Polyarylsilane dendrimers and method of obtaining them

FIELD: chemistry.

SUBSTANCE: invention relates to field of chemical technology of silicon-organic compounds. Technical task lies in synthesis of novel polyarylsilane links including dendrimers of large generations suitable for application as luminescent materials for organic electronics and photonics. Claimed are dendrimers of general formula (I) where R1 stands for substituent from group: linear or branched C1-C20alkyl groups; linear or branched C1-C20alkyl groups separated by at least one oxygen atom; linear or branched C1-C20 alkyl groups separated by at least one sulphur atom; branched C3-C20 alkyl groups separated by at least one silicon atom; C2-C20alkenyl groups; Ar represents, independently for each n and m, similar or different arylene radicals, selected from group: substituted or non-substituted thienyl-2,5-diyl of general formula (II-a) substituted or non-substituted phenyl-1,4-diyl of general formula (II-b) substituted or non-substituted 1,3-oxazol-2,5-diyl of general formula (II-c) substituted fluorene-4,4'-diyl of general formula (II-d) where R2, R3, R4, R5, R6 represent independently on each other H or said above for R1; R7 stands for said above for R1; K is equal 2 or 3 or 4; L is equal 1 or 3 or 7 or 15; m and n represent whole numbers from series from 2 to 6. Method of obtaining dendrimers lies in the following: monodendron of general formula (III) where X represents H or Br or I, first reacts with lithiumising agent of general formula R8Li, where R8 represents linear or branched C1-C10alkyl group, dialkylamide or phenyl group; then obtained compound reacts with functional compound selected from group of compounds of formula (CH3)4-KSiYK, where Y represents Cl, or Br, or -OCH3, or -OC2H5, or -OC3H7, or -OC4H9. Claimed method is technological, use of expensive catalysts is not required.

EFFECT: elaboration of technological method of synthesising novel polyarylsilane dendrimers which does not require use of expensive catalysts.

24 cl, 12 dwg, 1 tbl, 13 ex

 

The invention relates to the field of chemical technology organosilicon compounds and can find industrial application in obtaining new functional materials with luminescent properties. More specifically, the invention relates to new polarissilber the dendrimers and the way they are received.

Dendrimers are highly ordered spatial hyperbranched fully acyclic education, built on the law of the branching tree. There are two basic methods of obtaining dendrimers:

divergent and convergent. In the first case, the synthesis of dendritic molecules occurs in layers in the direction from the center to the periphery by repetition of at least two chemical reactions. This produces a number of individual dendrimers-homologues, called generations, and the generation number G matches the number of accreted layers of branching (Figure 1). In the case of a convergent synthesis of the molecule construction of dendrimers occurs from the periphery to the center. To do this, first get "branches", which are called monumentally and contain a single functional group at the focal point (Figure 2). The resulting monodendri attached to the center of the fork with the formation of dendrimers (S.M.Grayson, J.M.J.Frechet, Chem. Rev. 2001. V.101. P.3819-386). The original monodendri could the t can be obtained as convergent and divergent method. Depending on the functionality of the Central branch, which is usually equal to two, three or four, you get dendrimers with different number of branches-Andronov defined by the branching center NC=To (Figure 3). The branching structure of each branch of the dendrimer (Dendron) depends on the functionality of the recurring element of this macromolecule (NB) and is usually equal to 2 or 3. For example in figure 1, figure 2 and Figure 3 presents dendritic macromolecule with NB=2.

Unlike conventional polymers, dendrimers are individual connections, which allows them to allocate a purity available for low molecular weight compounds, which is especially important for organic electronics and Photonics. Specific three-dimensional architecture of dendritic macromolecules gives them also a number of valuable properties, such as good solubility and film formation, in combination with the possibility to adjust their optical and electrical properties by targeted molecular design.

Under organosilicon dendrimers as part of this invention we understand these dendrimers that contain silicon atoms as points of branching. Examples of such systems are polycarbosilane dendrimers (.Lang, .Liihmann, Adv. Mater. 2001, v.13, No.20, pp.1523-1540).

Under kilcranny in this image the attachment means connection, have a direct connection to the silicon-aryl or silicon-heteroaryl. Known linear and branched ailinani, as well as linear and branched polymers with arislanova fragments in the main chain or as lateral substituents.

Under polyarizovannymi the dendrimers of the present invention refers to compounds having as branching points of the silicon atoms, which are interconnected allenbyi or heteroaridarum fragments. This arrelano fragments are located in the entire volume, i.e. both internally and in the external sphere of dendritic macromolecules.

Organic light-emitting dendrimers and devices on their basis stated, for example, in European patent EP 1027398 B1, 2004, U.S. Patent US 6558818 B1, 2003 and US 6720093 B2, 2004. Used dendrimers may contain silicon fragments, and heteroarenes, including thiophene. These dendrimers, however, are not any silicon at all, nor polyarizovannymi in particular.

Linear and branched arisian containing as aryl several coumarin fragments described in W02006046416, 2006. Branched compounds on the basis of diarylpyrimidine described in U.S. patent US 6307083 B1, 2001. However, these compounds contain in the structure of the double bond, which makes them sensitive to oxide the structure and reduces the service life of functional materials based on them.

Copolymers arrelano with fluorenone described in U.S. patent US 6558819 B1, 2003. Each silicon atom contains two aryl and two arenovich Deputy, which makes the structure of the linear polymer. Linear heteroaromatic block copolymers, including on the basis of arrelano described in U.S. patent US 7279534 B2, 2007. Allenbyi polymers, including arislanova lateral substituents, patented in US 7084231 B2, 2006.

Known thiofentanyl dendrimer of the first generation And has the following structural formula (Tetrahedron Letters, 1997, v.38, No.34, pp.6043-6046):

which can be represented by the General formula (a-1):

The dendrimer was synthesized by otherovarian Tetra-2-tamilselvan butyllithium with subsequent interaction obtained poliitikaga connection with Tris-2-tamilmasala with the release of 19% at optimized conditions. Low yield due to exchange reactions of hydrogen and lithium in the thiophene rings. To get so dendrimers large size is not possible due to the insolubility polylithium compounds. In addition, dendrimer And luminescent properties is not.

The closest in structure to the claimed polarissilber the dendrimers is biliopancreatic dendrimer of the first gene is the radio B, has the following structural formula (proceedings of the Academy of Sciences, Series of Chemical, 2005, No. 3, S-679):

which can be represented by the General formula (B-1):

Dendrimer B, in contrast to the stated arrelano dendrimers, contained only three functional biliopancreatic fragment inside the macromolecule, as well as end groups contained monocytopenia fragments, does not exhibit fluorescent properties, and therefore not functional in the framework of this invention. In its structure there was no limit alkyl groups. In addition, the dendrimer B was obtained by reacting ORGANOMETALLIC education communication thiophene-thiophene from tribrom - and monofunctional magnesium or boron derivatives in terms Suzuki or Comedy. The disadvantages of these reactions is the need for use of expensive palladium catalysts.

Polyarylene the large dendrimers of generations (G>1) are not described in literature.

The task of the claimed invention to provide a new technical result consists in the synthesis of new polianilinovyh dendrimers containing at least six functional arrelano links, including large dendrimers of generations, has set its the TV for their use as luminescent materials for organic electronics and Photonics. As such, the properties within this invention are the good solubility, high luminescence efficiency and stability.

In addition, the object of the invention is to develop a new method of obtaining the claimed polianilinovyh dendrimers, allowing you to get the products given the structure of high purity and suitable for use in an industrial environment.

The task is solved in that the received polyarylene dendrimers General formula (I)

where R1means the Deputy from a range of: linear or branched C1-C20alkyl group; a linear or branched C1-C20alkyl groups separated by at least one oxygen atom; a linear or branched C1-C20alkyl groups separated by at least one sulfur atom; a branched C3-C20alkyl groups separated by at least one atom of silicon;

C2-C20alkeneamine group;

Ar means, independently for each n and m, the same or different allenbyi or heteroarenes radicals selected from the series of: substituted or unsubstituted thienyl-2,5-diyl General formula

substituted or unsubstituted phenyl-1,4-diyl General formula (II-b)

substituted or unsubstituted 1,3-oxazol-2,5-diyl General formula (II-b)

substituted fluoren-4,4'-diyl General formula (II-g)

where R2, R3, R4, R5, R6independently of one another denote H or a Deputy of the above series for R1preferably N or C1-C12linear or branched alkyl group; R7means the Deputy of the above series for R1preferably C1-C12linear or branched alkyl group;

It is 2 or 3 or 4, preferably 3;

L is 1 or 3 or 7 or 15, preferably 1 or 3 or 7;

m means an integer from the range from 2 to 6, preferably 2 or 3, or 4;

n means an integer from the range from 2 to 6, preferably 2 or 3, or 4.

