RU2422473C1 - Carbosilane-siloxane dendrimers - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry of organosilicon compounds with a branched structure. Disclosed are novel carbosilane-siloxane dendrimers from zero G-O(Cycle) to sixth generation G-6(Cycle), containing in the outer layer the corresponding number of eight-member dimethylsiloxane cycles connected with a silicon atom of the outer layer of the dendrimer by a propyl group of general formula

, where a, b, c, d, e, f and g denote the number of groups bonded with the branching centre and for the zero generation dendrimer, a equals 4, b, c, d, e, f and g equal 0; for the first generation dendrimer a equals 2, b equals 4, c, d, e, f and g equal 0; for the second generation dendrimer, a and b equal 2, c, d, e, f equal 0, g equals 4; for the third generation dendrimer, a, b and c equal 2, d, e, f equal 0, g equals 4; for the fourth generation dendrimer, a, b, c and d equal 2, e, f equal 0, g equals 4; for the fifth generation dendrimer a, b, c, d and e equal 2, f equals 0, g equals 4; for the sixth generation dendrimer, a, b, c, d, e and f equal 2, g equals 4.

EFFECT: obtaining novel chemical compounds.

Description

The invention relates to the field of chemistry of organosilicon compounds and may find industrial application in the preparation of branched polyorganosiloxanes, in particular multibeam star-shaped, and in the preparation of three-dimensional methylsiloxane network structures with multicenter dendritic nodes. Such compounds can be used in the medical and biological industries, as special-purpose membranes, as molecular containers, and also as precursors for the production of various hybrid organo-inorganic materials. More specifically, the invention relates to new organosiloxane polymers having an internal dendritic carbosilane structure and an outer layer consisting of eight-membered dimethylcyclosiloxanes connected to the terminal silicon atom of the dendrimer by a hydrocarbon spacer.

Carbosilane dendrimers are a relatively new polymer object, characterized by a branched three-dimensional spatial structure that does not contain cyclic fragments. Dendrimers have a given structure and molecular weight, a large and yet strictly defined number of functional groups in the outer layer. The synthesis of carbosilane dendrimers is carried out by alternating hydrosilylation reactions and the Grignard reaction, starting from a multifunctional branching center, for example, tetraallylisilane (Ponomarenko SA, Rebrov EA, Boyko NI, Muzafarov AM, Shibaev VP "Synthesis of liquid crystal carbosilane dendrimers of the first to fifth generations containing terminal cyanobiphenyl groups. "High Molecule. Comp. 1998. V.40. No. 8. p.1253-1265; E.A. Tatarinova, E.A. Rebrov, V.D. Myakushev, I. B. Meshkov, N. V. Demchenko, A. V. Bystrova, O. V. Lebedeva, AM Muzafarov "Synthesis and study of their homologous series of polyallylcarbosilane dendrimers and their non-functional analogues "Izv. AN, Ser. Khim., 2004, 11, pp. 2444-2493), tetravinylsilane - (US 5276110), alkyl (aryl) trivinylsilanes (US 5677410), etc. .

It is known that by modifying the surface of carbosilane dendrimers of various generations, compounds are obtained that have useful properties. For example, by introducing various types of sugars into the external sphere of carbosilane dendrimers (US2004040554), an antiviral preparation is obtained having a specific ability to bind certain types of viruses.

It is known to obtain and use carbosilane dendrimers with organic end groups as reagents for the neutralization of toxic substances (JP 2003212893).

It is known to produce carbosilane dendrimers with short polyester and polysulfide groups in the outer layer (CA 2279000) connected to the terminal silicon atoms of the dendrimer by hydrocarbon bridges. It is shown that such modifications of the outer layer make it possible to carry out further polymer-analogous transformations in order to obtain star-shaped structures of various nature, and at this stage the compounds are hydrolytically stable.

It is known to obtain carbosilane dendrimers with hydroxysilyl groups in the outer layer, on the basis of which it is possible to obtain hybrid organo-inorganic, including metal-containing, compounds for various coatings (US 5,677,410).

Carbosilane dendrimers modified in the outer layer by cyclic fragments based on siloxanes are not known.

