RU2424244C2 - Method of producing organosilicon dendrons - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: disclosed is two-step method of producing organosilicon metal-containing 12- and 24-multifunctional dendrons of general formula T₈Vi₄(CH(Cl)CH₂SAcAcMⁿ(AcAcSCH₂CH(Cl)Si(OR)₃)_(n-1))₄, in which T₈Vi₄ is a fragment of octavinyl silsesquioxane with residual four free vinyl groups; M is a metal ion; n is valence of the metal which is equal to 2 or 3; R is any organic radical which is chemically inert to components of the reaction system, AcAc is an acetylacetonate ring, involving at the first step reaction of sulphenyl chloride of a metal acetylacetonate with octavinyl silsesquioxane of general formula T₈Vi₈ in a medium of organic solvent, with molar ratio of the sulphenyl chloride of a metal acetylacetonate to the octavinyl silsesquioxane equal to (4-10):1, followed the second step comprising adding to the reaction product an amount of vinyl triorganyloxy silane of general formula ViSi(OR)₃, where R is an organic radical, calculated based on the sulphenyl chloride of the metal acetylacetonate, and is chemically inert to the rest of the components of the reaction system. The reaction system at each step is kept until complete reaction of the reactants.

EFFECT: obtaining dendrons with higher functionality.

10 cl, 2 dwg, 8 ex

Description

The invention relates to a method for producing multifunctional organosilicon metal-containing dendrons, which are used in various industries, agriculture, healthcare and others due to the presence of reactive end groups.

Dendrons are understood to mean highly branched molecules with a complex, most often three-dimensional, structure, the molecular weight of which lies in the molecular weight region of oligomers or polymers. However, the advantage of dendrons is the ability to obtain them with the same constant molecular weight and with a given number of functional end groups, which distinguishes them from ordinary polymers in which there is always a distribution of molecular weights.

Due to the presence of multifunctional end groups in dendrons, they are widely used in various high-tech industries. Thus, dendrons are nanoblocks for the production of nanohybrid polymer materials (Neumann D, Fisher M, Tran L, Matisons JG / J. Am. Chem. Soc. 2002. Vol.124. P.13998). The strictly defined spatial structure of dendrons allows one to obtain materials with a given spatial structure (Pielichowski K., Polyhedral Oligomeric Silsesquioxanes (POSS) -Containing Nanohybrid Polymers / K. Pielichowski 1, J. Njuguna, B. Janowskil, J. Pielichowskil // Adv. Polym. Sci. - 2006 .-- Vol. 201 - p. 225-296). The use of dendrons makes it possible to control the surface properties and surface morphology of materials (Liicke S., Polyhedral oligosilsesquioxanes (POSS) -building blocks for the development of nanostructured materials / S.Liicke, K.Stoppek-Langner // Appl. Surf. Sci. - 1999. - April .-- Vol. 144-145, - p. 713-715); (Strachota A., Chitosan-Oligo (silsesquioxane) Blend Membranes: Preparation, Morphology, and Diffusion Permeability / A. Strachota, G. Tishchenko, L. Matejka, M. Bleha // Journal of Inorganic and Organometallic Polymers. - 2001. - Sept. - Vol. - 11, No. 3. - p. 165-182). Therefore, dendrons are extremely important compounds for the production of various films and membranes.

The literature describes various methods for producing organosilicon dendrons.

A known method for producing organosilicon dendrons with a functionality of 6, 8, 10, depending on the initial cyclosylsesquioxane (RMLaine, Nanobuilding blocks based on the [OSiO _1.5 ] _x (x = 6, 8, 10) octasilsesquioxanes / Laine RM // J. Mater. Chem. - 2005 .-- Vol.15. - p. 3725-3744). According to this method, the formation of dendrons proceeds according to the exchange reaction between cyclosylsesquioxoxane and halide alkyl and silicon alkyl in the presence of tertiary alkylamine. As a result of the method, reaction by-products (alkyl ammonium salts) are formed, which significantly complicate the process of isolating the desired dendrons. The yield of the target product in such reactions is low and ranges from 2 to 50%. Moreover, a greater yield can only be achieved at sufficiently high temperatures, of the order of 80 ° C.

A known method for producing 36- and 108-functional organosilicon dendrons based on tetraalkylsilanes (JW Kriesel, Dendrimers as Building Blocks for Nanostructured Materials: Micro- and Mesoporosity in Dendrimer-Based Xerogels / Kriesel JW, Tilley TD // Chem. Mater. - 1999. - Vol.11. - p.1190-1193). The method of obtaining these dendrons is based on multistage hydrosilylation reactions carried out at a rather high temperature (60 ° C) using expensive platinum catalysts and solvents, which increases the cost of the target product.

