2,2'-di(3,4-alkylenedioxythiophene)s, their application, method of their obtaining, method of obtaining 5,5'-dihalogen-2,2'-(3,4-alkylenedioxythiophene)s and method of obtaining poly(3,4-alkylenedioxythiophene)s based on them

FIELD: chemistry.

SUBSTANCE: invention relates to 2,2'-di(3,4-alkylenedioxythiophene)s of general formula (I) , where A, R and x have given in description values, which are intended for obtaining electroconducting or semiconducting compounds and valuable semi-products for π-conjugated polymers. Also described is method of their obtaining and method of obtaining poly(3,4-alkylenedioxythophene)s based on them. Claimed method allows to obtain novel 2,2'-di(3,4-alkylenedioxythiophene)s by simplified techniques and extend possibilities of their application.

EFFECT: obtaining agents by simplified techniques and extension of possibilities of their application.

12 cl, 4 ex

 

The invention relates to new 2,2'-di(alkylenedioxy)am, also called in the literature 2,2'-bis(3,4-alkylenedioxy)s or 3,4-(alkylenedioxy)-2,2'-bithiophene, to a method for producing compounds of this class, to their use as important intermediates or to receive important intermediates for π-conjugated polymers, as well as to the way to obtain 5,5'-dihalogen-2,2'-(3,4-alkylenedioxy)s and to a method for producing poly(3,4-alkylenedioxy)s based on them.

Connection class π-conjugated polymers in recent decades have become the object of numerous publications. Also referred to as conductive polymers or synthetic metals.

Due to the significant delocalization π-electrons along the main chain, these polymers exhibit interesting (nonlinear) optical properties and after oxidation or recovery they are a good elektroprovodnog. Due to this, these compounds can be used in various practical areas such as data storage, processing optical signals, the suppression of magnetic disturbance (EMI) and in the conversion of solar energy and rechargeable batteries, light-emitting diodes (EDS), the transistors with field effect, circuit boards, sensors (sensing elements), conden is Torah and antistatic materials.

Examples of known π-conjugated polymers are polypyrrole, polythiophene, polyaniline polyacetylenes, Polyphenylene and poly(p-phenylenevinylene).

Especially important and technically demanded polythiophene are poly(3,4-ethylenedioxythiophene)s from the group of poly(3,4-alkylenedioxy)s, having in its cationic form a very high electrical conductivity. In addition, the number of known polymers containing the link 3,4-ethylenedioxythiophene, and due to their electroluminescence suitable as source material for light-emitting diodes. It is particularly valuable for regulating the wavelength of emission and luminescence intensity is also the possibility of reverse takeover (zurückgreifen) on the parts of 2,2'-di(3,4-ethylenedioxythiophene)and (e.g., ..Donat-Bouillud, I.Lèvesque, Utao, .D'lorio, S.Beauprè, P.Blondin, V.Ranger, J.Bouchard and M. Leclerc, Chem. Mater. 2000, 12, S.1931-1936).

Problematic for this use is that necessary 2,2'-di(3,4-ethylenedioxythiophene)s can be obtained only through expensive ORGANOMETALLIC synthesis, which, depending on the reaction conditions can lead to low yield and/or only mediocre purity of the product.

Known 2,2'-di(3,4-alkylenedioxy)s, namely 2,2'-di(3,4-ethylenedioxythiophene)s, up to this time according to whether returnin sources, typically, you receive the following way (reaction combinations of Ullmann):

3,4-ethylenedioxythiophene are liftirovaniyu n-butyllithium in absolute tetrahydrofuran at -78°under protective gas with subsequent reaction mix with chloride of divalent copper in the oxidation of 2,2'-di(3,4-ethylenedioxythiophene).

Following the original work illustrate the disadvantages of these methods of synthesis, especially in regard to the reaction conditions, yield and purity.

Based on G.A.Sotzing, J.R.Reynolds and .J.Steel, Adv. Mater. 1997, 9(10), S. 795-798, that was obtained only a dirty product (TPL183-185°). Although ..Donat-Bouillud, I.Levesque, Utao, .D'lorio, S.Beaupre, P.Blondin, V.Ranger, J.Bouchard and .Leclerc, Chem. Mater. 2000, 12, S.1931-1936, describes the retrieval similar to the way a cleaner product (TPL203°), but its output is only 27.7% of theoretical. With the increase in the reaction mix of Ullmann duration of the reaction time .K.Mochanakrishnan, A.Hucke, M.A.Lyon, M.V.Lakshmikantham and ..Cava (Tetrahedron 55 (1999), S. 11745-11754) received output 84% relative to the pure product (TPL203-204°). However, the reaction time must be increased six times.

Significant deficiencies are described in these publications ways to obtain 2,2'-di(3,4-ethylenedioxythiophene)and are the following: 1) litrovaya should be carried out at low temperature the arts (-78° C) using external cooling of the mixture, for example a mixture of acetone/dry ice; 2) n-utility as ORGANOMETALLIC reagent is expensive and, when manipulating them, sensitive to air and moisture, and easily inflammable, especially when the access of moisture; 3) all reactions should be carried out under protective gas (nitrogen or argon) because of the sensitivity of utility and formed as intermediate litrownik of thiophenol.

Specified S.S.Zhu and ..Swager in J.Am.Chem. Soc. 1997, 119, S. 12568-12577, a variant of this method (litrovaya at -10°with the addition of tetramethylethylenediamine and oxidative combination with ferric acetylacetonate with reverse flow in tetrahydrofuran) did not lead to any simplification, as this also requires cooling the mixture and technique of shielding gas. The actual yield was 50% of theoretical (0,99 g of the maximum of 1.97 g), and the above 99% are the result of typographical errors.

Another serious shortcoming cited ORGANOMETALLIC methods is the limited applicability. The substitution of the ethylene bridge 2,2'-di(3,4-ethylenedioxythiophene)s not hitherto described. They were not received purposefully method litrovaya with subsequent reaction of Ullmann, as many substituents at the ethylene bridge, for example hydroxylic groups, carbonyl or heterochronies groups, dual relationships, etc. that comes litrovaya these substituents as side reaction or the main reaction. 2,2'-Di(3,4-alkylenedioxy)s with other alkionovymi bridges than ethylene bridges, hitherto not described in literature.

Thus, there is a need for new 2,2'-di(3,4-alkylenedioxy)Oh and a new way of getting known and new 2,2'-di(3,4-alkylenedioxy)s, in which

- you can refuse the use of low temperatures for external cooling;

- you can process equipment without protective gas;

becomes possible wide applicability, for example, to obtain a functionally substituted at the ethylene bridge 2,2'-di(3,4-ethylenedioxythiophene)s or other, optionally substituted 2,2'-di(3,4-alkylenedioxy)s.