The closest in structure to the claimed dendrimer compounds with an external dimethylsiloxane layer of cyclic structure are multipath polydimethylsiloxanes with a carbosilane dendritic branching center (NGVasilenko, EARebrov, AMMuzafarov, B. Epwein, B. Striegel, M. Multi-Arm. star polymers with polylithiated carbosilane dendrimers. "Macromol. Chem. Phys. 1998. V.199. p.889-895.) This article presents carbosilane dendrimers with an outer layer modified by linear dimethylsiloxane rays with terminal functional lithiumoxy groups. The presence of these groups allows the use of such compounds both for the preparation of crosslinked structures and for further transformations with the aim of introducing new modifying groups. The disadvantage of the proposed compound is the high activity of the terminal siloxanolate active centers, since both storage and further transformations require an absolute absence of moisture, that is, expensive hardware design. Moreover, the method for producing such compounds — anionic polymerization of hexamethylcyclotrisiloxane — is not technologically advanced, and, moreover, this method does not allow obtaining short dimethylsiloxane oligomers on the surface of dendrimers and, accordingly, dense networks with a small distance between dendrimer units.

The following commonly used dendrimer notations are used in the description:

Gn (All) is a dendrimer of a carbosilane structure of generation n with allylic groups at terminal silicon atoms;

Gn (Cycle), which corresponds to [Si _m ^{m + 3} (Cycle)] - a carbosilane-siloxane generation dendrimer n containing m silicon atoms in the internal carbosilane structure and (m + 3) 1,3,3,5,5,7 , 7-heptamethylcyclotetrasiloxane fragments in the outer siloxane layer. G-0 (Cycle) corresponds to [Si ₁ ⁴ (Cycle)]; Gl (Cycle) corresponds to [Si ₅ ⁸ (Cycle)]; G-2 (Cycle) corresponds to [Si ₁₃ ¹⁶ (Cycle)]; G-3 (Cycle) corresponds to [Si ₂₉ ³² (Cycle)]; G-4 (Cycle) corresponds to [Si ₆₁ ⁶⁴ (Cycle)]; G-5 (Cycle) corresponds to [Si ₁₂₅ ¹²⁸ (Cycle)]; G-6 (Cycle) corresponds to [Si ₂₅₃ ²⁵⁶ (Cycle)].

The objective of this invention is to obtain a new result, which consists in the creation of new carbosilane-siloxane dendrimers with short dimethylsiloxane fragments in the outer layer that are not polydispersity and capable of further transformations and at the same time quite stable during storage.

The problem is solved in that new carbosilane-siloxane dendrimers from zero GO (Cycle) to the sixth generation of G-6 (Cycle) are obtained, containing in the outer layer a corresponding number of eight-membered dimethylsiloxane cycles connected to the silicon terminal atom of the dendrimer by a propyl group, of the general formula (I )

where a, b, c, d, e, f and g means the number of groups associated with the branch center, and is equal to:

a is 2 or 4;

b is 0; 2 or 4;

c, d, e and f are 0 or 2;

g is 0 or 4.

In particular, a zero-generation carbosilane-siloxane dendrimer G-0 (Cycle) was obtained, where a is 4, b, c, d, e, f and g is 0. The compound has the following structure and corresponds to [Si ₁ ⁴ (Cycle)] :

In particular, the first generation carbosilane-siloxane dendrimer Gl (Cycle) was obtained, where a is 2, b is 4, c, d, e, f and g is 0. The compound has the following structure and corresponds to [S ₁ ⁵ (Cycle)] :

In particular, the second-generation carbosilane-siloxane dendrimer G-2 (Cycle) was obtained, where a and equal to 2, c, d, e, f are 0, g is 4. The compound has the following structure and corresponds to [Si ₁₃ ¹⁶ (Cycle )]:

In particular, a third-generation carbosilane-siloxane dendrimer G-3 (Cycle) was obtained, where a, b and c are 2, d, e, f is 0, g is 4. The compound has the following structure and corresponds to Si ₂₉ ³² (Cycle) ]:

In particular, the fourth-generation carbosilane-siloxane dendrimer G-4 (Cycle) was obtained, where a, b, c and d are 2, e, f is 0, g is 4. The compound has the following structure and corresponds to [Si ₆₁ ⁶⁴ (Cycle )]:

In particular, the fifth generation carbosilane-siloxane dendrimer G-5 (Cycle) was obtained, where a, b, c, d and e are 2, f is 0, g is 4. The compound has the following structure and corresponds to [Si ₁₂₅ ¹²⁸ (Cycle )]:

In particular, the sixth generation carbosilane-siloxane dendrimer G-6 (Cycle) was obtained, where a, b, c, d, e and f are 2, g is 4. The compound has the following structure and corresponds to [Si ₂₅₃ ²⁵⁶ (Cycle)] :

The synthesis of Gn carbosilane-siloxane dendrimers (Cycle) was carried out using the well-known hydrosilylation reaction of unsaturated allyl groups of the starting Gn (All) carbosilane dendrimer with a 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane (US 5,210,247) hydride group in the presence of platinum catalysts according to the scheme:

- карбосилановый дендример генерации n.Where

- carbosilane dendrimer generation n.

соответствует

- атом кремния силоксанового цикла, связанный пропильной группой с карбосилановым дендримером. Кривые ГПХ карбосилан-силоксановых дендримеров по примерам 1, 4 и 7 (Фиг.2) указывают на мономодальное и узкодисперсное молекулярно-массовое распределение синтезированных соединений.As an illustration, figure 1 shows a schematic representation of a fourth generation dendrimer with a cyclosiloxane outer layer, where

corresponds to

- a silicon atom of the siloxane cycle bonded by the propyl group to a carbosilane dendrimer. GPC curves of carbosilane-siloxane dendrimers according to examples 1, 4 and 7 (Figure 2) indicate a monomodal and narrow molecular weight distribution of the synthesized compounds.

The completeness of the reaction was monitored by ¹ H-NMR spectra. Figure 3 shows the ¹ H-NMR spectra of the starting carbosilane dendrimer with an allyl functional outer layer - G-3 (All) - (curve 1) and the target carbosilane-siloxane dendrimer formed after the hydride addition reaction 1,3,3,5,5 , 7,7-heptamethylcyclotetrasiloxane - G-3 (Cycle) - (curve 2).

From the spectrum one can see the complete disappearance of the proton signals of the allylic groups of the outer layer of the dendrimer in the region of 4.8-5.0 and 5.6-5.9 ppm The ratio of the integral intensities of protons of various groups corresponds to the calculated values.

The starting compounds were synthesized by known methods.

A method for the synthesis of carbosilane dendrimers with an allyl-functional outer layer is described in the work of AM Muzafarov, O. B. Gorbatsevich, E. A. Rebrov, G. M. Ignatyev, T. B. Censkaya, V. D. Myakushev, A. F. Bulkin , BC Folders. Organosilicon Dendrimers: Bulk-growing Polyallylcarbosilanes. Highly. Connection 1993. V.35. No. 11. p. 1867-1872. The purity and structure of the dendrimers was proved using GPC data (Figure 2), 1H NMR (Figure 3) and ²⁹ Si NMR (Figure 4) and elemental analysis.

The synthesis of the agent for modification of the outer layer of dendrimers - 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane was carried out using the following sequence of known reactions:

Figure 2 shows the GPC curves of carbosilane-siloxane dendrimers:

1 - as in example 1; 2 - according to example 4; 3 - as in example 7.

Figure 3 shows the spectra of ¹ H NMR: 1 - the original carbosilane dendrimer G-3 (All) and 2-carbosilane-siloxane dendrimer G-3 (Cycle), as in example 4.

Figure 4 shows the spectrum of ²⁹ Si NMR of the carbosilane-siloxane dendrimer G-3 (Cycle) in example 4.

The invention is illustrated by the following examples.

Example 1

Synthesis of dendrimer G-0 (Cycle) [S ₁ ⁴ (Cycle)]

To a solution of a mixture of 0.36 g (0.0019 g-m) of tetraallyl silane and 2.63 g (0.0093 g-m) of 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane in 5 ml of dry hexane was added 12µ1 Carstedt catalyst. The reaction was carried out for 4 hours at a temperature of 25-40 ° C. After removal of volatile products and purification by preparative chromatography (Phenogel 75KD column, THF solvent), the yield of the product [Si ₁ ⁴ (Cycle)] was (72%).