When this fragment (N3C)4-K-Si is the center of branching dendrimers, and its branching is determined by the value of K; the inner part of the molecule of dendrimer consists of KL repetitive fragmentsand the outer layer of the dendrimer are fragmentsthe number of which is equal to K(L+1).

The principles mentioned in the formulas (II-a)to(II-g) sign * (asterisk)are points of connection, in which the structural fragments (II-a)to(II-g) are connected to each other in the form of a linear pair is the R oligomeric chains Ar n(or Armor ends of chains Arn(or Armassociated with silicon atoms at branching points or with integral substituents R1.

Possible spatial arrangement of structural fragments polianilinovyh dendrimers General formula (I) corresponds to the one presented in figure 1 and Figure 3, where the branching points are the silicon atoms, which are interconnected fragments Arn.

Figure 1 presents a schematic representation of the dendrimers of the first four generations G branching of the center of K=3. In this case, the dendrimer of the first generation (G=1) in the formula (I) corresponds to L=1, KL=3 and K(L+1)=4; the dendrimer of the second generation (G=2) in the formula (I) corresponds to L=3, KL=9 and K(L+1)=12; the dendrimer of the third generation (G=3) in the formula (I) corresponds to L=7, KL=21 and K(L+1)=28; the dendrimer of the fourth generation (G=4) in the formula (I) corresponds to L=15, KL=45 and K(L+1)=48.

Figure 3 is a schematic representation of a third generation dendrimers (G=3) with different branching center. In this case, the dendrimer with branching center NC=K=2 in the formula (I) corresponds to L=7, KL=14 and K(L+1)=16, the dendrimer with branching center NC==3 in the formula (I) corresponds to L=7, KL=21 and K(L+1)=24; dendrimer with branching center NC=K=4 in the formula (I) corresponds to L=7, KL=28 and K(L+1)=32.

Preferred examples of R1are linear or rasvet the Lenna C 1-C20alkyl group such as methyl, ethyl, n-propyl, ISO-propyl, m-butyl, n-butyl, ISO-butyl, sec-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl; C2-C20alkeneamine group, for example, 4-butene-1-yl, 5-penten-1-yl, 6-HEXEN-1-yl, 8-octene-1-yl, And-undecen-1-yl. The most preferred examples of R1ethyl and hexyl.

Preferred examples of Ar are unsubstituted, thienyl-2,5-diyl General formula (II-a), where R2=R3=N; substituted thienyl-2,5-diyl General formula (II-a), where R2=N, in particular, 3-methylthieno-2,5-diyl, 3-utiltity-2,5-diyl, 3-proprtional-2,5-diyl, 3-butylstannyl-2,5-diyl, 3-petitioner-2,5-diyl, 3-exertional-2,5-diyl, 3-(2-ethylhexyl)thienyl-2,5-diyl; unsubstituted phenyl-1,4-diyl General formula (II-b), where R4=R5=N; substituted phenyl-1,4-diyl General formula (II-b), where R4=N, in particular, (2,5-dimethyl)phenyl-1,4-diyl, (2,5-diethyl)phenyl-1,4-diyl, (2.5-dipropyl)phenyl-1,4-diyl, (2,5-dibutil)phenyl-1,4-diyl, (2,5-diphenyl)phenyl-1,4-diyl, (2.5-dihexyl)phenyl-1,4-diyl 2,5-bis(2-ethylhexyl)phenyl-1,4-diyl, (2,5-dimethoxy)phenyl-1,4-diyl, (2,5-diethoxy)phenyl-1,4-diyl, (2,5-dipropoxy)phenyl-1,4-diyl, (2,5-disoproxil)phenyl-1,4-diyl, (2,5-dibutoxy)phenyl-1,4-diyl, (2,5-dimentions)phenyl-1,4-diyl, (2,5-degeneracy)FeNi who -1,4-diyl, 2,5-bis(2-ethylhexyloxy)phenyl-1,4-diyl. The most preferred examples of Ar: an unsubstituted thienyl-2,5-diyl and (2,5-dimethyl)phenyl-1,4-diyl.

In the context of this invention under Arn(or Arm) means any combination of n (or m) parts of the same or different Ar selected from the above range. Preferred examples of such combinations are n (m) equal the unsubstituted thienyl-2,5-vilnyh fragments connected with each other at positions 2 and 5, for example, 2,2'-bithienyl-2,5'-diyl (II-a-1), 2,2':5',2"-tertiary-2,5-diyl (II-a-2), 2,2':5',2":5",2"'-quatations-2,5"'-diyl (II-a-3):

Another preferred example of such combinations are the combination of various unsubstituted thienyl fragments connected with each other at positions 2 and 5, and various 2,5-substituted phenyl-1,4-vilnyh fragments connected with each other in positions 1 and 4, so that their total number is n, for example, fragments represented by formulas (II-1)to(II-12):

In this case n(m)=2 corresponds to formula (II), n(m)=3 corresponds to any one of formulas (II-2)to(II-4), n(m)=4 corresponds to any one of formulas (II-5)to(II-12).

The principles mentioned in the formulas (II-a-1)to(II-a-3) and (II-1)to(II-12) sign * (asterisk)are points of connection, in which the structural fragments (II-a)to(II-g) are connected to each other in the form of linear conjugated oligomeric chains Arn(or Armor ends of chains Arn(or Armassociated with silicon atoms at branching points or with integral substituents R1.

Presents the values of R1And, Arnand Armare particular cases and do not exhaust all possible values and all possible combinations of n and m values Ar among themselves.

In particular, in the formula (I) Ar can mean thienyl-2,5-diyl selected from a series of compounds of the formula (II-a), and phenyl-1,4-diyl selected from a series of compounds of the formula (II-b), then the claimed compounds are politikfeldanalyse dendrimers, the General formula of which is as follows:

where R1, R2, R3, R4, R5, K, L have the above values, n1+n2=n and m1+m2=m.

While the number of n1and m12,5-tierenbach fragments (II-a), and n2and m21,4-filinovich fra the cops (II-b) within one link of the macromolecule are total. Mutual arrangement of these fragments within this section during any of the n1n2, m1or m2more than 1 may be a block or alternating in a certain way, but it is the same for all recurring KL or K(L+1) units of the dendrimer macromolecule.

In this case, for example, when R1=C6H13, R2=R3=R4=N, R5=CH3, K=3, L=1, n1=m1=2, n2=m2=1 difentirely dendrimer of the first generation with integral hexylene groups (Figure 4) can be represented by formula (I-1):

In particular, in the formula (I) Ar can mean thienyl-2,5-diyl selected from a series of compounds of the formula (II-a), then the claimed compounds are polythiophenylene dendrimers, the formula of which is as follows:

where R1, R2, R3, K, L, n, m have the above values.

In this case, for example, when R1=C6H13, R2=R3=H, K=3, L=1, n=m=2 biliopancreatic dendrimer of the first generation with integral hexylene groups (Figure 5) can be represented by the formula (1-2):

In particular, in the formula (I) Ar, directly associated with the center of the branching dendrimers, may mean thienyl-2,5-diyl selected from a series of compounds of the formula (IIA), while the rest of the Ar, the number of which is equal to n-1, can mean any of the above arenovich or heteroarylboronic fragments, then the formula stated polianilinovyh dendrimers takes the following form:

where R1, R2, R3, Ar, K, L, n and m have the above values.

Particular cases of the formula (I-b) are also dendrimer I-1 (Ar = thienyl-2,5-diyl (II-a) and phenyl-1,4-diyl (II-b), R1=C6H13, R2=R3=R4=N, R5=CH3, K=3, L=1, n=m=3)and dendrimer I-2 (Ar = thienyl-2,5-diyl (II-a), R1=C6H13, R2=R3=H, K=3, L=1, n=m=2).

In particular, in the formula (I) may be equal to 3, then the claimed compounds are dendrimers with branching center NCof the three , the formula of which is as follows:

where R1, Ar, L, n and m have the above values.

Particular cases of the formula (I-g) are also dendrimer I-1 (Ar = thienyl-2,5-diyl (II-a) and phenyl-1,4-diyl (II-b), R1=C6H13, R2=R3=R4=H, R5=CH3, L=1, n=m=3) and dendrimer I-2 (Ar = thienyl-2,5-diyl (II-a), R1=C6H13, R2=R3=H, L=1, n=m=2).

In particular, in the formula (I) n and m can be equal to 2, then the claimed compounds are ballsillie dendrimers, formula comoriginal the following:

where R1, Ar, K and L have the above values.

Dendrimer I-2 is a special case of the formula (I-d) when Ar = thienyl-2,5-diyl (II-a), R1=C6H13, R2=R3=H, K=3, L=1.