This problem is solved 2,2'-di(3,4-alkylenedioxy)AMI General formula (I)

where a represents optionally substituted residue of alkyl with 2 to 4 carbon atoms,

R means one or more identical or different linear or branched, optionally substituted alkyl residue with 1 to 18 carbon atoms, optionally substituted residues cycloalkyl with 5-12 carbon atoms, optionally substituted residues and the sludge with 6-14 carbon atoms, optionally substituted residue of hidroxil with 1-4 carbon atoms or one or more residues of hydroxyl,

x represents an integer from 0 to 8,

with the exception of the compounds of formula (I-a)

Compounds of General formula (I), in which, for example, And is the residue of ethylene and x is 1, according to the invention can comprise not only one of the three structural isomers in pure form:

but also their mixtures with each other in any ratio. In addition, various structural isomers can exist in different stereoisomeric forms, which are both in pure form and as mixtures in different ratios to each other according to the invention may be implied under the compounds of formula (I). This applies equally to compounds of General formula (I)in which a and/or x have a different meaning than the ethylene (A) or 1 (x), as structurally different possible isomers.

Preferred compounds of formula (I) are characterized by the fact that

And means optionally substituted residue of ethylene,

R means one or more identical or different linear or branched, optionally substituted alkyl residue with 1 to 18 carbon atoms, when the mu is a necessity, substituted residues cycloalkyl with 5-12 carbon atoms, optionally substituted aryl residue with 6 to 14 carbon atoms, optionally substituted residue of hidroxil with 1-4 carbon atoms or one or more residues of hydroxyl,

x represents an integer from 0 to 4.

Especially preferred according to the invention are the compounds of formula (I), in which

And means optionally substituted residue of ethyl,

R means methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl or hydroxymethyl,

x represents 0 or 1.

2,2'-Di(3,4-alkylenedioxy)s of the formula (I) according to the invention has a versatile applicability.

In addition, an object of the present invention is a method for 2,2'-di(3,4-alkylenedioxy)s the General formula (I)

where a represents optionally substituted residue of alkyl with 2 to 4 carbon atoms, preferably optionally substituted residue of ethylene;

R means one or more identical or different linear or branched, optionally substituted alkyl residue with 1 to 18 carbon atoms, optionally substituted residues cycloalkyl with 5-12 carbon atoms, optionally substituted aryl residue with 6 to 14 carbon atoms, optionally someseni the residue hydroxyalkyl with 1-4 carbon atoms or one or more residues of hydroxyl, preferably, methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl or hydroxymethyl,

x represents an integer from 0 to 8, preferably an integer from 0 to 4, most preferably 0 or 1,

characterized in that compounds of General formula (II)

where A, R and x have the meanings mentioned for the General formula (I), is subjected to the interaction with the agent dehydrogenation.

The preferred embodiment of the method according to the invention is such a method of producing compounds of the formula (I-a), also known as 2,2'-di(3,4-ethylenedioxythiophene)s

characterized in that compounds of the formula (II-a)

subjected to interaction with a dehydrogenation agent.

The compounds of formula (II) may include, according to the choice of a and x, different stereoisomers, i.e. enantiomers or diastereoisomers. In the framework of the present invention under the compounds of the formula (II) imply as pure enantiomers or diastereoisomers, and a mixture of them in different ratio with each other. For example, the compounds of formula (II-a) can be both enantiomers (II-a-S) or (II-a-R):

in its pure form or in the form of their mixtures in any ratio of (II-a-S) and (II-a-R)./p>

The compounds of formula (II) can be obtained by the method described in the unpublished patent application DE Germany 10229218. This is subjected to interact with one another compounds of the formula (VI)

where A, R and x have the meanings mentioned for the General formula (I),

in the presence as catalyst of Lewis acids, preferably not oxidize Lewis acids such as boron TRIFLUORIDE (for example, in the form of epirate or other complex compounds of boron TRIFLUORIDE, for example tetrahydrofuran), pentachloride antimony, trichloride aluminum, titanium tetrachloride, tin tetrachloride and zinc chloride, or in the presence of a proton acid, preferably selected from the group of sulfonic acids or carboxylic acids, such as p-toluensulfonate, methanesulfonate, camphor-10-acid or three ftorotana acid or superacids. Compounds of General formula (VI) is subjected to interaction, for example in organic solvents, including halogenated aliphatic hydrocarbons, such as methylene chloride or chloroform, alcohols, such as methanol or ethanol, or in aromatic compounds such as toluene or xylene, at temperatures from 0 to 40°optionally under protective gas with the catalyst. At the same time as the catalyst use is preferably from 0.01 to 50 wt.% the Lewis acid or from 0.5 to 80 wt.% proton acid (calculated on dimenisonal titanovyi monomer). Interaction can be done in a few hours or to accompany him1H-NMR spectroscopy and in the required time to interrupt the addition of bases (for example, an aqueous solution of sodium carbonate) or alcohols (e.g. ethanol). The compounds of General formula (II) can be subjected to purification by chromatography on a column.

According to the invention remains of alkyl with 2 to 4 carbon atoms in the radical a are ethylene, n-propylene or n-butylene. Linear or branched alkyl residues with 1 to 18 carbon atoms according to the invention are, for example, methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, n-panel, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. The remnants of cycloalkyl with 5-12 carbon atoms are, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclonona or cyclodecyl. The remnants of aryl with 6-14 carbon atoms are, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, benzyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, mesityl or naphthyl, and the remnants of hydroxyalkyl are, for example, hydroxymethyl, 1-hydroxyethyl, 2-hydroxide is, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl and 4-hydroxybutyl. The preceding enumeration is the explanation of the invention by way of examples, and not to consider it as finished.

As substituents of the above residues are treated to numerous organic groups, for example halogen, especially fluorine, chlorine or bromine, as well as simple ester, thioester, disulfide, sulfoxide, sulfonic, aldehyde, ketone, ether groups, carboxylic acid ester group of sulfonic acids, carbonate, cyanide, alkylsilane and alkoxysilane group and/or carboxylamide group.

As a dehydrogenation agent in the method according to the invention are suitable such agents, which are suitable for the dehydrogenation of 2,3-dihydro-, 2,5-dihydro - or tetrahydrothiophene, as well as their derivatives. Preferred are those which cause the dehydrogenation of compounds of General formula (II), however, does not contribute to any subsequent oxidative polymerization of the compounds obtained of General formula (I). When dehydration occurs scenting dihydrothiophenes or compounds of General formula (II). According to the invention, the dehydrogenation can be performed in different ways:

- milirovanie and the removal of hydrogen sulfide;

PHE is educa hydride ions;

- halogenoalkanes halogenation agents and the removal of galgenwaard;

- S-oxidation with a suitable oxidising agent and digitalizacie.