¹ H NMR (CDCl ₃ , 200 MHz), δ = 1.36 (m, 8H, -CH ₂ -CH ₂ -CH ₂ -), δ = 0.59 (m, 16H, Si-CH ₂ -), δ = 0.08-0.05 (s, s, 84H, Si- (CH ₃ ) in the cycle).

²⁹ Si NMR (CDCl ₃ , 500 MHz), δ = 0.83 (s, 1 Si, Si _center ), δ = -19.16 (s, 4Si, = Si ^k (CH ₃ ) (C ₃ H ₆ ) in the cycle), δ = -19.40 (s, 8Si, = Si ^{1, n} (CH ₃ ) ₂ in the cycle), δ = -20.29 (c, 4Si, = Si ^m (CH ₃ ) ₂ in the cycle )

Elemental analysis,%: calculated. Si - 36.06; C 36.36; H 8.18; found Si, 35.65; C, 37.01; H - 8.21.

Example 2

Synthesis of dendrimer G-1 (Cycle).

To a solution of a mixture of 2.30 g (0.0033 g-m) of the dendrimer Gl (All) and 8.93 g (0.0317 g-m) of 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane in 5 ml of dry hexane was added 26 µ1 Carstedt catalyst. The reaction was carried out for 4 hours at a temperature of 25-40 ° C. After removal of volatile products and purification by preparative chromatography, the product yield [Si ₅ ⁸ (Cycle)] was 71%. ¹ H NMR (CDCl ₃ , 200 MHz), δ = 1.36 (m, 24H, -CH ₂ -CH ₂ -CH ₂ -), δ = 0.58 (m, 48H, Si-CH ₂ -), δ = 0.08-0.05 (s, s, 168H, Si- (CH ₃ ) in the cycle), δ = -0.08 (s, 12H, Si _int. (CP ₃ ).

²⁹ Si NMR (CDCl ₃ ,), δ = 0.80 (s, ISi, Si _center ), δ = 1.09 (s, 4Si, (CH ₃ ) Si _ext. , (C ₃ H ₆ ) ₂ ), δ = -19.19 (s, 8Si, = Si ^k (CH ₃ ) (C ₃ H ₆ ) in the cycle), δ = -19.43 (c, 16Si, = Si ^{1, n} (CH ₃ ) ₂ in cycle), δ = -20.31 (c, 8Si, = Si ^m (CH ₃ ) ₂ in the cycle).

Elemental analysis,%: calculated. Si - 35.02; C 38.94; H 8.52; Found Si, 35.80; C, 38.31; H 8.44.

Example 3

Synthesis of carbosilane-siloxane dendrimer G-2 (Cycle).

To a solution of a mixture of 3.07 g (0.0018 g-m) of dendrimer G-2 (A11) and 9.75 g (0.0346 g-m) of 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane in 5 ml of dry hexane was added 26 µ1 Carstedt catalyst. The reaction was carried out for 4 hours at a temperature of 25-40 ° C. After removal of volatile products and purification by preparative chromatography, the product yield [Si ₁₃ ¹⁶ (Cycle)] was 77%. ¹ H NMR (CDCl ₃ , 200 MHz), δ = 1.36 (m, 56H, -CH ₂ -CH ₂ -CH ₂ -), δ = 0.58 (m, 112H, Si-CH ₂ -), δ = 0.08-0.05 (s, s, 336H, Si- (CH ₃ ) in the cycle), δ = -0.08 (s, 36H, Si _int . (CH ₃ ).

²⁹ Si NMR (CDCl _3, 500 MHz), δ = 0,77 (c, 5Si, Si _{ext.), Δ = 1,07 (c} , 8Si, (CH ₃₎ Si _Ext. (C ₃ H _{6) 2} ), δ = -19.22 (s, 16Si, = Si ^k (CH ₃ ) (C ₃ H ₆ ) in the cycle), δ = -19.46 (s, 32Si, = Si ^{1, n} (CH ₃ ) ₂ in the cycle), δ = -20.33 (c, 16Si, = Si ^m (CH ₃ ) ₂ in the cycle).