In particular, in the formula (I) n and m can be equal to 3, then the claimed compounds are triarylsulfonium dendrimers, the formula of which is as follows:

where R1, Ar, K, L have the above values.

Dendrimer I-1 is also a special case of the formula (I-e) when Ar = thienyl-2,5-diyl (II-a), R1=C6H13R2=R3=R4=N, R5=CH3, K=3, L=1.

In particular, for dendrimers of first generation L is 1, and for them the formula (I) takes the following form:

where R1, Ar, K, n and m have the above values.

Particular cases of the formula (I-g) are also dendrimer I-1 (Ar = thienyl-2,5-diyl (II-a), phenyl-1,4-diyl (II-b), R1=C6H13, R2=R3=R4=N, R5=CH3, K=3, n=m=3) and dendrimer I-2 (Ar = thienyl-2,5-diyl (II-a), R1=C6H13, R2=R3=H, K=3, n=m=2).

In particular, for dendrimers of the second generation of L is 3, and for them the formula (I) takes the following form:

where R1, Ar, K, n and m have the above values.

Inthis case, for example, when Ar = thienyl-2,5-diyl (II-a), R1=C6H13, R2=R3=H,K=3, n=m=2 biliopancreatic dendrimer of the second generation with integral hexylene groups (6) can be represented by formula (I-3):

In particular, for dendrimers of the third generation L is 7, and for them the formula (I) takes the following form:

where R1, Ar, K, n and m have the above values.

In this case, for example, when Ar = thienyl-2,5-diyl (II-a), R1=C6H13, R2=R3=H, K=3, n=m=2 biliopancreatic dendrimer of the third generation with integral hexylene groups (Fig.7) can be represented by formula (I-4):

In particular, for dendrimers of fourth generation L is 15, and for them the formula (I) takes the following form:

where R1, Ar, K, n and m have the above values.

In contrast to the known titansilber dendrimers, such as dendrimers and B declared polyarylene dendrimers contain all the silicon atoms of the same or different arrelano groups with efficient luminescence, and terminal substituents R1giving these macromolecules good solubility in various organic solvents.

Under good solubility is in the context of this invention refers to the solubility of the dendrimer with a concentration of not less than 5 mg/ml, preferably at least 20 mg/ml, in any organic solvent or their mixtures. Examples of such solvents can serve as aromatic compounds, e.g. benzene, toluene, xylene; chlorinated organic compounds, for example, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachlorethane, tetrachloroethylene, chlorobenzene; aliphatic compounds such as pentane, hexane, heptane, cyclohexane; aliphatic ethers, for example diethyl ether, methylisobutyl ether, THF, dioxane; ketones, for example acetone, methyl ethyl ketone; amides, such as dimethylformamide, dimethylacetamide; alcohols, e.g. methanol, ethanol, isopropanol, butanol. The necessary and sufficient condition is the solubility of the at least one organic solvent or at least one mixture of two or more solvents.

Polyarylene dendrimers possess fluorescent properties that can be illustrated by the spectra of the absorption and luminescence their diluted solutions (see, for example, Fig, 9). Optical characteristics of a number of polianilinovyh dendrimers are presented in the table. These are only examples and in no way limit the characteristics stated polianilinovyh dendrimers.

A distinctive feature of the claimed polianilinovyh dendrimers I have is their high thermal stability, defined in this invention as the temperature of 1% weight loss when heated substance in argon. This temperature is not less than 200°C., preferably not less than 300°C, most preferably at least 400°C. Data of thermogravimetric analysis (TGA), illustrating the high thermostability of the claimed polianilinovyh for example, dendrimers I-1,I-2,I-3 and I-4, shown in Figure 10 and 11.

The task is solved in that a method of obtaining polianilinovyh dendrimers General formula (I), namely, that montendre General formula (III)

where X is H or Br or I; R1, Ar, n, m and L have the abovementioned meanings, first reacts with layerwise agent of General formula (IV)

where R8means a linear or branched C1-C10alkyl group, dialkylamino or phenyl group, then the received monoliterate General formula (V)

where R1, Ar, n, m and L have the above values, interacts with a functional compound selected from a number of compounds of the General formula (VI)

where To have the above values, Y represents Cl or Br, or-och3or-OS2H5or-OS3H7or-OS4H9.

As otherwisehe agent R8Li can be any commercially available layerwise agent, such as n-utillity, t-utility, ISO-utility, finality, motility, sitedisability in a suitable solvent, such as hexane, heptane, toluene, THF. The most preferred reagent utility or its solution in hexane.

Preferred examples of functional compounds (VI) are: clear, methyltrichlorosilane, tetrachlorosilane, dimethylgermylene, methylcarbamyl, tetrabromide, dimethyldiethoxysilane, methyltrimethoxysilane, tetramethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraisopropoxide, dimethyldiethoxysilane, methyltrimethoxysilane, tetramethoxysilane. The most preferable example of methyltrichlorosilane.

The General scheme of the process can be represented as follows:

where X, Y, R1, R8, Ar, n, m, K and L have the above values.

In particular, the functional compound may be a compound selected from a number of compounds of the General formula (VI), where Y denotes Cl, then polianilinovyh dendrimer receive the following General scheme:

where X, R1, R8, Ar, n, m, With To have the above values.

In particular, the functional compound may be a compound selected from a number of compounds of the General formula (VI), where Y represents-och3then polianilinovyh dendrimer receive the following General scheme:

where X, R1, R8, Ar, n, m, L and K have the above values.

In particular, in Monterone formula (III) Ar can mean thienyl-2,5-diyl selected from a series of compounds of the formula (II-a), and phenyl-1,4-diyl selected from a series of compounds of the formula (II-b), then the following General scheme receive positiveparenting dendrimer:

where n1+n2=n, m1+m2=m, X, Y, R1, R2, R3, R4, R5, R8, K, L, n and m have the above values.

In particular, in Monterone formula (III) Ar can mean thienyl-2,5-diyl selected from a series of compounds of the formula (II-a), then the following General scheme receive positivenergy dendrimer:

where X, Y, R1, R2, R3, R8, K, L, n, m have the above values.

In particular, in the formula (III) X can mean N, with the proviso that Ar is directly linked to X means thienyl-2,5-diyl selected from a series of compounds of the formula (II-a), and the rest Ar, the number of which is equal to n-1, can mean any of the above Ari is anovich or heteroarylboronic fragments, then polianilinovyh dendrimer receive the following General scheme:

where Y, R1, R2, R3, Ar, K, L, n and m have the above values.

In particular, the functional connection can be selected from a number of compounds of the formula (VI), where K is 3, then polianilinovyh dendrimer receive according to the following scheme:

where X, Y, Ar, R1, R8, L, n and m have the above values.

In particular, in Monterone formula (III), n and m may be equal to 2, then the following General scheme receive polimerizovannye dendrimer:

where X, Y, Ar, R1, R8, K, L have the above values.

In particular, in Monterone formula (III), n and m may be equal to 3, then the following General scheme receive politicaleconomy dendrimer:

where X, Y, Ar, R1, R8, K, L have the above values.

In particular, in Monterone formula (III), L may be equal to 1, then the following General scheme receive a dendrimer of the first generation:

where X, Y, Ar, R1, R8, K, n and m have the above values.

In particular, in Monterone formula (III), L may be equal to 3, then the following General scheme receive a dendrimer of the second generation:

where X, Y, Ar, R1, R8, K, n and m have the above values.

In particular, in Monterone formula (III), L may be equal to 7, then the following General scheme receive a dendrimer of the third generation:

where X, Y, Ar, R1, R8, K, n and m have the above values.

In particular, in Monterone formula (III), L may be equal to 15, then the following General scheme receive a dendrimer of the fourth generation:

where X, Y, Ar, R1, R8, K, n and m have the above values.

In contrast to the known method of obtaining titansilber dendrimers B, in this case, after interaction with layerwise agent R8Li is formed monolitavia derived mantendremos formula (V), soluble in various organic solvents even at low temperatures. The presence of terminal substituents R1as in the original monodendrion and end dendrimers exclude the possibility of side reactions, the metabolism of hydrogen to lithium, which significantly increases the yield of the target product.

The above interaction can be performed in almost any anhydrous solvents or mixtures of solvents which do not react with organolithium derivatives, as well as with chlorine and alkoxysilane. For example, the reaction can be carried out in among the e organic solvent, selected from a number of ethers include tetrahydrofuran, dioxane, methyl tertiary butyl ether, diethyl ether, dimethyl ether of ethylene glycol, or from a number of aromatic compounds: benzene, toluene, xylene, or from a number of alkanes: pentane, hexane, heptane. Preferably either the use of tetrahydrofuran. A mixture of two or more solvents can also be used. For example, a mixture of tetrahydrofuran and hexane (present in commercially available Liteinyi agents, for example, a solution of utility in hexane). Thus the interaction of the source components can be carried out at a temperature in the range from -100°C to +30°C at a stoichiometric molar ratio of functional groups of the starting components or excess of one of them. Preferably, the interaction is carried out at a temperature in the range from -90°C to 0°C. Most preferably, the interaction is carried out at a temperature in the range from -80°C to -60°C at a stoichiometric molar ratio of functional groups of the starting components.