Preferred agents dehydrogenation in the method according to the invention are quinones, sulfur, bromine, N-bromo - or N-chlorosuccinimide, sulfurylchloride, hydrogen peroxide or hypervalent iodine compounds, such as iodosobenzene. When the dehydrogenation of the quinone is direct hydrogenation agent used dehydrogenation (transfer of hydride ions). When using, for example, bromine, N-bromo - or N-chlorosuccinimide or sulfurylchloride is halogenoalkane and subsequent cleavage of halogenation. The hydrogen peroxide or iodosobenzene, for example, is called S-oxidation followed by digitalizacie, and sulfur causes milirovanie with subsequent removal of hydrogen sulfide. Reactions of this type are described in Houben-Weyl, Methods der Organischen Chemie (4. Aufl., Band E 6a (Hetarene I Tell 1), Hrsg. R.P.Kreher, Georg Thieme-Verl., Stuttgart - New York 1994, Chapter "Thiophene" (author: W.-D. Rudolf) pages 370-388 in sections 3.3 to 3.8).

Especially preferred dehydrogenation agent for use in the method according to the invention are the quinones, and among them, particularly preferred 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil) or 2,3-dichloro-5,6-dicyan-1,4-benzoquinone.

Fundamentally the method according to the invention is carried out such about what atom, the compounds of General formula (II) is subjected to interaction with at least an equimolar or excess amount of a dehydrogenation agent at the corresponding temperature, and optionally in an organic solvent for from 0.5 to 48, preferably from 2 to 24 hours. On one mole of the compounds of General formula (II) preferably used from 1 to 2 mol, particularly preferably from 1 to 1.2 mol, agent dehydrogenation, and in many cases is sufficient equimolar ratio between the compound of General formula (II) and dehydrogenation agent. The precipitated solid is optionally filtered and freed from insoluble components by suspendirovanie followed by filtration. For suspension suitable, for example, a mixture of organic solvent and aqueous alkaline solution, such as a 4%aqueous solution of caustic potassium. After the main leaching with subsequent neutral leaching in water, as this vintage solution and the mother liquor obtained after filtering the reaction mixture, concentrated and dried in vacuum. For the main leaching is also suitable aqueous alkaline solutions, such as 4%aqueous solution of caustic potassium. The resulting crude product can be subjected to cleaning by the known methods such as chromatography is and the column or recrystallization. In addition, suitable also remove much of coloring impurities bleaching earth (montmorillonite), for example Tonsil®.

Suitable reaction temperatures for carrying out the method according to the invention are, for example, temperatures from 20 to 200°C, preferably from 100 to 170°and it may be useful to carry out the process of the reverse flow of used solvent. In principle, this is also suitable for low temperature from 20 and up to -78°With, however due to the complexity of external cooling or the use of cooling mixtures they are of secondary importance. Suitable solvents are, for example, optionally halogenated aromatic hydrocarbons such as toluene, xylene, chlorobenzene or o-dichlorobenzene. However, you can also use other inert under the reaction conditions, mainly organic solvents, optionally in a mixture with water.

The method according to the invention initially obtain 2,2'-di(3,4-alkylenedioxy)s the General formula (I), which can be substituted by an ethylene bridge, and some even contain other than ethylene bridge, optionally substituted alkylene bridges. Such compounds of formula (I) hitherto not described in literature.

2,2'-Di(3,4-alkylenedioxy)s the General formula (I) are especially suitable as intermediate, and to receive valuable intermediates in obtaining π-conjugated conductive or polyelectronic polymer or other conductive or polyelectronic connections.

Therefore, another object of the present invention is the use of compounds of General formula (I) as intermediates or to obtain intermediates for obtaining conductive or polyelectronic compounds and/or polymers. In this regard, the polymers comprise in addition to homopolymers, also π-conjugated, conductive or polyelectrolite copolymers containing in addition to the monomer unit of the General formula (V)

other suitable monomer units, such as optionally substituted fluorene, thiophene, furan, paralowie, aniline, pyridine, carbazole or phenylenebis links.

Under conductive or polyelectrolite compounds in this context implies, for example, optionally substituted π-conjugated oligomers, containing at least four identical or different (hetero)arenovich links, such as fluorene, thiophene, furan, paralowie, aniline, pyridine, carbazole or phenylenebis links, and containing at least one m is the number link of the General formula (V) (corresponding to two (hetero)Allenby links). In the field of semiconductors such compounds are also referred to as "small molecules".

A preferred object of the present invention is obtained by application according to the invention compounds or compounds according to the invention of General formula (I) to obtain a conductive or polyelectronic poly(3,4-ethylenedioxythiophene)s or to obtain 5,5'-dihalogen-2,2'-di(3,4-alkylenedioxy)s.

Obtained by the process according to the invention is 2,2'-di(3,4-alkylenedioxy)s the General formula (I) can be converted, for example, oxidative polymerization, for example, using as oxidant compounds of trivalent iron in the corresponding poly(3,4-ethylenedioxythiophene)s, which finds varied application as conductive or polyelectronic polymers.

Therefore, another object of the present invention is a method of obtaining a neutral or cationic poly(3,4-alkylenedioxy)s the General formula (IV)

where A, R and x have the above values,

m means an integer from 2 to 200,

moreover, the compounds of General formula (IV), when they are cationic, are from one to a maximum of (m+2) positive charges

characterized in that 2,2'-di(3,4-alkylenedioxy)s the General formula (I)

where A, R and x have you ukazannye values

is subjected to chemical or electrochemical oxidative polymerization.

Polythiophene General formula (IV) may be neutral or cationic. In the case when it comes to cation polythiophene, the positive charges of politikverflechtung not shown in the formula (IV), since their exact number and their position are not definitely established. The number of positive charges is, however, at least 1 and a maximum of (m+2).

To compensate the positive charge of the cationic form of polythiophenes mainly contains as counterions polyanion.

Polyanionic serve mainly the anions of polymeric carboxylic acids, such as polyacrylic acid, polymethacrylic acid or primaline acid, and polymeric sulfonic acids, such as polystyrenesulfonate and polyvinylacetate. These polycarboxylic and polysulphonate can also be copolymers vinylcarbazole acids and vinylsulfonic with other polymerizable monomers, such as esters of acrylic acid and styrene.

Particularly preferred counterion is an anion polystyrenesulfonate.

The molecular mass of PolicyKit forming polyanion is preferably from 1000 to 2000000, particularly preferably from 2,000 to 500,000. Polyacid and their alkali metal salts of the commercial and accessible, for example, polystyrenesulfonate and polyacrylic acid.

Compounds according to the invention of General formula (I) can be converted chemically or electrochemically by oxidation in polythiophene General formula (IV). Way as oxidative chemical and oxidative electrochemical polymerization of polythiophene or derivatives of 3,4-alkylenedioxy known to the expert and are described in detail in the literature (L.Groenendaal, F.Jonas, D.Freitag, H.Pielartzik und J.R.Reynolds, Adv. Mater. 2000, 12(7), S.481-494). As a suitable oxidant known in the art to obtain polythiophenes, for example, compounds of trivalent iron, such as ferric chloride or tosylate iron (III), potassium permanganate, pyrolusite (manganese dioxide), (b)potassium chromate or peroxydisulfate (persulfates), such as sodium persulfate or potassium, and hydrogen peroxide.