Elemental analysis,%: calculated. Si 34.61; C 40.07; H 8.67; found Si, 35.11; C, 39.37; H - 8.64.

Example 4

Synthesis of G-3 carbosilane-siloxane dendrimer (Cycle).

To a solution of a mixture of 0.17 g (0.000046 g-m) of the dendrimer G-3 (All) and 0.5 g (0.00177 g-m) of 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane in 5 ml of dry hexane was added 26 µ1 Carstedt catalyst. The reaction was carried out for 4 hours at a temperature of 25-40 ° C. After removal of volatile products and purification by preparative chromatography, the product yield [Si ₂₉ ³² (Cycle)] was 70%. ¹ H NMR (CDCl ₃ , 200 MHz), δ = 1.35 (m, 120H, -CH ₂ -CH ₂ -CH ₂ -), δ = 0.56 (m, 240H, Si-CH ₂ -), δ = 0.08-0.05 (s, s, 672H, Si- (CH ₃ ) in the cycle), δ = -0.08 (s, 84H, Si _int. (CH ₃ ).

²⁹ Si NMR (CDCl ₃ , 500 Hz), δ = 0.73 (s, 13Si, Si _int.dend. ), Δ = 1.06 (s, 16Si, Si _ext.dend. ), Δ = -19, 24 (s, 32Si, = Si ^k (CH ₃ ) (C ₃ H ₆ ) in the cycle), δ = -19.50 (s, 64S1, = Si ^{1, n} (CH ₃ ) ₂ in the cycle), δ = -20.36 (s, 32Si, = Si ^m (CH ₃ ) ₂ in the cycle).

Elemental analysis,%: calculated. Si 34.42; C 40.59; H 8.74; found Si, 35.02; C, 39.96; H - 8.72.

Example 5

Synthesis of carbosilane-siloxane dendrimer G-4 (Cycle).

To a solution of a mixture of 3.42 g (0.00044 g-m) of dendrimer G-4 (All) and 9.53 g (0.03386 g-m) of 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane in 5 ml of dry hexane was added 26 µ1 Carstedt catalyst. The reaction was carried out for 4 hours at a temperature of 25-40 ° C. After removal of volatile products and purification by preparative chromatography, the product yield [Si ₆₁ ⁶⁴ (Cycle)] was 74%. ¹ H NMR (CDCl ₃ , 200 MHz), δ = 1.35 (m, 248H, -CH ₂ -CH ₂ -CH ₂ -), δ = 0.56 (m, 496H, Si-CH ₂ -), δ = 0.08-0.05 (s, s, 1344H, Si- (CH ₃ ) in the cycle), δ = -0.08 (s, 180H, Si _int. (CH ₃ ).

²⁹ Si NMR (CDCl ₃ , 500 MHz), δ = 0.68 (s, 29Si, Si _{int. Dendr.} ), 5 = 1.04 (s, 32Si, Si _{ext. Dend} .), Δ = -19 , 28 (c, 64Si, = Si ^k (CH ₃ ) (C ₃ H ₆ ) in the cycle), δ = -19.55 (c, 128S1, = Si ^{1, n} (CH ₃ ) ₂ in the cycle), δ = -20.43 (s, 64Si, = Si ^m (CH ₃ ) ₂ in the cycle).

Elemental analysis,%: calculated. Si 34.33; C 40.84; H 8.77; found Si, 34.95; C, 40.32; H - 8.75.

Example 6

Synthesis of carbosilane-siloxane dendrimer G-5 (Cycle).

To a solution of a mixture of 0.35 g (0.000022 g-m) of the dendrimer G-5 (A11) and 0.95 g (0.0034 g-m) of 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane in 5 ml of dry hexane was added 26 µ1 Carstedt catalyst. The reaction was carried out for 4 hours at a temperature of 25-40 ° C. After removal of the volatile products and purification by preparative chromatography, the yield of the product [Si ₁₂₅ ¹²⁸ (Сс1е)] was 71%. ¹ H NMR (CDCl ₃ , 200 MHz), 5 = 1.35 (m, 504H, -CH ₂ -CH ₂ -CH ₂ -), δ = 0.56 (m, 1008H, Si-CH ₂ -), δ = 0.08-0.05 (s, s, 2688H, Si- (CH ₃ ) in the cycle), δ = -0.08 (s, 372H, 81 _int. (CH ₃ ).