In work (Z. Xiao, The First Organosiloxane Thin Films Derived from SiCl3-Terminated Dendrons. Thickness-Dependent Nano- and Mesoscopic Structures of the Films Deposited on Mica by Spin-Coating / Xiao Z., Cai C, Mayeux A., Milenkovic A. // Langmuir. - 2002. - Vol. 18. - p.7728-7739) describes a method for producing 81-functional organosilicon dendron (functional group Si-Cl). The production method is carried out in four stages, of which the first and third stages are the Grignard reaction between the corresponding alkylchlorosilane and allyl magnesium bromide, and the second and fourth stages are the hydrosilylation reaction of the corresponding allyl silane with trichlorosilane. The disadvantages of the described method are multistage and high complexity due to the need to isolate and purify intermediate easily hydrolyzed products, which leads to a low yield of dendrons and, accordingly, unprofitability of this method.

None of the above methods for producing organosilicon dendrons provides for the introduction of metal ions into dendrons, which can significantly change the properties of materials obtained on the basis of such dendrons (K. Wada, Preparation of novel materials for catalysts utilizing metal-containing silsesquioxanes / Wada K., Mitsudo T. // Catalysts Surveys from Asia. - 2005. - Vol. 9, No. 4. - p.229-241).

The closest analogue to the claimed method is a method for producing organosilicon metal-containing 9-functional dendrons, which are alkoxysilyl derivatives of β-diketonates of trivalent metals, in particular chromium (III), cobalt (III), aluminum (III), the interaction of sulfonyl chloride of trivalent metal acetylacetonates with unsaturated silicon compounds, namely with vinylalkoxysilanes. Using this method, tris (trialkoxy-β-chloroethyl-thio-2,4-pentanedionate) chromium (III), tris (trialkoxy-β-chloroethyl-thio-2,4-pentanedionate) cobalt (III) and tris (trialkoxy- β-chloroethyl-thio-2,4-pentanedionate) aluminum (III) (functional group -OR). (Shapkin N.P. Synthesis of alkoxysilyl derivatives of β-diketonates of metals and study of the process of hydrolytic polycondensation of these complexes / N.P. Shapkin, A.S. Skobun, I.V. Svistunova, S.V. Starostina, I.V. Kozlova / / Chemistry and chemical technology. - 2003. - T.46, issue 2. - p.143-146).

The synthesis of these compounds is based on the reaction of addition of vinyltriethoxysilane or vinyltributoxysilane to sulfonyl chloride acetylacetonates of the above trivalent metals:

M (AcAcSCl) ₃ + 3ViSi (OR) ₃ → M (AcAcSCH ₂ CH (Cl) Si (OR) ₃ ) ₃ ,

.where M = Cr (III), Co (III), Al (III); R = -C ₂ H ₅ , -C ₄ H ₉ ; Vi = -C ₂ H ₃ , AcAc - acetylacetonate ring

.

The synthesis of organosilicon dendrons by a known method is carried out in an organic solvent - in toluene. Subsequent isolation and purification of the formed dendrons is carried out by extraction with a benzene-hexane mixture taken respectively in a ratio of 1:10. This method of obtaining organosilicon metal-containing 9-functional dendrons is characterized by a sufficiently high yield of target products (from 60 to 85%), as well as the simplicity of synthesis and isolation of target products.

However, the known method does not allow to increase the functionality and size of the molecules of dendrons, which is a significant disadvantage in obtaining dendrons of this kind. In addition, the toluene used in the method as an organic medium refers to flammable liquids, which is unsafe in the production environment.

The objective of the invention is to develop a method for producing new organosilicon metal-containing multifunctional dendrons, which provides, in comparison with the known method, the production of dendrons with higher functionality, namely with 12- and 24-functional groups, which contributes to a more dense filling of the space in the polymer based on dendron and obtaining in particular, films with more stable mechanical properties and higher thermal stability.

.The problem is solved by the proposed method for producing new organosilicon metal-containing 12- and 24-functional dendrons of the general formula T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcM ⁿ (AcAcSCH ₂ CH (Cl) Si (OR) ₃ ) _(n-1) ) ₄ (1), in which T ₈ Vi ₄ is a fragment of octavinylsilsesquioxoxane with the remaining four free vinyl groups; M is a metal ion; n is the valency of the metal, equal to 2, 3; R - any organic radical chemically inert to the components of the reaction system during the synthesis, AcAc - acetylacetonate ring

.

The invention is illustrated by graphic images that show the structural formulas of the new organosilicon metal-containing multifunctional dendrons - with 24 functional groups, with a trivalent metal (Fig. 1) and with 12 functional groups, with a divalent metal (Fig. 2).