In addition, obtained according to the invention, the compound or compounds according to the invention can be transformed by halogenoalkanes, preferably chlorine or bromirovanii, in compounds of General formula (III) (also known as 5,5'-dihalogen-2,2'-di(3,4-alkylenedioxy)s, which represent valuable intermediates for catalyzed by transition metals to get π-conjugated polymers. The principal method known to the expert and are described, for example, in A.Donat-Bouillud, I.Lévesque, Y.Tao, MD'lorio, S.Beaupré, P.Blondin, V.Ranger, J.Bouchard and M.Leclerc, Chem. Mater. 2000, 12, S.1931-1936.

Therefore, an object of the present invention is also a method of obtaining 5,5'-dihalogen-2,2'-di(3,4-alkylenedioxy)s the General formula (III)

where A, R and x have the above values,

Hal signifies chlorine or bromine,

with the exception of the compounds of formula (III-a)

characterized in that are galogenirovannyie compounds of General formula (I)

where A, R and x have the above values.

Examples

The General prescription for the synthesis of compounds of General formula (II)

The synthesis of compounds of General formula (II) can be carried out, for example, as follows. A solution of 3,4-alkylenedioxy in methylene chloride is subjected to interaction with 0.5-80 wt.% proton acid, for example p-toluenesulfonic acid or triperoxonane acid, or from 0.01 to 50 wt.% a Lewis acid such as boron TRIFLUORIDE in the form of epirate or other complex compounds of boron TRIFLUORIDE as a catalyst at a temperature from 0 to 40°With, if necessary, in an atmosphere of nitrogen. Interaction can be done in a few hours or be accompanied by1H-NMR spectroscopy and at the appropriate moment be interrupted by addition of bases (for example, an aqueous solution is carbonate sodium) or alcohols (for example, ethanol). The compounds of General formula (I) can then be purified by chromatography on a column, for example, on silica gel with methylene chloride as solvent.

Getting 2,2',3,3',5,7-hexahydro-5,5'-betiana[3,4-b][1,4]dioxin (II-a) (EDB-dimer) catalysis with triperoxonane acid

As described in the General instruction, to a solution of 42.6 g (0.3 mol) of 3,4-ethylenedioxythiophene (EDB) in 70 ml of methylene chloride was added to 2.13 g triperoxonane acid in 90 ml of methylene chloride at 18°C. the Reaction mixture was stirred for 48 hours at 18°C under nitrogen. After that, the reaction was interrupted by intense stirring in 150 ml of 5%aqueous sodium carbonate solution. Separated organic phase was washed with water until neutral and the solvent was removed in a rotary evaporator at 20 mbar. The residue (42.2 g) was separated on silica gel by chromatography on a column with methylene chloride as solvent.

Fraction 1: 21 g of EDB.

Fraction 2: 11 g of EDB-dimer identified by1H-NMR in CDCl3crystals (Beige Kristalle).

TPL115-119°C.

Fraction 3: 1 g of EDB-trimer in the form of a mixture of isomers identified by1H-NMR in CDCl3crystals (Beige Kristalle).

The product from fraction 2 used in examples 1 and 2 according to the invention.

On the doctrine of dimethyl-2,2',3,3',5,7-hexahydro-5,5'-betiana[3,4-b][1,4]dioxin (II-b) (methyl-EDB-dimer) catalysis with boron TRIFLUORIDE

As described in the General instruction, to a solution of 6.25 g (40 mmol) of 2-methyl-2,3-dihydrothieno[3,4-b][1,4]dioxin (methyl-EDB) in 30 ml of methylene chloride was added to 0.24 ml epirate of boron TRIFLUORIDE (respectively 269 mg = 1,89 mmol) in 40 ml of methylene chloride at 23°C. the Reaction mixture was stirred at 23°With under nitrogen for 7 hours. After that, the reaction was stopped by adding 20 ml of ethanol. The organic phase is washed with water until neutral and the solvent was removed in a rotary evaporator at 20 mbar. The residue was separated on silica gel by chromatography on a column with methylene chloride as solvent. Yield 1.3 g of methyl-technical publications-dimer (II-b) (20,8% of theoretical).

Getting [(hydroxymethyl)-2,2',3,3',5,7-hexahydro-5,5'-betiana[3,4-b][1,4]dioxines]methanol (II-C) (hydroxymethyl-EDB-dimer)

As described in the General instruction to the solution 6,89 g (40 mmol) of 2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethanol (hydromethyl-EDB, EDB-methanol) in 90 ml of methylene chloride was added to 0.24 ml epirate of boron TRIFLUORIDE (respectively 269 mg = 1,89 mmol) in 120 ml of methylene chloride at 0°C. the Reaction mixture was stirred at 0°C under nitrogen for 4 hours. Then the reaction was stopped by addition of a mixture of 60 ml of ethanol/120 ml water. delali the organic phase and the solvent was removed in a rotary evaporator at 20 mbar. The residue was separated on silica gel by chromatography on a column with methylene chloride as solvent. Yield 2.0 g hydroxymethyl-technical publications-dimer (II-C) (29% of theoretical).

Example 1. Getting 2,2'-di(3,4-ethylenedioxythiophene)and (I-a) (invention).

28,64 g (0.1 mol) of EDB-dimer (II-a) was dissolved in 500 ml of xylene. To this solution was added 24,59 g (0.1 mol) of chloranil. The mixture was heated at 140°C for 10 hours with reverse flow. After cooling, was sucked out the precipitated crystals, and as the crystals and the mother liquor is subjected to further processing.

The mother liquor was washed four times with 50 ml of 4%aqueous solution of caustic potash, and finally washed with water until neutral. The solution is evaporated and dried in high vacuum. Got to 15.8 g of crude product in the form of green crystals (fraction A).

Sucked away the crystals suspended in 150 ml of xylene and 100 ml of 4%aqueous solution of caustic potash, and nerastvorim part (5.5 g) was filtered. The mother liquor is subjected to further processing as the above-mentioned mother liquor. After evaporation got 6.4 g of crude product in the form of green crystals (fraction B).

The crude product (fractions a and b) was dissolved in 370 ml of methylene chloride and suspended with 21 g of Tonsil® (bleaching earth type montmorillonite, manufacturer: Süd-Chemie, M is nchen). After bleaching solution Tonsil® was filtered and the methylene chloride was removed in a rotary evaporator.

Selected 18 g (63% of theory) of 2,2'-di(3,4-ethylenedioxythiophene)s (I-a) in the form of light yellow crystals. TPL204-205°C.