²⁹ Si NMR (CDCl ₃ , 500 MHz), δ = 0.63 (s, 61 Si, Si _int.dend. ), Δ = 1.03 (s, 64Si, 81 _ext.dend. ), Δ = -19 , 34 (c, 128Si, = Si ^k (CH ₃ ) (C ₃ H ₆ ) in the cycle), δ = -19.61 (c, 256S1, = Si ^{1, n} (CH ₃ ) ₂ in the cycle), δ = -20.43 (s, 128Si, = Si ^m (CH ₃ ) ₂ in the cycle).

Elemental analysis,%: calculated. Si 34.29; C 40.97; H 8.79; found Si, 34.90; C 40.65; H - 8.75.

Example 7

Synthesis of carbosilane-siloxane dendrimer. G-6 (Cycle).

To a solution of a mixture of 0.42 g (0.000013 g-m) of dendrimer G-6 (All) and 1.14 g (0.004 g-m) of 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane in 5 ml of dry hexane was added 26 µ1 Carstedt catalyst. The reaction was carried out for 7 hours at a temperature of 25-40 ° C. After removal of volatile products and purification by preparative chromatography, the product yield [Si ₂₅₃ ²⁵⁶ (Cycle)] was 69%. ¹ H NMR (CDCl ₃ , 200 MHz), δ = 1.35 (m, 1016H, -CH ₂ -CH ₂ -CH ₂ -), δ = 0.55 (m, 2032H, Si-CH ₂ -), δ = 0.07-0.04 (s, s, 5376H, Si- (CH ₃ ) in the cycle), δ = -0.08 (s, 756H, Si _int. (CH ₃ ).

29Si NMR (CDCl ₃ , 500 MHz), δ5 = 0.59 (s, 125Si, Si _int.dend. ), 5 = 1.02 (s, 128Si, 81 _ext.dend. ), Δ = -19.39 (c, 256Si, = Si ^k (CH ₃ ) (C ₃ H ₆ ) in the cycle), δ = -19.65 (c, 512Si, = Si ^{1, n} (CH ₃ ) ₂ in the cycle), δ = - 20.52 (s, 256Si, = Si ^m (CH ₃ ) ₂ in the cycle).

Elemental analysis,%: calculated. Si 34.26; C 41.03; H 8.80; found Si, 34.93; C 40.55; H - 8.77.

Claims (8)

1. Carbosilane-siloxane dendrimers from zero to sixth generation with a modified surface of eight-membered dimethylsiloxane cycles of the surface of the general formula (I):

where a, b, c, d, e, f and g means the number of groups associated with the center of branching and is equal to: a is 2 or 4; b is 0; 2 or 4; c, d, e and f are 0 or 2; g is 0 or 4. 2. The carbosilane-siloxane dendrimer according to claim 1, characterized in that for the zero-generation dendrimer, a is 4, b, c, d, e, f and g is 0. 3. The carbosilane-siloxane dendrimer according to claim 1, characterized in that for the first generation dendrimer a is 2, b is 4, c, d, e, f and g is 0. 4. The carbosilane-siloxane dendrimer according to claim 1, characterized in that for the second generation dendrimer a and b are 2, c, d, e, f is 0, g is 4. 5. The carbosilane-siloxane dendrimer according to claim 1, characterized in that for the third generation dendrimer a, b and c are 2, d, e, f is 0, g is 4. 6. The carbosilane-siloxane dendrimer according to claim 1, characterized in that for the fourth generation dendrimer a, b, c and d are 2, e, f is 0, g is 4. 7. The carbosilane-siloxane dendrimer according to claim 1, characterized in that for the fifth generation dendrimer a, b, c, d and e are 2, f is 0, g is 4. 8. The carbosilane-siloxane dendrimer according to claim 1, characterized in that for the sixth generation dendrimer a, b, c, d, e and f are 2, g is 4.

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