After the reaction the product produce by known methods. For example, add water and an organic solvent. The organic phase is separated, washed with water until neutral and dried, then the solvent evaporated. As the organic solvent can be used on any non-mixing is the action scene or partially miscible with water, the solvent, for example, selected from a number of esters: diethyl ether, methyl tertiary butyl ether, or selected from a number of aromatic compounds: benzene, toluene, xylene, or selected from a number chlororganics connections: dichloromethane, chloroform, carbon tetrachloride, chlorobenzene. For selections, you can use a mixture of organic solvents. The selection of product can be produced without the use of organic solvents, for example, by planting water followed by separation of the product from the aqueous layer by filtration, centrifugation, or any other known method.

Purification of the crude product is carried out by any known method, for example, column chromatography, recrystallization, fractional precipitation, fractional dissolution or any combination.

The purity and structure of the synthesized compounds confirm the set data of physico-chemical analysis, well known in the art, such as chromatography, spectroscopy, mass spectroscopy, elemental analysis. The most preferred confirmation of the purity and structure polianilinovyh dendrimers are NMR spectra of the nuclei1H,13C and29Si, a civil act. Curves civil dendrimers correspond to narrow monodisperse distribution of molecular weight (see, for example, Figure 10).

On Phi is .1 presents a schematic representation of dendrimers of different generations (G (G=1, 2, 3, or 4 for dendrimers of the first, second, third and fourth generations, respectively) with the branching center Nc=3 and the branching level NB=2.

Figure 2 presents a schematic representation of mantendremos different generations G (G=1, 2, 3 or 4 for mantendremos first, second, third and fourth generations, respectively) with the branching center nc=3 and the branching level NB=2.

Figure 3 presents a schematic representation of a third generation dendrimers (G=3) with different branching center NC(NC=2, 3 or 4) and branching link NB=2 in all cases.

Figure 4 presents a schematic representation of the structural formula lifeprolonging of the dendrimer of the first generation I-1.

Figure 5 presents a schematic structural formulas biliopancreatic of the dendrimer of the first generation I-2.

Figure 6 presents a schematic structural formulas biliopancreatic dendrimers of the second generation I-3.

Figure 7 presents a schematic representation of the structural formula biliopancreatic of the dendrimer of the third generation I-4.

On Fig presents absorption spectra (a) and luminescence (b) a dilute solution of dendrimer I-1 in hexane.

Figure 9 presents absorption spectra (a) and luminescence (b) times ablanovo solution of dendrimer (I-3 in THF.

Figure 10 presents TGA curve lifeprolonging dendrimers and I-1.

Figure 11 presents TGA curves of a number of biliopancreatic dendrimers from the first to the third generation of compound I-2 (G1), I-3 (G2) and I-4 (G3).

On Fig presents GPC curves of a number of biliopancreatic dendrimers from the first to the third generation of compound I-2 (G1), I-3 (G2) and I-4 (G3).

The table lists the optical properties of some polianilinovyh dendrimers in dilute solutions in various solvents, including the maxima of the absorption spectra and luminescence quantum yield of luminescence, characterizing its effectiveness.

The invention can be illustrated by the following examples. Used commercially available reagents and solvents. The source reagent 5-bromo-2,2'-Bethoven and 5-hexyl-2,2'-Bethoven received by known methods (S.Gronowitz, A.-B.-Hornfeldt, Thiophenes, Elsevier Academic press, 2004, pp.755). Other source compounds were obtained according to the following examples. All reactions were carried out in anhydrous solvents in an argon atmosphere.

Synthesis of initial reagents

Example 1. Synthesis of methyl(Tien-2-yl)dichlorsilane (VII)

To a suspension of 6.09 g (0.25 mol) of magnesium in 15 ml diethyl ether was added, and the solution 27.25 g (0.167 mol) of 2-bromothiophene in 250 ml of diethyl ether. To the obtained reagent Gringa is and added 17.82 ml (0.152 mol) of methyltrichlorosilane at a temperature of 0°C. After filtration under argon and distillation in vacuo (TKip=73°C./15 mbar) received 16.7 g (57% of theoretically possible) connection IX.1H NMR (CDCl3): 1,09 (s, 3H); to 7.25 (DD, 1H, J1=3.1 Hz, J2=4,9 Hz); EUR 7.57 (d, 1H, J=3,l Hz); to 7.77 (d, 1H, J=4,9 Hz).

Example 2. Synthesis of methyl-(2,2'-beteen-5-yl)dichlorsilane (VIII)

The solution 26.30 g (0.107 mol) of 5-bromo-2,2'-bithiophene in 270 ml of dry THF was added to a suspension of 2.71 g (0.113 mol) of magnesium in 10 ml of THF. The resulting Grignard reagent was added to the solution 160.36 g (1.073 mol) of methyltrichlorosilane at a temperature below -50°C. the Reaction mixture was stirred for four hours. The precipitate was filtered, the solvent was distilled. The product was purified by distillation in vacuo (TKip=110°C/0.11 mbar). Output: 21.00 g (70% of theoretically possible).1H NMR (CDCI3, δ, ppm, J/Hz): 1.07 (s, 3H), 7.04 (DD, 1H, J1=3.7 Hz, J2- 4.9 Hz), 7.23-7.30 (overlapping signals, 4H), 7.43 (d, 1 H, J=3.7 Hz).13With NMR (δ in CDCl3): 6.71, 124.97, 125.00, 125.66, 128.02, 131.49, 138.08, 138.14, 145.98.29Si NMR (δ in CDCl3): 11.24.

Example 3. Synthesis of 2-(4-bromo-2,5-dimetilfenil)thiophene (IX)

To a solution 29.60 g (122 mmol) of 1,4-dibromo-2,5-xylene and 330 mg (0.45 mmol) of the catalyst Pd(dppf)Cl2in 200 ml of THF at a temperature of 0°C was added a solution of 2-thienylmagnesium in THF, freshly prepared from 20.95 g (129 mmol) of 2-brantii is on, 3.24 g (135 mmol) of magnesium and 200 ml THF. The reaction mixture was stirred at 20°C for 6 hours. The reaction yield was 55% (according to GPC). After extraction and recrystallization, followed by purification by the method of column chromatography was obtained 15.80 g (53% of theoretically possible) chromatographically pure compounds (IX).1H NMR (CDCl3, δ, ppm, J/Hz): 2.36 (s, 3H), 2.38 (s, 3H), 7.04 (DD, 1H, J1=3.7 Hz, J2=1.2 Hz), 7.09 (DD, 1H, J1=3.7 Hz, J2=4.9 Hz), 7.26 (s, 1H), 7.34 (DD, 1H, J1=4.9 Hz, J2=1.2 Hz), 7.44 (s, 1H).

Example 4. Synthesis of 2-[2,5-dimethyl-4-(2-thienyl)phenyl]-5-hexylthiophene (X)

Compound X was obtained analogously to the synthesis of compound IX from 20.50 g (768 mmol) of compound IX, 300 mg (0.4 mmol) of the catalyst Pd(dppf)Cl2and solution of 5-hexyl-2-thienylmagnesium in THF, freshly prepared from 19.93 g (81 mmol) of 2-bromo-5-hexylthiophene and 2.03 g (85 mmol) of magnesium. The reaction yield was 84% (according to GPC). After separation and purification by the method of column chromatography the chromatographic output of the pure product was 21.89 g (81% of theoretically possible).1H NMR (CDCl3, δ, ppm, J/Hz): 0.90 (t, 3H, J=6.7 Hz), 1.24-1.50 (overlapping signals, 6N), 1.72 (m, 2N, M=5, J=7.3 Hz), 2.41 (s, 3H), 2.44 (s, 3H), 2.84 (t, 2H, J=7.3 Hz), 6.76 (d, 1H, J=3.7 Hz), 6.90 (d, 1H, J=3.7 Hz), 7.10 (overlapping signals, 2H), 7.33 (overlapping signals, 3H).13With NMR (δ CDCl 3): 14.10, 20.61, 20.75, 22.59, 28.87, 30.13, at 31.58, 31.65, 124.09, 125.05, 126.05, 126.32, 133.02, 133.07, 133.24, 133.88, 139.96, 142.76, 145.93.