1H-NMR spectrum (400 MHz, CDCl3, ppm): 4,24 (4H, m), or 4.31 (4H, m), 6,27 (2H, s).

Of 5.5 g of insoluble components by dispersion with Tonsil® in methylene chloride by the same method obtained 1.5 g of 2,2'-di(3,4-ethylenedioxythiophene)s. The overall yield of 69% of theoretical.

Example 2. Getting 2,2'-di(3,4-ethylenedioxythiophene)s (I-a) with 2,3-dichloro-5,6-dicyan-p-benzoquinone.

8.53 g (30 mmol) of EDB-dimer (II-a) was dissolved in 150 ml of xylene. To this solution was added to 7.15 g (to 31.5 mmol) of 2,3-dichloro-5,6-dicyan-p-benzoquinone. The mixture was heated at 140°reverse thread within 24 hours. After cooling, was dissolved in a 4%solution of caustic potash until such time as a solution of caustic potash remained colorless. In conclusion, washed with water until neutral. The solution was evaporated and dried in vacuum. Got 3,68 g (43.5% of theoretical) of crude product in the form of gray-brown residue. This crude product was purified chromatographically, passing through silicagel the column, the solvent is methylene chloride.

Allocated to 1.32 g (15.6% of theoretical) of pure 2,2'-di(3,4-ethylenedioxythiophene)s (I-a). Tp is 207-209°C.

Data1H-NMR (400 MHz, CDCl3) identical to example 1.

Example 3. Getting dimethyl-2,2',3,3'-tetrahydro-5,5'-betiana[3,4-b][1,4]dioxin (I-b).

0,85 g (2.7 mmol) of methyl-EDB-dimer (II-b) was dissolved in 50 ml of xylene. To this solution was added 0,668 g (2.7 mmol) of chloranil. The mixture was heated at 140°With reverse flow within 14 hours. After cooling it was diluted with methylene chloride and shaken with 4%solution of caustic potash until such time as a solution of caustic potash remained colorless. In conclusion, washed with water until neutral. The solution was evaporated and dried in high vacuum. Got to 0.48 g (56,7% of theoretical) of crude product (I-b) as a residue. The product was purified chromatographically on silica gel with the solvent - methylene chloride. The net yield of 0.38 g (44,8% of theoretical).

1H-NMR spectrum (400 MHz, CDCl3, ppm): 6,24, 6,235, 6,23 (3s, together 2H), 4,39 (optional split q3J=6,56 Hz) and 4,32 (optional split q3J=6,56 Hz, both q together 2H); to 4.28 (dd,2J=11,60 Hz3J=2,04 Hz) and is 4.15 (dd,2J=11,60 Hz3J=2,04 Hz, both dd, together 2H); 3,91 (dd,2J=11,60 Hz3J=8,56 Hz) and 3,865 (dd,2J=11,60 Hz3J=8,56 Hz, both dd, together 2H); 1,42 (d3J=6,56 Hz) and 1,355 (d3J=6,56 Hz, both d, together 6N). The NMR spectrum showed the presence of a mixture of products about SL is blowing components:

Example 4. Getting [(hydroxymethyl)-2,2',3,3'-tetrahydro-5,5'-betiana[3,4-b][1,4]dioxines]methanol (I-C).

2.4 g (7 mmol) of hydroxymethyl-EDB-dimer (II-C) was dissolved in 50 ml of xylene. To this solution was added 1,713 g (7 mmol) of chloranil. The mixture was heated at 140°reverse thread within 24 hours. After cooling, was dissolved in a 4%solution of caustic potash until such time as a solution of caustic potash remained colorless. In conclusion, washed with water until neutral. The solution was evaporated and dried under high vacuum. Received 0.2 g (8.3% of theoretical) (I-C) as a residue.

1H-NMR spectrum (400 MHz, CDCl3, parts per million): 6,285; 6,275; 6,27; 6,26; (4s, together 2H), 4,21-to 3.73 (several m, together 6N). The NMR spectrum showed the presence of a mixture of products of approximately the following components:

1. 2,2'-Di(3,4-alkylenedioxy)s the General formula (I)

where a represents optionally substituted residue of alkyl with 2 to 4 carbon atoms,

R means one or more identical or different linear or branched, optionally substituted what's the remnants of alkyl with 1-18 carbon atoms, optionally substituted residues hydroxyalkyl with 1-4 carbon atoms or one or more residues of hydroxyl,

x means an integer from 0 to 8,

with the exception of the compounds of formula (I), in which

And means unsubstituted residue of ethylene and

x is 0.

2. 2,2'-Di(3,4-alkylenedioxy)s the General formula (I) according to claim 1, wherein a represents optionally substituted residue of ethylene,

R means one or several identical or different, linear or branched, optionally substituted alkyl residue with 1 to 18 carbon atoms, optionally substituted residues hydroxyalkyl with 1-4 carbon atoms or one or more residues of hydroxyl,

x means an integer from 0 to 4.

3. 2,2'-Di(3,4-alkylenedioxy)s the General formula (I) according to claim 2, characterized in that a represents optionally substituted residue of ethylene,

R means methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl or hydroxymethyl,

x is 0 or 1.

4. The use of 2,2'-di(3,4-alkylenedioxy)s the General formula (I) according to one of claims 1 to 3 as intermediates or to obtain intermediates for obtaining conductive or polyelectronic compounds and/or electrically conductive or polyelectronic polymer is.

5. The way to obtain 2,2'-di(3,4-alkylenedioxy)s the General formula (I)

where a represents optionally substituted residue of alkyl with 2 to 4 carbon atoms,

R means one or several identical or different, linear or branched, optionally substituted alkyl residue with 1 to 18 carbon atoms, optionally substituted residues cycloalkyl with 5-12 carbon atoms, optionally substituted aryl residue with 6 to 14 carbon atoms, optionally substituted residues hydroxyalkyl with 1-4 carbon atoms or one or more residues of hydroxyl,

x means an integer from 0 to 8,

characterized in that compounds of General formula (II)

where A, R and x have the above meanings, is subjected to the interaction with the dehydrogenation agent selected from the group of quinones.

6. The method according to claim 5, characterized in that the use of the compounds of formula (II)in which a represents optionally substituted residue of ethylene,

R means one or several identical or different, linear or branched, optionally substituted alkyl residue with 1 to 18 carbon atoms, optionally substituted residues cycloalkyl with 5-12 carbon atoms, optionally samisen the x residue of the aryl with 6-14 carbon atoms, optionally substituted residues hydroxyalkyl with 1-4 carbon atoms or one or more residues of hydroxyl,

x means an integer from 0 to 4.

7. The method according to claim 6, characterized in that the use of the compounds of formula (II)in which a represents optionally substituted residue of ethylene,

R means methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl or hydroxymethyl,

x is 0 or 1.