The method involves reacting in an organic solvent medium a metal acetylacetonate sulfonyl chloride with an unsaturated organosilicon compound, which is octavinylsilsesquioxane of the general formula T ₈ Vi ₈ , with a molar ratio of metal acetylacetonate sulfonyl chloride to octavinylsilsesquioxane equal to (4-10) to 1 for a time sufficient for the complete passage of the reaction of accession; the subsequent addition to the product of the metal sulfonyl chloride acetylacetonate calculated in the first step of the product of an amount of vinyltriorganyloxysilane of the general formula ViSi (OR) ₃ , where R is any organic radical chemically inert to the other components of the system; holding the reaction system for a time sufficient to completely undergo the interaction of the reacting substances with the formation of the target product, and isolating the resulting target product.

As sulfenyl chloride metal acetylacetonates take any sulfonyl chloride acetylacetonates of divalent or trivalent metals, such as chromium (III), cobalt (III), aluminum (III), Be (II).

As vinyltriorganyloxysilane, vinyltrialkoxysilanes with aliphatic radicals inert to the other components of the reaction system, for example vinyltriethoxysilane (ViSi (OEt) ₃ , where Vi = -C ₂ H ₃ , Et = -C ₂ H ₅ ), vinyltrimethoxysilane (Vi) ₃ , where Me is CH ₃ ) and vinyltributoxysilane (ViSi (OBu) ₃ , where Bu = —C ₄ H ₉ ).

The method for producing new organosilicon metal-containing multifunctional dendrons of the general formula T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcM ⁿ (AcAcSCH ₂ CH (Cl) Si (OR) ₃ ) _(n-1) ) _{4 is} carried out in two stages.

Accordingly, the proposed method for the production of organosilicon metal-containing multifunctional dendrons of the general formula (1) is based on two addition reactions:

the first reaction is the addition of sulfonyl chloride of metal acetylacetonate to an unsaturated organosilicon compound, which is octavinylsilsesquioxane according to the equation:

T ₈ Vi ₈ + 4 M ⁿ (AcAcSCl) _n → T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcM ⁿ (AcAcSCl) _(n-1) ) ₄ ;

the second reaction is the addition of vinyltriorganyloxysilane to the product resulting from the first reaction to obtain the target product according to the equation:

T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcM ⁿ (AcAcSCl) _(n-1) ) ₄ +4 (nl) ViSi (OR) ₃ →

T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcM ⁿ (AcAcSCH ₂ CH (Cl) Si (OR) ₃ ) _(n-1) ) ₄

In the first stage of the process, divalent or trivalent metal sulfonyl chloride acetylacetonate is reacted with octavinylsilsesesquioxane taken in a molar ratio of (4-10) to 1 in a suitable organic solvent for a time sufficient to completely complete the addition reaction. It was experimentally established that upon completion of the interaction of the taken starting materials, the viscosity of the reaction solution begins to increase, which can be used as a means of controlling the completeness of the reaction.

It was found that in the General case, the interaction time of the reagents in the first stage is 10-30 minutes.

As the solvent in the framework of the present invention, any organic solvents and / or mixtures thereof are suitable in which they completely dissolve and with which all substances involved in the reaction do not chemically interact. However, it is preferable to use, as organic solvents, safer than toluene, halide alkanes, for example chloroform, carbon tetrachloride, dichloromethane.

The addition of sulfonyl chlorides of metal acetylacetonates to octavinylsilsesesquioxane in the first stage of the process is carried out strictly according to four of the eight vinyl groups of octavinylsilsesquioxoxane. Four vinyl groups remain free. Therefore, in the present invention, the quantitative passage of the reaction of addition of sulfenyl chloride of metal acetylacetonates to octavinylsilsesquioxane means the complete addition of four molecules of sulfonyl chloride of metal acetylacetonate to one molecule of octavinylsilsesquioxane.

Then, the amount of vinyltriorganyloxysilane of the general formula ViSi (OR) ₃ calculated according to metal sulfonyl chloride of the metal acetylacetonate obtained in the first stage is added and the reaction system is maintained for 4-6 hours.

It was experimentally established that keeping in the second stage of the reaction mass for less than 4 hours is not enough for the complete passage of the interaction of the reacting substances, which affects the yield of the target product. On the other hand, an increase in the aging time of the reaction mass of more than 6 hours is impractical because in the indicated time interval, the yield of the target products approaches 100%.

It has also been shown experimentally that it is possible to carry out a method for producing new organosilicon metal-containing multifunctional dendrons of the general formula (1) based on addition reactions at both stages in a wide range of concentrations and temperatures, determined by the solubility of the starting compounds and reaction products. However, it is most preferable to carry out the method under normal conditions.

After the two-stage process for obtaining the target products is completed, they are isolated.