Example 5. Synthesis of bis{5-[4-(5-hexyl-2-thienyl)-2,5-dimetilfenil]-2-thienyl} (methyl)-2-tamilselvan (XI)

To a solution of 14.00 g (40 mmol) of compound X in THF was added 15.80 ml (40 mmol) of a 1.6 M solution of n-utility in hexane at -78°C. the Reaction mixture was stirred for one hour, then added 4.09 g (20 mmol) of compound VII. After 15 minutes stirring the reaction mixture upon cooling, the reaction yield was 94% (according to GPC). After the standard selection of reaction and purification method column chromatography the chromatographic output of the pure product was 15.47 g (90% of theoretically possible).1H NMR (250 MHz, δ in CDCl3, TMS/ppm): 0.89 (t, 6N, J=6.7 Hz), 1.00 (s, 3H), 1.25-1.45 (overlapping signals, 12 H), 1.71 (m, 4H, M=5, J=7.3 Hz), 2.42 (s, N), 2.82 (t, 4H, J=7.3 Hz), 6.75 (DD, 2H, J1=3.7 Hz, J2=1.2 Hz), 6.90 (d, 2H, J=3.7 Hz), 7.20-7.30 (overlapping signals, 3H), 7.31 (s, 2H), 7.33 (s, 2H), 7.40 (d, 2H, J=3.7 Hz), 7.50 (DD, 1H, J1=3.7 Hz, J2=1.2 Hz), 7.72 (DD, 1H, J1=4.9 Hz, J2-1.2 Hz).13With NMR (500 MHz, δ in CDCl3): 0.16, 14.10, 20.75, 22.59, 28.86, 30.13, at 31.58, 31.64, 124.11, 126.08, 127.83, 128.19, 128.38, 129.00, 132.32, 132.44, 132.59, 132.77, 133.05, 133.99, 134.83, 137.05, 137.18, 139.94, 145.95, 150.18.29Si NMR (500 MHz, δ in CDCl3): -25.00.

Example 6. Synthesis of {5-[2,5-dimethyl-4-(2-thienyl)phenyl]-2-thienyl}bis{5-[4(5-hexyl-2-thienyl)-2,5-dimetilfenil]-2-thienyl}methylsilane (III-1)

To a solution of 13.00 g (15.6 mmol) of compound XI in THF was added 6.20 ml (15.6 mmol) of a 2.5 M solution of n-utility in hexane at -78°C. the Reaction mixture was stirred for one hour, then added a solution of the ether complex of magnesium bromide, freshly prepared from 490 mg (20.3 mmol) of magnesium and 3.52 g (18.7 mmol) of dibromoethane and 25 ml diethyl ether. Thus obtained Grignard reagent was added to a solution of 3.96 g (14.8 mmol) of compound IX and 200 mg of catalyst Pd(dppf)Cl2in 20 ml of THF at 0°C. the Reaction mixture was stirred for 18 hours. The reaction yield was 64% (according to GPC). After the standard selection of reaction and purification method column chromatography on silica gel output chromatographically pure product amounted to 8.85 g (58.5% from theoretically possible).1H NMR (250 MHz, δ in CDCl3, TMS/ppm): 0.89 (t, 6N, J=6.7 Hz), 1.03 (s, 3H), 1.25-1.45 (overlapping signals, 12 H), 1.71 (m, 4H, M=5, J=7.3 Hz), 2.42 (s, 3H), 2.43 (s, N), 2.44 (s, 3H), 2.82 (t, 4H, J=7.3 Hz), 6.75 (DD, 2H, J1=3.7 Hz, J2=1.2 Hz), 6.90 (d, 2H, J=3.7 Hz), 7.10 (d, 2H, J=3.7 Hz), 7.22 (d, 2H, J=3.1 Hz), 7.23 (d, 2H, J=3.7 Hz), 7.30 - 7.40 (overlapping signals, 6N), 7.45 (DD, 3H, J1=3.7 Hz, J2=1.2 Hz).13With NMR (500 MHz, δ in CDCl3): 0.15, 14.10, 20.61, 20.76, 22.59, 28.87, 30.13, at 31.58, 31.64, 124.11, 125.16, 126.08, 126.42, 127.14, 127.86, 127.94, 132.45, 132.61, at 132.72, 132.78, 133.07, 133.14, 133.24, 133.33, 133.59, 134.01, 134.80, 134.97, 137.23 139.94, 142.63, 145.96, 150.06, 150.22.29Si NMR (500 MHz, δ in CDCl3): -25.32.

Example 7. Synthesis of 2,2'-beteen-5-yl[bis(5'-hexyl-2,2'-beteen-5-yl)]methylsilane (III-

2)

Montendre III-2 was obtained similarly to the method of synthesis of compound XI of 15.04 g (57.2 mmol) of 5-hexyl-2,2'-bithiophene, 23.55 ml of a 2.5 M solution of n-utility (57.2 mmol) in hexane, 7.99 g (28.6 mmol) of compound VIII and 400 ml of THF. After 30 minutes stirring the reaction mixture, the reaction yield was 98% (according to GPC). After extraction and purification was obtained 18.20 g (90% of theoretically possible) chromatographically pure compound III-2.1H NMR (DMSO-CCl4, δ, ppm, J/Hz): 0.88 (t, 6N, J=6.7 Hz), 0.92 (s, 3H), 1.24-1.40 (overlapping signals, N), 1.64 (m, 4H, M=5, J=7.3 Hz), 2.76 (t, 4H, J=7.3 Hz), 6.69 (d, 2H, J=3.05 Hz), 7.01 (d, 1H, J=3.05 Hz), 7.03 (d, 2H, J=3.7 Hz), 7.21 (d, 2H, J=3.7 Hz), 7.26 (d, 1H, J=3.7 Hz), 7.29 (d, 2H, J=3.7 Hz), 7.31 (d, 2H, J=3.7 Hz), 7.37 (d, 1H, J=3.7 Hz).13With NMR (δ in CDCl3): -0.16, 14.07, 22.56, 28.72, 30.15, 31.52, 31.55, 123.96, 124.26, at 124.35, 124.79, 124.82, 125.12, 127.83, 132.96, 134.05, 134.30, 136.97, 137.78, 137.81, 144.47, 145.17, 145.94.29Si NMR (δ in CDCl3): -25.27. Found for C37H42S6Si (%): C, 62.59; H 5.89; S 27.17; Si 3.69. Calculated (%): 62.84; H 5.99; S 27.20; Si 3.97.

Example 8. Synthesis of [[2,2'-beteen-5-yl(methyl)silander]bis(2,2'-biotene-5',5-diyl)]bis[bis(5'-hexyl-2,2'-beteen-5-yl)(methyl)silane] (III-3)

Montendre III-3 was obtained similarly to the method of synthesis of the compounds XI from 16.20 g (22.90 mmol) monterona III-2, 9.16 ml of a 2.5 M solution of n-utility (22.90 mmol) in hexane, 3.20 g (11.45 mmol) of compound VIII and 450 ml of THF. After 60 minutes of stirring the reaction mixture, the reaction yield was 90% (according to GPC). After extraction and purification was obtained 15.00 g (81% of theoretically possible) chromatographically pure compound III-3.1H NMR (δ in DMSO-CCl4, TMS/ppm): 0.87 (t, N, J=6.7 Hz), 0.91 (s, 6N), 0.94 (s, 3H), 1.22-1.39 (overlapping signals, 24N), 1.63 (m, 8 H, M=5, J=7.3 Hz), 2.75 (t, 8H, J=7.3 Hz), 6.68 (d, 4H, J=3.7 Hz), 7.00 (d, 1H, J=3.7 Hz), 7.03 (d, 4H, J=3.7 Hz), 7.20 (d, 4H, J=3.7 Hz), 7.24 (d, 1H, J=3.7 Hz), 7.28 (d, 4H, J=3.7 Hz), 7.30-7.35 (overlapping signals, 6N), 7.35-7.40 (overlapping signals, 5H).13With NMR (δ in CDCl3): -0.24, -0.19, 14.07, 22.55, 28.71, 30.14, 31.50, at 31.54, 123.97, here is 124.34, 124.81, 125.15, 125.67, 125.69, 127.82, 132.87, 133.61, 134.26, 134.28, 134.74, 136.90, 137.82, 137.88, 137.91, 143.91, 144.12, 145.18, 145.92.29Si NMR (δ in CDCl3): -25.23, -25.08. Found for C83H90S14Si3(%): C, 61.39; H 5.64; S 27.60; Si 5.08. Calculated (%): at 61.51; H 5.60; S 27.70; Si 5.20.