8. The method according to claim 7, characterized in that the use of the compounds of formula (II)in which a represents unsubstituted residue of ethylene, x is 0.

9. The method according to claim 5, characterized in that as a dehydrogenation agent use 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil) or 2,3-dichloro-5,6-dicyan-1,4-benzoquinone.

10. A method of obtaining a neutral or cationic poly(3,4-alkylen-dioxythiophene)s the General formula (IV)

where a represents optionally substituted residue of alkyl with 2 to 4 carbon atoms,

R means one or several identical or different, linear or branched, optionally substituted alkyl residue with 1 to 18 carbon atoms, optionally substituted residues cycloalkyl with 5-12 carbon atoms, optionally substituted aryl residue with 6 to 14 carbon atoms, if necessary, replace the i.i.d. residual hydroxyalkyl with 1-4 carbon atoms or one or more residues of hydroxyl,

x means an integer from 0 to 8,

m means an integer from 2 to 200, and

moreover, the compounds of General formula (IV) if they are cationic, are from one to a maximum of (m+2) positive charge, characterized in that

2,2'-di(3,4-alkylen-dioxythiophene)s the General formula (I)

where A, R and x have the above values,

is subjected to chemical or electrochemical oxidative polymerization.

11. The method according to claim 10, characterized in that the use of the compounds of formula (I)in which a represents optionally substituted residue of ethylene,

R means one or several identical or different, linear or branched, optionally substituted alkyl residue with 1 to 18 carbon atoms, optionally substituted residues cycloalkyl with 5-12 carbon atoms, optionally substituted aryl residue with 6 to 14 carbon atoms, optionally substituted residues hydroxyalkyl with 1-4 carbon atoms or one or more residues of hydroxyl,

x means an integer from 0 to 4.

12. The method according to claim 11, characterized in that the use of the compounds of formula (I)in which a represents optionally substituted residue of ethylene,

R means methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, is-dodecyl, n-tetradecyl or hydroxymethyl,

x is 0 or 1.



 

Same patents:

FIELD: electricity.

SUBSTANCE: invention is related to the field of electric engineering and is designed for preparation of piezoresistive composite used in devices that transform mechanical deformation into electric signal. For this purpose piezoresistive composite is suggested, which consists of polymer elastic nonconducting layer and conducting material made in the form of nanostructured layer with thickness of 10-20 nm applied on polymer nonconducting layer. Piezoresistive composite is prepared by formation of polymer elastic nonconducting layer, on which layer of conducting material is applied with thickness of 10-20 nm, and then both layers are subjected to monaxonic tensile deformation at the value of relative deformation of 50-100% for preparation of conducting nanostructured layer.

EFFECT: simplification of method of piezoresistive composite preparation and increase of its economy, expansion of functional resources of sensors used on the basis of prepared composite.

2 cl, 1 dwg

FIELD: electricity.

SUBSTANCE: invention relates to electric engineering and, particularly to electro conductive, corrosion preventing compounds used for releasable contact joints operation in order to decrease transient resistance and environmental corrosion effects. Electro-conductive lubricant consists of cupreous filling compound and bounding material. Besides, graphite powder is additionally introduced into filling compound. Copper is introduced in the form of dust and lithol is used as bounding material at the following mas.% ratio of components: graphite powder 35-45, cupreous dust 15-25, lithol 35-45. Cost of lubricant is reduced and its manufacture process is simplified owing to application of copper wastes in the form of cupreous dust and to corrosion proofing.

EFFECT: simplification of technology and cost reduction of electro-conductive lubricant with corrosion stable properties.

1 tbl

Resistive material // 2330342

FIELD: electric engineering.

SUBSTANCE: resistive engineering contains chrome, modifying additives of manganese, cobalt and nickel dioxide, alloying additives of iron and titanium at the following quantitative ratio of components, in weight %: chrome 90-94, manganese dioxide 1-4, nickel dioxide 1-2, cobalt dioxide 4-6, iron 0.03-0.1, and titanium 0.1-0.2. Proposed resistive material provides for national production of heat-resistant targets which are used for electro-conductive films production of low resistors having 0.1-3.0 Ohm resistance and temperature coefficient of resistance - to ±100×10-6 1/°C.

EFFECT: decrease of thermal film resistance and temporary instability of resistance temperature from low resistors.

1 tbl

FIELD: electricity, chemistry.

SUBSTANCE: electroconductive lubricant includes filler and binder where zinc plant clinker is used as the filler and lithol is used as the binder with the following percentage of components in % weight: clinker 40÷60; lithol 60÷40. This will allow for achievement of lower cost of lubricant, to simplify its manufacturing process, and to provide lubricant with anticorrosion properties.

EFFECT: decrease of transfer resistance, corrosion impact of environment.

1 tbl

FIELD: electricity, chemistry.

SUBSTANCE: electroconductive lubricant includes filler and binder where zinc plant clinker is used as the filler and lithol is used as the binder with the following percentage of components in % weight: clinker 40÷60; lithol 60÷40. This will allow for achievement of lower cost of lubricant, to simplify its manufacturing process, and to provide lubricant with anticorrosion properties.

EFFECT: decrease of transfer resistance, corrosion impact of environment.

1 tbl

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of conducting polyaniline without adding any acid to the reaction. Method involves dissolving oxidizing agent in pure solvent and addition of aniline monomer at stirring by drops. Then the reaction mixture is kept at temperature 10-35°C for 4-10 h. Prepared conducting polyaniline is precipitated by immersion in distilled water and separated. Invention provides development of noncorrosion method for synthesis of polyaniline that shows safety for environment.

EFFECT: improved method of synthesis.

12 cl, 4 ex

FIELD: electrical engineering including cable engineering.

SUBSTANCE: proposed cold- and heat-resistant cable incorporating at least one metal conductor entirely covered with shielding coat and with single-layer or multilayer insulation has its shielding coat of at least one conductor made of composite material including metal matrix and at least one ultra-dispersed nonmetal filler whose particles are distributed throughout metal matrix; mentioned shielding coat prevents damage to polymeric insulation by ions of copper and/or other transition metals of mentioned conductor.

EFFECT: enlarged functional capabilities.

14 cl, 1 dwg

FIELD: electrical engineering; electricity-conductive compound in the form of flocculent particles.

SUBSTANCE: proposed compound has titanium oxide with mean large diameter of 1 to 100 μm and mean thickness of 0.01 to 1.5 μm, potassium in amount of 0.03 to 5 mass percent in the form of potassium oxide (K2O), as well as first electricity-conductive layer which is formed on surface and has in its composition tin oxide and antimony, and second electricity-conductive layer which is formed on first electricity-conductive layer and has in its composition tin oxide. Proposed electricity-conductive composition in the form of flocculent particles is capable of imparting good electricity-conductive properties even when formed in layer of 1 to 10 μm in thickness.