The proposed method for producing new organosilicon metal-containing multifunctional dendrons can be implemented with a quantitative ratio of metal sulfonyl chloride acetylacetonate and octavinyl silsesesquioxane equal to 4: 1, i.e. without an excess of sulfenyl chloride of metal acetylacetonate, as well as with its excess. The need to introduce an excess of sulfenyl chloride of metal acetylacetonate in the particular case of the invention is justified by the following.

With an increase in synthesis volumes (for example, in the production process), it becomes possible for a side reaction between octavinylsilsesquioxane and sulfonyl chloride of metal acetylacetonate to form a spatial polymer. The use of an excess of sulfonyl chloride of metal acetylacetonate avoids the occurrence of a side reaction of the formation of a spatial polymer without the use of such methods as strong dilution of the reaction system or the use of more intensive mixing. The introduction of an excess of more than 2.5-fold into the reaction system is not economically feasible.

In the particular case of the invention, the synthesis of 12- and 24-functional organosilicon metal-containing dendrons in the first stage is carried out with a molar ratio of metal acetylacetonate sulfonyl chloride and octavinyl silsesesquioxane equal to 4: 1, i.e. without an excess of sulfonyl chloride of metal acetylacetonate (addition of sulfonyl chloride of metal acetylacetonate to octavinylsilsesquioxane occurs in quantitative yield). In this case, when implementing the proposed method, the reaction produces only the target product — a 12- or 24-functional organosilicon dendron. This allows you to select the target dendron by distillation of the organic solvent on a rotary evaporator under reduced pressure and a temperature of not higher than 45 ° C.

If necessary, to achieve greater purity of the product, re-precipitation is recommended, which is carried out by adding small portions of the precipitator dendron, a limiting alkane, preferably hexane, to the solution, followed by filtration.

In another embodiment of the invention, the synthesis of 12- and 24-functional organosilicon metal-containing dendrons in the first stage is carried out with an excess of metal acetylacetonate sulfenyl chloride (no more than 2.5-fold excess of the stoichiometric amount). Moreover, as a result of the synthesis, not only the target 12- or 24-functional organosilicon metal-containing dendrons are formed, but also the secondary 9-functional dendron, the product of the interaction of an excess of sulfenyl chloride of metal acetylacetonate and vinyltriorganorganoxysilane. The separation of the resulting products is carried out by gel permeation chromatography on a column with any suitable organic sorbent (polymer or copolymer), after preliminary concentration of the solution on a rotary evaporator under reduced pressure and a temperature of no higher than 45 ° C.

The target dendron is separated first, as it has a much higher molecular weight compared to the by-product. Detection of products at the outlet of the column can be carried out by any method, including visually when colored metal sulfonyl chlorides are introduced into the reaction, since the color of the reaction products is determined by the color of the initial metal acetylacetonate sulfenyl chloride and differs slightly from it.

After separation, the target product is in an eluent solution, which was used in chromatography. The selection of the target dendron is also carried out by distillation of the solvent on a rotary evaporator. To achieve greater purity of the product, it is additionally possible to carry out reprecipitation, which is carried out by adding small portions to the solution of the dendron of the precipitating agent — a limiting alkane, preferably hexane, followed by filtration.

.As a result of the implementation of the proposed method receive multifunctional organosilicon metal-containing dendrons of the General formula T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcM ⁿ (AcAcSCH ₂ CH (Cl) Si (OR) ₃ ) _(n-1) ) ₄ , in which T ₈ Vi ₄ is a fragment of octavinylsilsesesquioxane with the remaining four free vinyl groups, M is a metal ion, n is a metal valency of 2, 3, R is any organic radical chemically inert to the system components during synthesis, AcAc is an acetylacetonate ring

.

Thus, the technical result of the claimed invention is the development of a method for producing previously unknown organosilicon metal-containing multifunctional dendrons of the general formula T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcM ⁿ (AcAcSCH ₂ CH (Cl) Si (OR) ₃ ) _(n-1) ) ₄ with 12- and 24-functional groups, providing the target products with almost 100% yield.

Information on the fame of the new organosilicon metal-containing multifunctional dendrons of the above composition from the prior art is not revealed.

Additional advantages of the developed method are the simplicity of the synthesis when quantifying the addition reactions at both stages, the ease of isolation and separation of the resulting products, and the use of less hazardous organic solvents. Both stages of the method are carried out in one technological volume; during the implementation of the method, mixing is carried out only for the purpose of homogenizing the reaction system, which allows to reduce the cost of the method.

To implement the method, chemical equipment manufactured by industry is used.

Obtained according to the claimed method, organosilicon metal-containing 12- and 24-functional dendrons were investigated by the following physicochemical methods.

IR spectra in the region of 4000-400 cm ^-1 were recorded on a Spectrum 1000 BX-11 instrument (Perkin-Elmer) in potassium bromide, chloroform and a thin layer.