Example 9. Synthesis of {[2,2'-beteen-5-yl(methyl)silander]bis[2,2'-beteen-5',5-diyl(methylsilane)bis(2,2'-beteen-5',5-diyl)]}tetrakis[bis(5'-hexyl-2,2'-beteen-5-yl)(methyl)silane] (III-4)

Montendre III-4 was obtained similarly to the method of synthesis of compound XI of 10.98 g (6.77 mmol) of montengrin III-4, 2.71 ml of a 2.5 M solution of n-utility (6.77 mmol) in hexane, 0.95 g (3.39 mmol) of compound VIII and 330 ml of THF. After 90 minutes per what masiania the reaction mixture, the reaction yield was 70% (according to GPC). After extraction and purification was obtained 7.02 g (60% of theoretically possible) chromatographically pure compound III-4.1H NMR (δ in DMSO-CCl4, TMS/ppm): 0.87 (t, 24N, J=6.7 Hz), 0.90 (s, N), 0.93 (s, N), 1.22-1.39 (overlapping signals, N), 1.62 (m, 16 H, M=5, J=7.3 Hz), 2.74 (t, N, J=7.3 Hz), 6.66 (d, 8H, J=3.7 Hz), 6.99 (d, 1H, J=3.7 Hz), 7.01 (d, 8H, J=3.7 Hz), 7.18 (d, 8H, J=3.7 Hz), 7.22 (d, 1H, J=3.7 Hz), 7.27 (d, 8H, J=3.7 Hz), 7.29-7.33 (overlapping signals, 15 NM), 7.33-7.38 (overlapping signals, N).13With NMR (δ in CDCl3): -0.24, -0.22, -0.18, 14.07, 22.56, 28.71, 30.14, 31.51, at 31.54, 123.97, at 124.35, 124.82, 125.15, 125.67, 125.70, 125.73, 127.83, 132.87, 134.17, 134.28, 134.30, 134.72, 137.82, 137.89, 137.94, 143.90, 144.05, 144.14, 145.17, 145.92.29Si NMR (δ in CDCl3): -25.24, -25.08, -25.04.

Found for C175H186S30Si7(%): 61.22; H 5.49; S 27.95; Si 5.49.

Calculated (%): 60.96; N, 5.44; S 27.90; Si 5.70.

The synthesis of dendrimers

General methods of synthesis of dendrimers: to a solution of 0.1 mmol of compound III in THF was added 0.1 mmol of a solution of utility in hexane at a temperature of -60 to -80°C. Then add 0.033 mol of compound VI and stirred for 30-180 min After the end of the reaction product produce by known methods. The product was then purified by the method of column chromatography on silica gel.

Example 10. Synthesis lifeprolonging of the dendrimer of the first generation (I-1)

Dendrimer I-1 was obtained according to the General procedure of the synthesis of dendrimers of 2.08 g montendre the III-1, 0.82 ml of a 2.5 M solution of n-utility in hexane, 96.9 mg of methyltrichlorosilane in 30 ml of THF. The reaction yield was 50% (according to GPC). After extraction and purification was obtained 0.70 g (33% of theoretically possible) of pure dendrimer I-1.1H NMR (250 MHz, δ in CDCl3, TMS/ppm): 0.89 (t, N, J=6.7 Hz), 1.02 (s, N), 1.25-1.45 (overlapping signals, 36 H), 1.70 (m, N, M=5, J=7.3 Hz), 2.42 (s, 36N), 2.44 (s, N), 2.82 (t, N, J=7.3 Hz), 6.75 (d, 6N, J=3.7 Hz), 6.90 (d, 6N, J=3.1 Hz), 7.21 (d, 6N, J=3.7 Hz), 7.23 (d, 6N, J=3.1 Hz), 7.30 (s, 6N), 7.34 (s, 6N), 7.37 (s, 6N), 7.45 (d, N, J=3.7 Hz).13With NMR (500 MHz, δ in CDCl3): 0.16, 14.10, 20.76, 22.58, 28.86, 30.13, at 31.58, 31.64, 124.11, 126.08, 127.86, 127.95, 132.44, 132.61, 132.65, 132.78, 133.06, 133.15, 133.35, 133.38 is awaited, 134.01, 134.78, 134.90, 134.98, 137.24, 139.94, 145.95, 150.05, 150.08, 150.21.29Si NMR (500 MHz, δ in CDCl3): -25.32, -25.29. Found for C112H126S18Si4(%): C, 71.48; H, 6.55; S, 18.14; Si, 3.64. Calculated (%): C, 71.31; H, 6.44; S, 18.62; Si, 3.63.

Example 11. Synthesis biliopancreatic of the dendrimer of the first generation (I-2)

Dendrimer I-2 was obtained according to the General procedure of the synthesis of dendrimers from 0.90 g monterona III-2, 0.8 ml of a 1.6 M solution of n-utility in hexane, 63.5 mg of methyltrichlorosilane in 35 ml THF. The reaction yield was 87% (according to GPC). After extraction and purification was obtained 0.58 g (65% of theoretically possible) of pure dendrimer 1-2.1H NMR (250 MHz, δ in DMSO-CCl4, TMS/ppm): 0.86 (t, N, J=6.7 Hz), 0.91 (s, N), 0.93 (s, 3H), 1.23-1.40 (overlap is iesa signals, 36 H), 1.61 (m, N, M=5, J=7.3 Hz), 2.74 (t, N, J=7.3 Hz), 6.68 (d, 6N, J=3.7 Hz), 7.02 (d, 6N, J=3.1 Hz), 7.21 (d, 6N, J=3.7 Hz), 7.28(d, 6N, J=3.1 Hz), 7.31(d, 3H, J=3.1 Hz), 7.33 (d, 3H, J=3.7 Hz), 7.38 (d, 6N, J=3.1 Hz).13With NMR (500 MHz, δ in CDCl3): -0.23, -0.16, 14.05, 22.55, 28.72, 30.16, 31.51, at 31.54, 123.99, 124.37, 124.81, 125.72, 132.94, 134.26, 134.32, 134.77, 137.82, 137.94, 143.94, 144.16, 145.20, 145.93.29Si NMR (500 MHz, δ in CDCl3): -25.24, -25.05. Found for C112H126S18Si4(%): C, 62.37; H, 5.85; S, 26.18; Si, 5.32. Calculated (%): C, 62.23; H, 5.88; S, 26.70; Si, 5.20.

Example 12. Synthesis biliopancreatic dendrimers of the second generation (I-3)

Dendrimer I-3, was obtained according to the General procedure of the synthesis of dendrimers from 1.00 g of montengrin III-3, 0.38 ml of a 1.6 M solution of n-utility in hexane to hexane, 30.6 mg of methyltrichlorosilane and 35 ml of THF. The reaction yield was 67% (from GPC data). After extraction and purification was obtained 0.51 g (51% of theoretically possible) of pure dendrimers and I-3.1H NMR (250 MHz, δ in DMSO-CCl4, TMS/ppm): 0.84 (t, 36N, J=6.7 Hz), 0.88 (s, N), 0.90 (s, N), 1.21-1.37 (overlapping signals, 72 H), 1.59 (m, 24N, M=5, J=7.3 Hz). 2.71 (t, 24N, J=7.3 Hz), 6.64 (d, N, J=3.7 Hz), 6.98 (d, N, J=3.1 Hz), 7.16 (d, N, J=3.7 Hz), 7.25(d, N, J=3.1 Hz), 7.28(d, N,.7=3.1 Hz), 7.29 (d, N, J=3.7 Hz), 7.30-7.35 (overlapping signals, J=18H).13C NMR (500 MHz, δ in CDCl3): -0.25, -0.20, 14.10, 22.56, 28.71, 30.14, 31.51, 31.53, 123.94, 124.32, 124.81, 125.66, 125.68, 125.72, 132.80, 134.10, 134.16, 134.20, 134.24, 134.65, 137.83, 137.94, 143.87, 144.01, 144.10, 145.14, 145.90.29Si NMR (500 MHz, δ in CDCl ): -25.25, -25.05. Found for C251H272S42Si10(%): C, 62.00; H, 5.60; S, 26.65; Si, 5.70. Calculated (%): C, 61.32; H, 5.58; S, 27.39; Si, 5.71.

Example 13. Synthesis biliopancreatic of the dendrimer of the third generation (I-4)

Dendrimer I-4 was obtained according to the General procedure of the synthesis of dendrimers from 1.02 g of montengrin III-4, 0.18 ml of a 1.6 M solution of n-utility in hexane, 14.4 mg of methyltrichlorosilane and 35 ml of THF. The reaction yield was 25% (according to GPC). After extraction and purification was obtained 0.14 g (13% of theoretically possible) of pure dendrimers and I-4.1H NMR (250 MHz, δ in DMSO-CCl4, TMS/ppm): 0.84 (t, N, J=6.7 Hz), 0.86 (s, N), 0.88 (s, N), 1.21-1.37 (overlapping signals, 144 H), 1.59 (m, N, M=5, J=7.3 Hz), 2.70 (t, N, J=7.3 Hz), 6.62 (d, 24N,.7=3.7 Hz), 6.96 (d, 24N, J=3.1 Hz), 7.14 (d, 24N, J=3.7 Hz), 7.18-7.34 (overlapping signals, N).13With NMR (500 MHz, δ in CDCl3): -0.27, -0.21, 14.10, 22.56, 28.70, 30.12, 31.49, 31.52, 123.93, 124.31, 124.80, 125.65, 125.67, 125.70, 132.78, 134.08, 134.12, 134.16, 134.23, 134.61, 137.81, 137.93, 143.85, 144.00, 144.08, 145.12, 145.87.29Si NMR (500 MHz, d in CDCl3): -25.26, -25.06. Found for C526H558S90Si22(%): C, 62.05; H, 5.62; S, 25.62; Si, 6.00. Calculated (%): C, 60.84; H, 5.42; S, 27.79; Si, 5.95.

