OR0, where R0 stands for non-substituted -C1-3-alkyl; non-substituted -C3-6-cycloalkyl-C1-4-alkyl; non-substituted -C1-4-alkyl-C3-6-cycloalkyl; -C6-16-aryl, non-substituted or mono- or poly-substituted with -F, -Cl, -Br, -I, -CN, -R0 or -OR0, where R0 stands for non-substituted -C1-8-alkyl; or heteroaryl; n stands for 0; X stands for -NRA-; RA stands for -H or -R0; where R0 stands for non-substituted -C1-4-alkyl; and RB stands for -C(=O)R0; where R0 stands for non-substituted -C2-8-alkenyl-C6-16-aryl or non-substituted -C1-8-alkyl-(C6-16-aryl)1-2.

EFFECT: obtaining compounds for obtaining medications, suitable for treatment of pain, fear, stress and other diseases or conditions.

10 cl, 14 tbl, 164 ex

FIELD: chemistry.

SUBSTANCE: invention includes (a) at least one optical bleaching agent of formula (1) , wherein R1 denotes hydrogen or SO3M, R2 denotes hydrogen or SO3M, R3 denotes hydrogen or CH2CO2M, R4 denotes CH2CO2M, CH(CO2M)CH2CO2M or CH(CO2M)CH2CH2CO2M, where M denotes hydrogen, a cation of an alkali metal, ammonia, mono-methyl-di-C2-C3-hydroxyalkylammonium, dimethyl-mono-C2-C3- hydroxyalkylammonium, ammonium, which is mono-, di- or trisubstituted with a C2-C3 hydroxyalkyl radical, or a mixture of said compounds, (b) a magnesium salt or (c) binder, which is selected from a group consisting of natural starch, enzyme-modified starch, and chemically modified starch, wherein there are 0.1-15 parts of component (b) for one part of component (a). The invention also relates to a method of bleaching paper using said composition.

EFFECT: composition is a more efficient means of achieving high paper whiteness.

9 cl, 4 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a compound of formula (1) where R1 denotes hydrogen or SO3, R2 denotes hydrogen or SO3, R3 denotes hydrogen or CH2CO2, R4 denotes CH2CO2, CH(CO2)CH2CO2 or CH(CO2)CH2CH2CO2, and where M denotes a stoichiometric cation equivalent required to balance the anionic charge in formula (1) and is a combination of Mg2+ with at least 1 additional cation. The additional cations are selected from a group consisting of H+, a cation of an alkali metal, a cation of an alkali-earth metal other than Mg2+, ammonium, mono-C1-C4 alkyl-di-C2-C3-hydroxyalkylammonium, di-C1-C4-alkyl-mono-C2-C3-hydroxyalkylammonium, ammonium, which is mono-, di- or trisubstituted with a C2-C3 hydroxyalkyl radical, and mixtures thereof. The invention also relates to versions of the method of producing said compound and use of said compound in binding compositions for bleaching paper.

EFFECT: compound is a more efficient paper bleaching agent.

8 cl, 4 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: described is an improved method of producing melamine cyanurate which is used in different compositions as a flame retardant. The method involves reaction of cyanuric acid and melamine in molar ratio of 1:1 in the presence of 2-30% water of the weight of dry reactants at temperature ranging from 10 to 100°C in countercurrent air streams at pressure of 2-10 kgf/cm2. The method can be realised continuously.

EFFECT: end product is obtained with high output with low power consumption.

1 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: described is an improved method for synthesis of 2,5,8-triazido-sim-heptazine of formula (I) by reacting 2,5,8-trichloro-sim-heptazine with an azidation agent in form of sodium azide in the medium of aqueous acetone at room temperature, followed by extraction of the end product via deposition from water. The invention can be used in organic synthesis.

EFFECT: high-tech and cheap method for synthesis of 2,5,8-triazido-sim-heptazine of formula (I) from commercially available 2,5,8-trichloro-sim-heptazine and a cheap azidation agent in simpler conditions for synthesis and extraction of the end product with high output and purity.

FIELD: synthesis of phosphorus-containing derivatives of organic compounds.

SUBSTANCE: invention relates to method of preparing polyphosphates of organic compounds, to mixture of polyphosphates of organic nitrogenous bases, and to use of polyphosphates and mixture of polyphosphates as fire retardants for plastics, preferably thermoplastics and, more particularly, polyamides and polyesters. Polyphosphates of organic compounds are prepared via exchangeable decomposition of mixture of phosphorus pentoxide and at least one organic nitrogenous base with a compound releasing water when decomposed under reaction conditions, the latter compound being used in such molar proportion that water would release in amount corresponding to essentially two moles of water per one mole of phosphorus pentoxide. Water-releasing compound can be compound forming, along with water, only volatile decomposition products and this compound can be selected from group including anhydrous oxalic acid, oxalic acid dehydrate, and formic acid. Exchangeable decomposition reaction is conducted at 100 to 250°C. Mixture of polyphosphates of organic nitrogenous bases is characterized by following properties: when heated to 320°C it looses less than 2% of its mass; pH value of its 10% water suspension exceeds 5 at 25°C, preferably from 5.2 to 7.7 and, more preferably, from 5.8 to 7; its solubility in water is less than 0.1 g and preferably less than 0.01 g per 100 mL water.

EFFECT: expanded synthetic possibilities.

6 cl, 5 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to the improved method for synthesis of melamine adducts with acids of the order: cyanuric, phosphoric, boric acid in the presence of liquid medium that are modifying agents of polymers. Method involves homogenization of melamine and acid powders in a mixer at temperature from 20°C to 80°C and then prepared mixture is subjected for effect by deformation shift at temperature from 20°C to 150°C at the shift rate value 5-400 s-1 and the total deformation shift value from 1.5 x 103 to 2.0 x 105%. The ratio of melamine to acid is from 2:1 to 1:2 preferably. Effect by the deformation shift is carried out in mechanical reactor of auger type. Invention provides simplifying process in synthesis of end substances, significant decreasing consumptions and avoiding pollution of environment.

EFFECT: improved method of synthesis.

2 cl, 10 ex

The invention relates to organic chemistry, in particular to derivatives of 1,3,5-triazine - 2-trimethylammoniumchloride-4,6-bis(nonaxisymmetric)-1,3,5-triazine structure

as cationic type surfactant 1 table.

The invention relates to organic chemistry and chemistry of surface-active substances (surfactants), specifically to new, substituted 1,3,5-triazine - 2-trimethylammoniumchloride-4,6-bis(nonaxisymmetric)-1,3,5-triazine structure

as cationic type surfactants

The invention relates to agriculture, namely, to increase the resistance of plants to fetotoksicheskoe impact of herbicide

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to the improved method for synthesis of melamine adducts with acids of the order: cyanuric, phosphoric, boric acid in the presence of liquid medium that are modifying agents of polymers. Method involves homogenization of melamine and acid powders in a mixer at temperature from 20°C to 80°C and then prepared mixture is subjected for effect by deformation shift at temperature from 20°C to 150°C at the shift rate value 5-400 s-1 and the total deformation shift value from 1.5 x 103 to 2.0 x 105%. The ratio of melamine to acid is from 2:1 to 1:2 preferably. Effect by the deformation shift is carried out in mechanical reactor of auger type. Invention provides simplifying process in synthesis of end substances, significant decreasing consumptions and avoiding pollution of environment.

EFFECT: improved method of synthesis.

2 cl, 10 ex

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