NMR spectra were recorded on a Bruker Avance AV-300 spectrometer with a proton resonance frequency of 300 MHz. The methods used were cross-polarization, suppression of dipole-dipole interactions, and rotation at a magic angle (VMU). The duration of the 90 ° pulse for protons was 4 μs, the polarization transfer time was 500–3000 ms, the rotation speed was 3, 5, 7 kHz, the diameter of the sample was 4 mm, the time between pulses was 2–5 s, and the number of accumulations was 500–2000. Tetramethylsilane was used as the standard for carbon and silicon nuclei, and the chemical shift zero (CS) was set in a separate experiment. The error in the determination of cholesterol did not exceed 1-2 ppm. depending on the resolution of the peak. Spectra were recorded at a temperature of 300 K.

The possibility of carrying out the invention is confirmed by the following examples. Examples 1 and 2 relate to the preparation of the starting octavinylsilsesquioxane and sulfonyl chlorides of acetylacetonates Cr (III), Al (III) and Be (II).

Example 1

Obtaining the original octavinylsilsesquioxane.

The synthesis was carried out according to the procedure described in (Konig, H.J.Silsesquioxane mit oligomeren Kafigstrukturen: Diss ...: abgabetermin 05/29/2002: priifungstermin 07/05/2002 / H.J. Konig. - Lugde, 2002, 114 p.).

650 ml of 95% ethanol (EtOH) (ρ = 0.8042 g / ml, n (EtOH) = 9.6 mol, n (H ₂ O) = 1.5 mol) were placed in a one-necked round-bottom flask with stirring 0.5 mol of vinyl trichlorosilane was added dropwise. The resulting homogeneous solution was left to mix for three days. A white crystalline precipitate precipitated, which was filtered off, washed with absolute ethyl alcohol and dried in a desiccator under vacuum. Yield 4.6 g of octavinylsilsesquioxane, η = 11.64%. The purity of the product was confirmed by IR, ²⁹ Si-NMR and ¹³ C-NMR spectra, data of elemental and x-ray phase analysis.

In the IR spectrum, well-resolved absorption bands are observed ν (C = C) 1604 cm ^-1 , δ (CH) 1410 cm ^-1 , 1277 cm ^-1 , ν (Si-O) 1111 cm ^-1 , ν (Si-C ) 780 cm ^-1 , δ (O-Si-O) 584 cm ^-1 , ν (Si-O) 465 cm ^-1 , ν (CH) 3067 cm ^-1 , 2962 cm ^-1 , which correspond to the literature data (Voronkov M.G. Octavinylsilsesquioxane / M.G. Voronkov, Martynova T.N. // Zhokh, - 1979.- T. 49. - P.1522-1525).

The ²⁹ Si-NMR and ¹³ C-NMR spectra are in good agreement with the literature data in the work of Konig, HJ, indicated at the beginning of this example. Two signals in the range of -80.04 and -80.48 m are present in the spectrum of solid-state ²⁹ Si-NMR of octavinylsilsesquioxoxane. d., with a ratio of signal intensities 1: 3. The spectrum of solid-state ¹³ C-NMR cyclooctavinylsilsesquioxane contains two signals in the region of 129.67 (CH) and 138.92 ppm. (CH ₂ ).

Example 2

Preparation of the starting sulfenyl chlorides of acetylacetonates Cr (III), Al (III) and Be (II). The synthesis was carried out according to the method described in (Kluiber R. Inner complexes. IV. Chelate Sulfenil Clorides and Tiocianates / R. Kluiber // J. Am. Cem. Soc. - 1961. - Vol. 83., N 14. - P .3030-3033).

Synthesis of Cr (AcAcSCl) ₃ .

To 2 g of finely ground Cr (AcAc) ₃ suspended in 10 ml of dry hexane, 2 ml of sulfur dichloride was added dropwise with stirring on a magnetic stirrer. The resulting brown precipitate was filtered off, washed with dry hexane from sulfur dichloride and dried. Received 2.81 g, η = 90%.

Synthesis of Be (AcAcSCl) ₂ .

To 2 g of finely ground Be (AcAc) ₂ suspended in 15 ml of dry hexane, 2 ml of sulfur dichloride was added dropwise with stirring on a magnetic stirrer. The resulting bright yellow solution was left for one day at a temperature of -20 ° C. Then the precipitated yellow crystals were filtered off, washed with cold dry hexane from sulfur dioxide and dried. Obtained 3.28 g, η = 64%.

Synthesis of Al (AcAcSCl) ₃ .

To 2 g of finely ground Al (AcAc) ₃ suspended in 10 ml of dry hexane, 2 ml of sulfur dichloride was added dropwise with stirring on a magnetic stirrer. The resulting yellow crystalline precipitate was filtered off, washed with dry hexane from sulfur dioxide and dried. Received 2.66 g, η = 82.4%.