EFFECT: improved properties of electricity-conductive composition.

6 cl 3 tbl, 6 ex

FIELD: electronic engineering.

SUBSTANCE: invention relates to manufacture of gas-discharge indicator panels and provides a method for preparing pastes used to form elements of gas-discharge indicator panels, which method comprises preparation of filler powder, reduction from solution, and washing with organic solvent having boiling temperature T1=100-200°C. This solvent may be the same as is used in organic binder composition and, when another solvent is used, the latter is selected from those having boiling temperatures T2 meeting the following inequality: T1 ≤ 0.8T2.

EFFECT: enabled formation of gas-discharge indicator panels with high resolution level.

3 cl

FIELD: electronic engineering, applicable in production of gas-discharge indicating panels.

SUBSTANCE: use is made of pastes, in the production of process of which the filler powder is mixed and ground in and organic solvent taken in amounts respectively 1.5 to 245 percent by mass and 75 to 98.5 percent by mass. To improve the paste quality, the filler powder and organic solvent mix is agitated with addition of balls, 2 to 5 mm in diameter, taken in amounts of 60 to 100 percent of the mix mass,, for preparation of the paste use is also made of am organic binder heated to 45-65 C.

EFFECT: provided forming of components of the gas-discharge panel with a high degree of resolution.

3 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention concerns polymer material displaying optically detectable response to load (pressure) change, including polyurethane elastomer adapted for load change detection, containing aliphatic diisocyanate, polyol with end hydroxyl, and photochemical system including fluorescent molecules for distance probing, modified and transformed into chain-extending diols, with molar diol to polyol ratio approximately within 10:1 to 1:2 range, and photochemical system selected out of group of exciplex and fluorescence resonance energy transfer (FRET) systems. The invention also concerns solution containing the said polymer material, and polymer material displaying detectable response to pressure change, including polyacryl or silicon elastomer and photochemical system including definite number of fluorescent molecules for distance probing, modified for penetration into the said elastomer, selected out of group including exciplex and fluorescence resonance energy transfer (FRET), and solution containing this polymer material. To eliminate oxygen sensitivity in pressure detection the material includes photochemical system selected out of group including exciplex and fluorescence resonance energy transfer (FRET). Systems including these photochemical systems enable fast response to pressure change; in addition, compression of material containing these systems is reversible, therefore elimination of oxygen influence on pressure change detection allows shorter response time and higher sensitivity when the claimed material is used.

EFFECT: increased material sensitivity to loads and reduced sensitivity to oxygen presence.

24 cl, 2 ex, 6 dwg

FIELD: chemistry.

SUBSTANCE: description is given of the method of obtaining a water dispersion containing a complex of poly(3,4-dialkoxythiophen) and polyanion, including polymerisation of 3,4-dialkoxy-thiophen, with general formula (I): where R1 and R2 independently represent a hydrogen atom or alkyl with 1-4 atoms of carbon, or together form an alkylene group with 1-4 carbon atoms, which can be substituted in the presence of polyanion with use of peroxodisulphuric acid as an oxidiser in a water solution with pH equal to or less than 1.5, or use of an oxidiser in a water solution, in which acid has been added, chosen from a group, consisting of water soluble inorganic acids and water soluble organic acids, in quantity providing for pH of the obtained reaction mixture equal to 1.5 or less. Description is also given of the composition of the coating, containing water dispersion which contains the complex of poly(3,4-dialkoxythiophen) and polyanion. The substrate with a conducting transparent film, obtained through deposition of the above given composition is also described.

EFFECT: obtaining of water dispersion, providing the coating obtained from it with lower surface resistivity.

4 cl, 2 tbl, 1 dwg, 18 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of neutral polythiophenes. Invention relates to neutral polythiophenes of the general formula (I): wherein R1 and R2 mean independently of one another hydrogen atom or alkyl with 1-9 carbon atoms being in case when R1 means hydrogen atom then R2 can mean -CH2-O-R3 also wherein R3 means hydrogen atom or alkyl with 1-9 carbon atoms, cycloalkyl or aralkyl; n means a number from 2 to 200. These compounds are soluble in organic solvents and free of organically bound halogen. Except for, invention relates to a method for synthesis of neutral polythiophenes. Neutral polythiophenes can be used in different fields, for example, in memory device, in optical transformation of signal, blocking electromagnetic radiations and in transformation of solar energy in over-charged batteries, light-diode, field transistors, printing boards, sensitive units, condensers and others.

EFFECT: valuable technical properties of compounds, improved method of synthesis.

16 cl, 5 ex

FIELD: waterless conducting solutions.

SUBSTANCE: invention, in particular, relates to preparation of solutions containing optionally substituted polythiophenes in waterless or low-water organic solvents, to solutions themselves, an to their technical applications. Solution preparation method of invention is characterized by that to an aqueous solution of ionic complexes polythiophene+An+ (wherein polythiophene+ denotes polymers containing positively charged repetitive units of formula I) is added a water-miscible organic solvent or a water-miscible mixture of organic solvents. Resulting mixture is then at least partially freed of water. Invention also includes solutions of ionic complexes prepared according to above-indicated method. Further included are also: method of imparting electrical conductivity to substrates, method of imparting antistatic properties to substrates, method of preparing solid electrolytes in solid condensers, and method of manufacturing electroluminescent devices.

EFFECT: extended choice of waterless conducting solutions for a variety of technical applications.

11 cl, 2 tbl, 3 ex

The invention relates to the field of production of unsaturated oligoaryleneetherketones that can be used to obtain a heat-resistant polymers in various fields of technology

FIELD: chemistry, pharmaceutics.

SUBSTANCE: claimed invention relates to novel azaheterocycles of general formula 1.1-13 and 2, as well as their pharmaceutically acceptable salts, which possess anti-carcinogenic activity, pharmaceutical composition with their application and combinatorial and focused libraries including novel azaheterocycles. In general formulae 1.1-1.3 and 2.

.

For compounds 1.1-1.3 each of R1a R2a independently on each other represent possibly substituted C1-C6alkyl; each of R1d, R2d, R3d, R4d, R5d, R6d and R7d independently on each other represent substitutes of cyclic system, preferably hydrogen atom, or for compounds 1.1 and 1.3 independently R1d and R2d, R3d and R4d, R5d and R6d together with atoms with which they are bound can form through R1d and R2d, R3d and R4d, R5d and R6d respectively, possibly substituted aromatic cycle, such as benzole, 5-6-member heterocycle which includes, at least, one of heteroatoms, selected from S; or for compounds 1.2 independently R1d and R2d, R3d and R4d, R4d and R5d, R6d and R7d together with atoms with which they are bound can form through R1d and R2d, R3d and R4d, R4d and R5d, R6d and R7d respectively, possibly substituted aromatic cycle, such as benzole, 5-6-member heterocycle which includes, at least, one of heteroatoms, selected from S; for compound 2 R1a represents amino group substitute, excluding hydrogen atom, such as possibly substituted C1-C6alkyl, possibly substituted phenyl; R2a represents possibly substituted C1-C6alkyl; R3a represents amino group substitute, such as hydrogen atom, possibly substituted C1-C6alkyl; Rnd represents one or two substitutes of cyclic system, preferably hydrogen atom, solid line with accompanying it dotted line represent single or double bond.