Polyarylene dendrimers and the retrieval method

Table
DendrimerThe solvent/td> The maximum of the absorption spectrum, nmThe maximum of the luminescence spectrum, nmQuantum yield of luminescence Q, %
I-1THF299375/38836
I-1hexane308380/39840
I-2THF333374/38830
I-3THF334375/39031
I-4THF336376/39030

1. Polyarylene dendrimers General formula (I)

where R1means the Deputy from a range of: linear or branched C1-C20alkyl group; a linear or branched C1-C20alkyl groups separated by at least one oxygen atom; a linear or branched C1- 20alkyl groups separated by at least one sulfur atom; a branched C3-C20alkyl groups separated by at least one atom of silicon; C3-C20alkeneamine group;
Ar means, independently for each n and m, the same or different allenbyi or heteroarenes radicals selected from the series of: substituted or unsubstituted thienyl-2,5-diyl General formulasubstituted or unsubstituted phenyl-1,4-diyl General formula (II-b)substituted or unsubstituted 1,3-oxazol-2,5-diyl General formula (II-b)substituted fluoren-4,4'-diyl General formula (II-g),
where R2, R3, R4, R5, R6mean independently from each other H or Deputy of the above series for R1; R7means the Deputy of the above series for R1;
It is equal to 2, or 3, or 4;
L is 1 or 3, or 7, or 15;
m means an integer from the range from 2 to 6;
n means an integer from the range from 2 to 6;
when this fragment (N3C)4-K-Si is the center of branching dendrimers.

2. Polyarylene dendrimers according to claim 1, wherein Ar means thienyl-2,5-diyl selected from a series of compounds of the formula (II-a), and phenyl-1,4-diyl selected from a series of compounds of the formula (II-b).

3. Polyaryl wilanowie dendrimers according to claim 1, wherein Ar means thienyl-2,5-diyl selected from a series of compounds of the formula (II-a).

4. Polyarylene dendrimers according to claim 1, characterized in that Ar directly related to the Central branch of the dendrimer, means thienyl-2,5-diyl selected from a series of compounds of the formula (II-a).

5. Polyarylene dendrimers according to any one of claims 1 to 4, characterized in that It is 3.

6. Polyarylene dendrimers according to any one of claims 1 to 4, wherein n and m independently of one another denote integers selected from the range from 2 to 4.

7. Polyarylene dendrimers according to any one of claims 1 to 4, wherein L is 1.

8. Polyarylene dendrimers according to any one of claims 1 to 4, characterized in that L is equal to 3.

9. Polyarylene dendrimers according to any one of claims 1 to 4, characterized in that L is 7.

10. Polyarylene dendrimers according to any one of claims 1 to 4, characterized in that their solubility is at least 5 mg/ml

11. Polyarylene dendrimers according to any one of claims 1 to 4, characterized in that they are thermally stable up to a temperature of at least 200°C.

12. Polyarylene dendrimers according to any one of claims 1 to 4, characterized in that they possess fluorescent properties.

13. The method of obtaining polianilinovyh dendrimers according to any one of claims 1 to 12, namely, that montendre General formula (III)

where the means H or Br or I; R1, Ar, n, m and L have the abovementioned meanings, first reacts with layerwise agent of General formula (IV)

where R8means a linear or branched C1-C10alkyl group, dialkylamino or phenyl group, then the received monoliterate General formula (V)

where R1, Ar, n, m and L have the above meanings;
interacts with a functional compound selected from a number of compounds of the General formula (VI)

where To have the above values, Y represents Cl or Br, or-och3or-OS2H5or-OS3H7or-OS4H9.

14. The method according to item 13, wherein the functional compound is selected from a number of compounds of the formula (VI), where Y denotes Cl.

15. The method according to item 13, characterized in that Monterone formula (III) Ar means thienyl-2,5-diyl selected from a series of compounds of the formula (II-a), and phenyl-1,4-diyl selected from a series of compounds of the formula (II-b).

16. The method according to item 13, characterized in that Monterone formula (III) Ar means thienyl-2,5-diyl selected from a series of compounds of the formula (II-a).

17. The method according to item 13, characterized in that Monterone formula (III) X is N, with the proviso that Ar is directly linked to X means thienyl-2,5-diyl selected from a range connected the th formula (II-a).

18. The method according to any of PP-17, characterized in that the functional compound selected from a number of compounds of the formula (VI), where K is equal to 3.

19. The method according to any of PP-17, characterized in that Monterone formula (III), n and m independently of one another denote integers selected from the range from 2 to 4.

20. The method according to any of PP-17, characterized in that Monterone formula (III) L is equal to 1.

21. The method according to any of PP-17, characterized in that Monterone formula (III) L is equal to 3.

22. The method according to any of PP-17, characterized in that Monterone formula (III) L is 7.

23. The method according to any of PP-17, characterized in that the interaction of the components is carried out at a temperature from minus 90 to 0°C.

24. The method according to any of PP-17, characterized in that the interaction of the components is carried out in an environment of tetrahydrofuran.



 

Same patents:

FIELD: organosilicon polymers.

SUBSTANCE: novel polycyclic poly- and copolyorganocyclocarbosiloxanes with variable cycle size including structural motif of general formula: , wherein (1) x=3 or 4 and y=1, (2) x=2 and y=2, (3) x=3, and suitable as preceramic templates for manufacturing oxygen-free silicon carbide ceramics are prepared by Würtz reaction in toluene via interaction of chloro-derivatives of organocarbosilanes with metallic sodium in the form of suspension.

EFFECT: enlarged assortment of preceramic templates.

2 cl, 1 tbl, 3 ex

FIELD: organosilicon polymers.

SUBSTANCE: polydimethylsilane is obtained by reaction of dimethyldichlorosilane with sodium at 150-170°C followed by decomposition of unreacted sodium with methyl alcohol, isolation of desired polymer, washing on filter with distilled water, drying on air and the in vacuum. Process is characterized by that sodium reagent is added as deposited on water-soluble solid, incombustible, inorganic substrate.

EFFECT: reduced fire risk of synthesis process and labor intensity of polymer isolation stage.

2 dwg, 1 tbl, 5 ex

FIELD: chemical technology.

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EFFECT: improved preparing method.

1 tbl, 9 ex

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< / BR>
(patent N 4220600, CL

FIELD: chemical technology.

SUBSTANCE: invention describes a method for preparing metallopolycarbosilanes. Method involves interaction of polycarbosilanes with molecular mass above 200 Da and with the main chain consisting of links of the formula: [-(R)2Si-CH2-] wherein R means hydrogen atom (H), (C1-C4)-alkyl or phenyl groups with metalloorganic compounds of the formula MXz wherein M means transient metal of III-VIII group of Periodic system; z = 2-4; X means NR12 wherein R1 means (C1-C4)-alkyl group in organic solvent medium at temperatures from 20°C to 400°C under pressure from 5.05 MPa to 0.2 kPA. Method provides preparing fusible soluble polymers with homogeneous distribution of chemically bound metal atoms that elicit high capacity for fiber- and film-formation from solutions or melts that are hardened in thermochemical treatment and provides high yield of ceramic residue in pyrolysis (up to 85 wt.-%).

EFFECT: improved preparing method.

1 tbl, 9 ex

FIELD: organosilicon polymers.

SUBSTANCE: polydimethylsilane is obtained by reaction of dimethyldichlorosilane with sodium at 150-170°C followed by decomposition of unreacted sodium with methyl alcohol, isolation of desired polymer, washing on filter with distilled water, drying on air and the in vacuum. Process is characterized by that sodium reagent is added as deposited on water-soluble solid, incombustible, inorganic substrate.

EFFECT: reduced fire risk of synthesis process and labor intensity of polymer isolation stage.

2 dwg, 1 tbl, 5 ex

FIELD: organosilicon polymers.