Example 3

Synthesis of a 24-functional organosilicon dendron T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcCr (AcAcSCH ₂ CH (Cl) Si (OEt) ₃ ) ₂ ) ₄ in an excess of chromium (III) acetylacetonate sulfenyl chloride.

A mixture of 0.84 g (1.53 mmol, n (Cr (AcAcSCl) ₃ ): n (T ₈ Vi ₈ ) = 10: 1) Cr (AcAcSCl) ₃ and 0.0910 g (144 μmol) octavinylsilsesquioxoxane was dissolved in 6 , 1 ml of dried chloroform (the solvent volume was calculated based on the required concentration of vinyl groups, in this example 0.19 mmol / ml). After 30 minutes, 0.97 ml (0.872 g, 4.6 mmol) of ViSi (OEt) _{3 was} added to the solution, after which the solution was left to stand for 6 hours. Then, chloroform and the excess part of ViSi (OEt) ₃ were removed on a rotary evaporator (bath temperature 40 ° C, P = 10-15 mm Hg). The resulting glassy mixture of products was dissolved in dried toluene (in this example, toluene was used as eluent for gel chromatography). The necessary aliquot of the resulting solution was introduced into the gel chromatography column. The yield of the target product was 0.6264 g (100%). The molecular weight of the obtained dendron is 4346 g / mol.

In the IR spectrum of the obtained dendron there are absorption bands of both the substituted chelate ring 1552 cm ^-1 and the Si-O bond in the 1104 cm ^-1 octasilsesquioxane fragment. There is also a group of absorption bands of CH bonds of the triethoxysilyl group — Si (OCH ₂ CH ₃ ) ₃ , 2976 cm ⁻¹ .

Example 4

Synthesis of a 24-functional organosilicon dendron T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcAl (AcAcSCH ₂ CH (Cl) Si (OEt) ₃ ) ₂ ) ₄ in an excess of aluminum (III) sulfenyl chloride.

A mixture of 0.90 g (1.72 mmol, n (Al (AcAcSCl) ₃ ): n (T ₈ Vi ₈ ) = 10: 1) Al (AcAcSCl) ₃ and 0.1019 g (161.2 mmol) octavinylsilsesquioxoxane was dissolved in 6.8 ml of dried chloroform (the solvent volume was calculated based on the required concentration of vinyl groups, in this example 0.19 mmol / ml). After 30 minutes, 1.09 ml (0.98 g, 5.16 mmol) of ViSi (OEt) _{3 was} added to the solution, after which the solution was left to stand for 5 hours. Then, chloroform and the excess part of ViSi (OEt) ₃ were removed on a rotary evaporator (bath temperature 40 ° C, P = 10-15 mm Hg). The resulting glassy mixture of products was dissolved in dried toluene (in this example, toluene was used as eluent for gel chromatography). The necessary aliquot of the resulting solution was introduced into the gel chromatography column. The yield of the target product was 0.6816 g (99.56%). The molecular weight of the obtained dendron is 4246 g / mol.

The IR spectrum contains absorption bands of both a substituted chelate ring of 1570 cm ^-1 and Si-O bonds in the 1104 cm ^-1 octasilsesquioxane fragment. There is also a group of absorption bands of CH bonds of the triethoxysilyl group-Si (OCH ₂ CH ₃ ) ₃ , 2927 cm ^-1 .

In the ²⁹ Si-NMR spectrum of the obtained dendron there is a signal in the region of 57.68 ppm related to silicon atoms in the fragment - Si (OEt) ₃ , as well as two signals - 73.86 ppm, 78.21 ppm related to atoms silicon in the octasilsesquioxane fragment. The signal - 78.21 ppm refers to silicon atoms with an unaffected vinyl group, and in the region - 73.86 ppm to silicon atoms in the SCH ₂ CH (Cl) SiO _1.5 fragment.

In the ¹³ C-NMR spectrum, there is a signal of 138.38 ppm related to CH ₂ carbon atoms and 129.94 ppm related to CH carbon atoms in the remaining vinyl groups at silicon atoms. Signals of carbon atoms of chelate rings are present: 197.44 ppm (-C = O), 104.06 ppm (CS), 28.13 ppm (-CH ₃ ). There are also signals of carbon atoms related to the fragment - CH ₂ CH (Cl) Si (OCH ₂ CH ₃ ) ₃ : 19.13 ppm (OCH ₂ C H ₃ ), 60.19 ppm (O C H ₂ CH ₃ ), 39.94 ppm (-S C H ₂ CH (Cl) -), 44.44 ppm (-SCH ₂ C H (Cl) -).

Example 5

Synthesis of 12-functional organosilicon dendron T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcBe (AcAcSCH ₂ CH (Cl) Si (OEt) ₃ )) ₄ in an excess of beryllium (II) acetylacetonate sulfenyl chloride.