EFFECT: obtaining novel azaheterocycles and their pharmaceutically acceptable salts, which possess anti-carcinogenic activity.

9 cl, 4 dwg, 3 tbl, 7 ex

FIELD: chemistry, pharmaceutics.

SUBSTANCE: invention relates to method of obtaining 4-amino-3-quinolinecarbonitryl, which includes: a) combining aminocompound with cyanoacetic acid and acid catalyst obtaining cyanoacetomide; b) condensing cyanoacetomide from stage a with aniline, alcohol solvent and trialkylorthoformiate obtaining 3-amino-2-cyanoakrylamide; and c) combining 3-amino-2-cyanoakrylamide with phosphorus oxychloride in acetonitryl, butyronitrile, toluol or xylol, optionally in presence of catalyst, obtaining 4-amino-3-quinolinecarbonitryl. Also described is method (version) of obtaining 4-amino-3-quinolinecarbonitryl, method of obtaining 7-aminothieno[3,2-b]pyridine-6-carbonitrile and method of obtaining cyanoacetamide.

EFFECT: creation of efficient method of obtaining 4-amino-3-quinolinecarbonitryl.

24 cl, 50 ex

FIELD: medicine; pharmacology.

SUBSTANCE: new annelated asaheterocycles include pyrimidine fragment of general formula I in the form of free bases or pharmaceutically acceptable salts. Compounds of this invention possess properties of PI3 kinase inhibitors. In general formula I X represents oxygen atom or sulphur atom; Z represents oxygen atom, R1 represents hydrogen atom or optionally substituted C1-C6alkyl, or Z represents nitrogen atom together with bound carbon atom forming through Z and R1 optionally substituted annelated imidazoline cycle; R2 represents optionally substituted C1-C6alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted phenyl, possibly annelated with 5-6-term heterocyclyl containing heteroatoms chosen from oxygen and nitrogen, optionally substituted 5-6-term heterocyclyl containing heteroatoms chosen from nitrogen, oxygen and/or sulphur, possibly annelated with phenyl ring. Invention also concerns method of production of compounds, pharmaceutical compositions and medical products.

EFFECT: effective application for preparation of medical products for oncologic therapy.

14 cl, 3 dwg, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: novel compounds are selected from group, consisting of: 4-(2-cyclopropyl-ethyl)-piperazine-1-carboxylic acid 2-methyl-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclopropylmethyl-piperazine-1-carboxylic acid 3-methyl-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclopropylmethyl-piperazine-1-carboxylic acid 3-fluorine-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-(2-hydroxymethyl-cyclopropylmethyl)-piperazine-1-carboxylic acid 2-methyl-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclopentylmethyl-piperazine-1-carboxylic acid 2-methyl-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclopropylmethyl-piperazine-1-carboxylic acid 3-chlorine-4-(3-methyl- 4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclobutylmethyl-piperazine-1-carboxylic acid 3-chlorine-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclobutylmethyl-piperazine-1-carboxylic acid 2-methyl-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-(2-cyclopropyl-ethyl)-piperazine-1-carboxylic acid 3-methyl-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclobutylmethyl-piperazine-1-carboxylic acid 3-methyl-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclobutylmethyl-piperazine-1-carboxylic acid 3-fluorine-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclobutylmethyl-piperazine-1-carboxylic acid 2-fluorine-4-(3-methyl-4,10-dihudro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclopropylmethyl-piperazine-1-carboxylic acid 2-fluorine-4-(3-methyl-4,10-dihydro-3H-2,3,4;9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclobutylmethyl-piperazine-1-carboxylic acid 4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclopropylmethyl-piperazine-1-carboxylic acid 3-ethyl-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclobutylmethyl-piperazine-1-carboxylic acid 2-chlorine-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide; 4-cyclopropylmethyl-piperazine-1-carboxylic acid 2-chlorine-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-benzylamide and 4-cyclobutylmethyl-piperazine-1-carboxylic acid 3-methoxy-4-(3-methyl-4,10-dihydro-3H-2,3,4,9-tetraazabenzo[f]azulene-9-carbonyl)-benzylamide. Invention also relates to pharmaceutical composition and to application of compounds of general formula 1.

EFFECT: obtaining novel biologically active compounds and based on them pharmaceutical composition, possessing antagonistic activity with respect to vasopressin receptors.

60 cl, 153 ex

FIELD: agriculture.

SUBSTANCE: new chemically biologically active compound 3-amino-4,5,6-trimethyl-2-(benzimidazolyl-2)tieno[2,3-b]pyridine of formula 1 revealing growth regulating properties is described.

EFFECT: increasing sugar beet crop yield and sugar content.

1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel substituted indoles of general formula , where: X stands for -S(O)n-, -C(O)-; A stands for C1-C6alkyl, -(CH2)p-NRaRb; R1, R2, R3 and R4 each is independently selected from group including H, halogen, halogen(C1-C6)alkyl, C1-C6alkyl, C1-C6alkoxy, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, NO2, -NRaRb, phenyl, benzyl and benzyloxy, said phenyl cycles are optionally substituted with substituent, selected from group including C1-C6alkyl, halogen, NO2, halogen(C1-C6)alkyl, C1-C6alkoxy; R5 stands for H, C1-C6alkyl, C1-C6alkoxy, C1-C6alkoxy C1-C6alkyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, hydroxyl-(C1-C6)alkyl, hydroxy(C1-C6)alkylamino, halogen, halogen(C1-C6)alkyl-NRaRb, -NRc-( C1-C6)alkylene-NRaRb, or R5 and A together form radical C2-C3alkylene; R6 stands for H, C1-C6alkyl; R' and R" each independently stand for H, C1-C6alkyl; Ra, Rb and Rc each is independently chosen from group including H, C1-C6alkyl, hydroxy(C1-C6)alkyl, C2-C6alkenyl, C3-C6cycloalkyl-(C1-C6)alkyl, or Ra and Rb together with nitrogen atom, to which they are attached, form 5-7 member non-aromatic heterocyclic cycle, optionally containing in cycle O as additional heteroatom; m is equal 1 or 2; n is equal 0, 1 or 2 under condition that, if n is equal 0, R5 does not stand for NRaRb, and p is equal 0, 1 or 2; or their pharmaceutically acceptable salts.

EFFECT: obtaining compounds possessing agonistic activity which allows using them in pharmaceutical composition.

24 cl, 2 tbl, 22 ex

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