SUBSTANCE: novel polycyclic poly- and copolyorganocyclocarbosiloxanes with variable cycle size including structural motif of general formula: , wherein (1) x=3 or 4 and y=1, (2) x=2 and y=2, (3) x=3, and suitable as preceramic templates for manufacturing oxygen-free silicon carbide ceramics are prepared by Würtz reaction in toluene via interaction of chloro-derivatives of organocarbosilanes with metallic sodium in the form of suspension.

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2 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of chemical technology of silicon-organic compounds. Technical task lies in synthesis of novel polyarylsilane links including dendrimers of large generations suitable for application as luminescent materials for organic electronics and photonics. Claimed are dendrimers of general formula (I) where R1 stands for substituent from group: linear or branched C1-C20alkyl groups; linear or branched C1-C20alkyl groups separated by at least one oxygen atom; linear or branched C1-C20 alkyl groups separated by at least one sulphur atom; branched C3-C20 alkyl groups separated by at least one silicon atom; C2-C20alkenyl groups; Ar represents, independently for each n and m, similar or different arylene radicals, selected from group: substituted or non-substituted thienyl-2,5-diyl of general formula (II-a) substituted or non-substituted phenyl-1,4-diyl of general formula (II-b) substituted or non-substituted 1,3-oxazol-2,5-diyl of general formula (II-c) substituted fluorene-4,4'-diyl of general formula (II-d) where R2, R3, R4, R5, R6 represent independently on each other H or said above for R1; R7 stands for said above for R1; K is equal 2 or 3 or 4; L is equal 1 or 3 or 7 or 15; m and n represent whole numbers from series from 2 to 6. Method of obtaining dendrimers lies in the following: monodendron of general formula (III) where X represents H or Br or I, first reacts with lithiumising agent of general formula R8Li, where R8 represents linear or branched C1-C10alkyl group, dialkylamide or phenyl group; then obtained compound reacts with functional compound selected from group of compounds of formula (CH3)4-KSiYK, where Y represents Cl, or Br, or -OCH3, or -OC2H5, or -OC3H7, or -OC4H9. Claimed method is technological, use of expensive catalysts is not required.

EFFECT: elaboration of technological method of synthesising novel polyarylsilane dendrimers which does not require use of expensive catalysts.

24 cl, 12 dwg, 1 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel branched oligoarylsilanes and their synthesis method. The engineering problem is obtaining branched oligoarylsilanes which contain not less than 5 functional arylsilane links and have a set of properties which enable their use as luminescent materials. The disclosed branched oligoarylsilanes have general formula where R denotes a substitute from: straight or branched C1-C20 alkyl groups; straight or branched C1-C20 alkyl groups separated by at least one oxygen atom; straight or branched C1-C20 alkyl groups separated by at least one sulphur atom; branched C3-C20 alkyl groups separated by at least one silicon atom; C2-C20 alkenyl groups; Ar denotes identical or different arylene or heteroarylene radicals selected from: substituted or unsubstituted thienyl-2,5-diyl, substituted or unsubstituted phenyl-1,4-diyl, substituted or unsubstituted 1,3-oxazole-2,5-diyl, substituted fluorene-4,4'-diyl, substituted cyclopentadithiophene-2,7-diyl; Q is a radical selected from the same group as Ar; X is at least one radical selected from the same group as Ar and/or a radical selected from: 2,1,3-benzothiodiazole-4,7-diyl, anthracene-9,10-diyl, 1,3,4-oxadiazole-2,5-diyl, 1-phenyl-2-pyrazoline-3,5-diyl, perylene-3,10-diyl; L equals 1 or 3 or 7 and preferably 1 or 3; n is an integer from 2 to 4; m is an integer from 1 to 3; k is an integer from 1 to 3. The method of obtaining branched oligoarylsilanes involves reaction of a compound of formula where Y is a boric acid residue or its ester or Br or I, under Suzuki reaction conditions with a reagent of formula (IV) A - Xm - A (IV), where A denotes: Br or I, provided that Y denotes a boric acid residue or its ester; or a boric acid residue or its ester, provided that Y denotes Br or I.

EFFECT: obtaining novel compounds distinguished by high luminescence efficiency, efficient intramolecular transfer of energy between molecule fragments and high thermal stability.

24 cl, 12 dwg, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention relates to macromolecular compounds with a nucleus-shell structure. The invention discloses macromolecular compounds with a nucleus-shell structure, whereby the nucleus has a macromolecular dendritic and hyperbranched structure based on carbon or based on silicon and carbon is bonded to at least three, in particular at least six external atoms through a carbon-based coupling chain (V) which is selected from a group consisting of straight and branched alkylene chains with 2-20 carbon atoms, straight or branched polyoxyalkylene chains, straight or branched siloxane chains or straight or branched carbosilane chains, with straight chains based on carbon oligomeric chains (L) with conjugated double bonds on the entire length. Conjugated chains (L) in each separate case are bonded at the end opposite the coupling chain (V) to one more, specifically, aliphatic, arylaliphatic or oxyaliphatic chain (R) without conjugated double bonds. The chains (V), (L) and (R) form the shell. The invention also discloses a method for synthesis of the said compounds.

EFFECT: novel organic compounds which can be synthesised using conventional solvents and have good semiconductor properties.

16 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing polycarbosilanes. Disclosed is a method of producing polycarbosilane via thermal decomposition of polydimethylsilane in the presence of zirconium tetrachloride in an inert atmosphere at excess pressure of 0.4-0.5 MPa in three steps: holding at 350-380°C for 2-10 hours, releasing low-boiling point components and then holding at 350-420°C for 20-30 hours.

EFFECT: method of producing polycarbosilane which enables to cut time and lower temperature of the process.

1 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemical engineering of organosilicon compounds. Disclosed are novel dendronised polyarylsilanes of general formula

, where R denotes a substitute from: linear C1-C12 or branched C3-C20 alkyl groups; linear C1-C12 or branched C3-C20 alkyl groups, separated by at least one oxygen atom; linear C1-C12 or branched C3-C20 alkyl groups, separated by at least one sulphur atom; branched C3-C20 alkyl groups, separated by at least one silicon atom; C2-C20 alkenyl groups; Ar denotes identical or different arylene or heteroarylene radicals selected from: substituted or unsubstituted thienyl-2,5-diiyl; substitured or unsubstituted phenyl-1,4-diiyl, substituted fluorene-4,4'-diiyl. X denotes identical or different arylene or heteroarylene radicals selected from said group for Ar and/or a radical from 2,1,3-benzothiodiazole-4,7-diiyl, anthracene-9,10-diiyl; L equals 0 or a an integer from 1, 3, 7, 15; k is an integer from 1 to 6; m is an integer from 1 to 6; t is an integer from 2 to 10; n is an integer from 5 to 10000. A method of producing said compounds is also disclosed.

EFFECT: synthesis of novel chemical compounds, characterised by high efficiency of luminescence, high molar absorption coefficient and high thermal stability.

FIELD: physics.

SUBSTANCE: invention relates to organic light-emitting diode (OLED) solid-state light sources used to make colour information screens and colour display devices with high consumer properties, as well as cheap and efficient light sources. Disclosed is an OLED, having a base in form of a transparent substrate having a transparent anode layer and a metal cathode layer with a light-emitting layer in between, which is based on a dendronised polyaryl silane of general formula (I) or (II) , where n is an integer from 5 to 1000.

EFFECT: wide range of OLEDs with high operational characteristics, particularly in the radiation range of 400-700 nm, which enables use thereof as light sources.

7 cl, 3 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: disclosed are novel branched oligoarylsilanes of general formula (I) , where R denotes a substitute selected from: linear or branched C1-C20 alkyl groups; including separated by at least one oxygen or sulphur atom; branched C3-C20 alkyl groups, separated by at least one silicon atom; C2-C20 alkenyl groups; Ar denotes identical or different arylene or heteroarylene radicals selected from: substituted or unsubstituted thienyl-2,5-diiyl, substituted or unsubstituted phenyl-1,4-diiyl, substituted or unsubstituted 1,3-oxazole-2,5-diiyl, substituted fluorene-4,4'-diiyl, substituted cyclopentadithiophene-2,7-diiyl; Q denotes a radical selected from the series for Ar; X denotes at least one radical selected from the series for Ar and/or a radical selected from: 2,1,3-benzothiiodiazole-4,7-diiyl, anthracene-9,10-diiyl, 1,3,4-oxadiazole-2,5-diiyl, 1-phenyl-2-pyrazoline-3,5-diiyl, perylene-3,10-diiyl; n is an integer from 2 to 4; m is an integer from 1 to 3; k is an integer from 1 to 3. Also disclosed is a method of producing said compounds.

EFFECT: obtaining novel compounds characterised by high luminescence efficiency, efficient intramolecular energy transfer from some molecule fragments to others and high thermal stability.

20 cl, 5 dwg, 1 tbl, 15 ex

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