A mixture of 0.67 g (1.96 mmol, n (Be (AcAcSCl) ₂ ): n (T ₈ Vi ₈ ) = 10: 1) Be (AcAcSCl) ₂ and 0.1161 g (183.8 μmol) octavinylsilsesquioxoxane was dissolved in 7.7 ml of dried chloroform (the solvent volume was calculated based on the required concentration of vinyl groups, in this example 0.19 mmol / ml). After 30 minutes, 0.83 ml (0.745 g, 3.92 mmol) of ViSi (OEt) _{3 was} added to the solution, after which the solution was left to stand for 6 hours. Then, chloroform and the excess part of ViSi (OEt) ₃ were removed on a rotary evaporator (bath temperature 40 ° C, P = 10-15 mm Hg). The resulting glassy mixture of products was dissolved in dried toluene (in this example, toluene was used as eluent for gel chromatography). The necessary aliquot of the resulting solution was introduced into the gel chromatography column. The yield of the target product was 0.5042 g (99.73%). The molecular weight of the obtained dendron is 2752 g / mol.

The IR spectrum contains absorption bands of both a substituted chelate ring of 1560 cm ^-1 and Si-O bonds in the 1104 cm ^-1 octasilsesquioxane fragment. There is also a group of absorption bands of CH bonds of the triethoxysilyl group-Si (OCH ₂ CH ₃ ) ₃ , 2894 cm ^-1 .

In the ²⁹ Si-NMR spectrum of the obtained dendron, there is a signal in the region of 57.92 ppm related to silicon atoms in the -Si (OEt) ₃ fragment, as well as two signals -74.33 ppm, -78.45 ppm related to atoms silicon in the octasilsesquioxane fragment. The -78.45 ppm signal refers to silicon atoms with an unaffected vinyl group, and in the -74.33 ppm region to silicon atoms in the SCH ₂ CH (Cl) SiO _1.5 fragment.

In the ¹³ C-NMR spectrum, a signal of 139.92 ppm related to CH ₂ carbon atoms and 129.11 ppm related to CH carbon atoms in the remaining vinyl groups at silicon atoms is present. Signals of carbon atoms of chelate rings are present: 198.18 ppm (-C = O), 105.58 ppm (CS), 27.26 ppm (-CH ₃ ). There are also signals of carbon atoms related to the —CH ₂ CH (Cl) Si (OCH ₂ CH3) ₃ fragment: 19.04 ppm (OCH ₂ C H ₃ ), 60.15 ppm (O C H ₂ CH ₃ ), 39 , 38 ppm (-S C H ₂ CH (C1) -), 46.30 ppm (-SCH ₂ C H (C1) -).

Example 6

Synthesis of a 24-functional organosilicon dendron T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcCr (AcAcSCH ₂ CH (Cl) Si (OEt) ₃ ) ₂ ) ₄ .

A mixture of 3.475 g (6.33 mmol, n (Cr (AcAcSCl) ₃ ): n (T ₈ Vi ₈ ) = 4: l) Cr (AcAcSCl) ₃ and 1.0000 g (1.58 mmol) octavinylsilsesquioxoxane was dissolved in 66 , 6 ml of dried chloroform (the volume of solvent was calculated based on the required concentration of vinyl groups, in this example 0.19 mmol / ml). After 30 minutes, 2.66 ml (2.405 g, 12.7 mmol) of ViSi (OEt) _{3 was} added to the solution, after which the solution was left to stand for 4 hours. Then, chloroform and the excess part of ViSi (OEt) ₃ were removed on a rotary evaporator (bath temperature 40 ° C, P = 10-15 mm Hg). After reprecipitation with hexane from a solution of chloroform, the yield of the target product was 6.8601 g (99.73%).

The data of IR spectroscopy are similar to those presented in example 3.

Example 7

Synthesis of a 24-functional organosilicon dendron T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcAl (AcAcSCH ₂ CH (Cl) Si (OEt) ₃ ) ₂ ) ₄ .

A mixture of 3.313 g (6.33 mmol, n (Al (AcAcSCl) ₃ ): n (T ₈ Vi ₈ ) = 4: l) Al (AcAcSCl) ₃ and 1.0000 g (1.58 mmol) octavinylsilsesquioxoxane was dissolved in 66 6 ml of dried chloroform (the volume of solvent was calculated based on the required concentration of vinyl groups, in this example 0.19 mmol / ml). After 30 minutes, 2.66 ml (2.405 g, 12.7 mmol) of ViSi (OEt) _{3 was} added to the solution, after which the solution was left to stand for 5 hours. Then, chloroform and the excess part of ViSi (OEt) ₃ were removed on a rotary evaporator (bath temperature 40 ° C, P = 10-15 mm Hg). After reprecipitation with hexane from a solution of chloroform, the yield of the target product was 6.6958 g (99.66%).

The data of IR, ²⁹ Si-NMR and ¹³ C-NMR spectroscopy are similar to those presented in example 4.

Example 8

Synthesis of a 24-functional organosilicon dendron T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcAl (AcAcSCH ₂ CH (Cl) Si (OEt) ₃ ) ₂ ) ₄ .

A mixture of 2.152 g (6.33 mmol, n (Be (AcAcSCl) ₂ ): n (T ₈ Vi ₈ ) = 4: l) Be (AcAcSCl) ₂ and 1.0000 g (1.58 mmol) octavinylsilsesquioxoxane was dissolved in 66 , 6 ml of dried chloroform (the volume of solvent was calculated based on the required concentration of vinyl groups, in this example 0.19 mmol / ml). After 30 minutes, 1.33 ml (1.203 g, 6.33 mmol) of ViSi (OEt) _{3 was} added to the solution, after which the solution was left to stand for 6 hours. Then, chloroform and the excess part of ViSi (OEt) ₃ were removed on a rotary evaporator (bath temperature 40 ° C, P = 10-15 mm Hg). After reprecipitation with hexane from a solution of chloroform, the yield of the target product was 4.3489 g (99.87%).

The data of IR, ²⁹ Si-NMR and ¹³ C-NMR spectroscopy are similar to those presented in example 5.

Claims (10)

1. A method of producing organosilicon multifunctional dendrons, comprising reacting a metal sulfonyl chloride acetylacetonate with an unsaturated organosilicon compound in an organic solvent medium, characterized in that octavinylsilsesquioxoxane of the general formula T ₈ Vi _{8 is} used as an unsaturated organosilicon compound, with a molar ratio of metal sulfylphenyl chloride to metal octavoxylacetone to octavoxanilose (4-10) to 1, for a time sufficient to complete the reaction unity, then adding to the resulting reaction product sulfenyl chloride of the metal acetylacetonate oktavinilsilseskvioksanom calculated by sulphenylchlorides acetylacetonate metal amount viniltriorganiloksisilana general formula ViSi (OR) _3, where R - an organic radical which is chemically inert to the other components of the reaction system, heating the reaction system for a time sufficient for the complete passage of the interaction of reacting substances with the formation of the target product of the General formula T ₈ Vi ₄ (CH (Cl) CH ₂ SAcAcM ⁿ (AcAcSCH ₂ CH (Cl) Si (OR) ₃ ) _(n-1) ) ₄ , in which T ₈ Vi ₄ is a fragment of octavinylsilsesquioxane with the remaining four free vinyl groups; M is a metal ion; n is the valency of the metal, equal to 2, 3; R - any organic radical chemically inert to the components of the reaction system during the synthesis, AcAc - acetylacetonate ring

, and the selection of the resulting target product. 2. The method according to claim 1, characterized in that as sulfenyl chloride metal acetylacetonates take sulfenyl chloride acetylacetonates of divalent or trivalent metals. 3. The method according to claim 1, characterized in that as vinyltriorganoxysilane take vinyltrialkoxysilanes with aliphatic radicals, preferably vinyltriethoxysilane, vinyltrimethoxysilane or vinyltriboxysilane. 4. The method according to claim 1, characterized in that the molar ratio of sulfonyl chloride of metal acetylacetonate to octavinylsilsesquioxane is 4 to 1. 5. The method according to claim 1, characterized in that the sulfonyl chloride of metal acetylacetonate is taken in excess not exceeding a 2.5-fold amount with respect to the stoichiometric. 6. The method according to claim 1, characterized in that the reaction time of sulfenyl chloride of metal acetylacetonate with octavinylsilsesquioxane is 10-30 minutes 7. The method according to claim 1, characterized in that the reaction time of vinyltriorganyloxysilane with the product obtained by the interaction of metal sulfonyl chloride acetylacetonate with octavinylsilsesquioxane is 4-6 hours 8. The method according to claim 1 or 4, characterized in that the selection of the target product is carried out by distillation of the organic solvent on a rotary evaporator under reduced pressure and a temperature of not higher than 45 ° C. 9. The method according to claim 1 or 5, characterized in that for the separation of the target 12- or 24-functional organosilicon metal-containing dendrons from the by-product, the solution is preconcentrated on a rotary evaporator under reduced pressure and a temperature of not higher than 45 ° C, after which separation is carried out formed target 12- and 24-functional dendrons from by-products by gel chromatography. 10. The method according to claim 1, characterized in that in order to increase the purity of the target product, it is reprecipitated by adding to the solution containing the target product a precipitating agent — a limiting alkane, preferably hexane, followed by filtration.

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