Catalyst and method for valence isomerisation of quadricyclane in norbornadiene

FIELD: chemistry.

SUBSTANCE: invention relates to a cobalt complex with a modified phthalocyanine ligand which is covalently bonded with silica gel and has the following general formula: , where: R=Cl, NHAlk, NAlk2, n = 5-7, M = Co. Also disclosed is a method for valence isomerisation of quadricyclane in norbornadiene in the presence of the complex.

EFFECT: invention enables to obtain a cobalt complex with a modified phthalocyanine ligand, which can be used as a heterogeneous catalyst having high activity and high stability.

3 cl, 1 tbl, 29 ex

 

The present invention relates to chemistry and chemical technology, namely, catalysts and method of the valence isomerization of quadricyclane in norbornadiene with their use. The invention can find application in the field of energy to accumulate solar energy and convert it into heat.

The known method exothermic isomerization quadricyclane derivatives in the appropriate norbornadiene derivatives using as catalysts of cobalt porphyrins [K.Maruyama, H.Tamiaki. Catalytic isomerization of water-soluble quadricyclane to norbornadiene derivatives induced by cobalt-porphyrin complexes. J. Org. Chem. 1986. V.51. P.602-606]. The isomerization proceeds at room temperature in an aqueous solution of sodium carbonate. The disadvantage of this method is not sufficiently high activity of the catalyst.

The closest method is a method of isomerization of quadricyclane (Q) in norbornadiene (NBD) with the use of heterogeneous catalysts [K.Maruyama, H.Tamiaki, S.Kawabata. Exothermic isomerization of water-soluble quadricyclanes to norbornadienes by soluble and insoluble catalysts. J. Chem. Soc. Perkin Trans. II. 1986. P.543-549] (prototype). As the active phase in the method used phthalocyanines and porphyrins cobalt, as media - charcoal, silica gel and an organic polymer, and the best results are obtained with cobalt phthalocyanine adsorbed on coal. However, long-term use, so what about the catalyst is inevitably a gradual leaching of the active phase and the decrease of catalytic activity.

The present invention is the finding of heterogeneous catalyst with high catalytic activity and high stability, i.e. having a constant profile activity for a long time, as well as the development method of isomerization of Q in NDS using the obtained catalyst.

The problem is solved by the synthesis of heterogeneous catalysts, which can be represented the following General formula.

Heterogeneous catalyst comprising a complex of cobalt with phtalocyanines ligand, characterized in that it is a complex of cobalt with modified phtalocyanines ligand, covalently bound with silica, and having the following General formula:

where R = Cl, NHAlk, NAlk2,

n = 5-7, M = With.

Catalysts containing as the active phase chlorotoluene phthalocyanines (R = Cl), obtained by proshivkoi to aminopropiophenone the silica chloromethylphosphonic phthalocyanines MPc(CH2Cl)n+1. Processing heterogenizing on aminopropiophenone silica gel polychloroethene phthalocyanine amines allows modification of substituents in a wide range. For example, processing diethylamino gives the catalysts containing as the active phase (diethylamino)methylsiloxane phthalocyanines(R = NEt 2):

...-Si-O(CH2)3NH2+MPc(CH2Cl)n+1→ ...-Si-O(CH2)3NHCH2-[MPc(CH2Cl)n] →

→ ... -Si-O(CH2)3NHCH2-[Mrs(CH2NEt2)n]

Used for the synthesis of polychloroethene phthalocyanines are chlorotoluene phthalocyanines by known methods described, for example, in the patent of the Russian Federation WITH the 7D 487122, 2010

As the carrier can be used aminopropiophenone silica gels with different pore size, such as diasorb-100 Amin, diasorb-250 Amin, diasorb-750 Amin.

The task is also solved by a method of isomerization of Q in NDS using the proposed catalysts at a temperature of 0-60°C in an indifferent solvent. The invention is illustrated by the following examples.

Example 1

A solution of 5 μm octakis(chloromethyl)phthalocyanine cobalt in 5 ml of DMF is added to a suspension of 2 g of diasorb-100 amine in 10 ml of DMF. The mixture is heated to bleaching solution at 70-90°C for 30-40 minutes Bleaching solution illustrates the complete binding taken in response phthalocyanine with aminopropiophenone silica gel. The precipitate was separated, washed with acetone, water and dried. Get a heterogeneous catalyst SiO2(100am)/cm Source(CH2Cl)7: media - aminopropionic silica gel diasorb-100 amine content Akti is phase - 2.5 µm/year

Example 2

The process is conducted as in example 1, but the mixture obtained after heating, add 0.5 ml of diethylamine and heating continued for another hour. The precipitate was separated, washed with water and dried. Get a heterogeneous catalyst SiO2(100am)/cm-CoPc(CH2NEt2)7: media - aminopropionic silica gel diasorb-100 Amin, the content of the active phase - 2.5 µm/year

Example 3

The process is conducted according to example 2, but octakis(chloromethyl)phthalocyanine cobalt take 10 μm. Get a heterogeneous catalyst SiO2(100am)/5 m-CoPc(CH2NEt2)7on aminopropiophenone the silica gel diasorb-100 amine content of the active phase 5 μm/year

Example 4

The process is conducted according to example 2, but as media use aminopropionic silica gel diasorb-250 Amin. Get a heterogeneous catalyst SiO2(250am)/cm-CoPc(CH2NEt2)7with the content of the active phase 2.5 µm/year

Example 5

The process is conducted according to example 4, but as media use aminopropionic silica gel diasorb-750 Amin. Get a heterogeneous catalyst SiO2(750am)/cm-CoPc(CH2NEt2)7with the content of the active phase 2.5 µm/year

Example 6

The process is conducted according to example 2 using hexacis(chloromethyl)phthalocyanine cobalt. Get a heterogeneous catalyst SiO (100am)/cm-CoPc(CH2NEt2)5: media - aminopropionic silica gel diasorb-100 Amin, the content of the active phase - 2.5 µm/year

Example 7

The process is conducted according to example 2 using butylamine instead of diethylamine. Get a heterogeneous catalyst SiO2(100am)/cm-CoPc(CH2NHBu)7: media - aminopropionic silica gel diasorb-100 Amin, the content of the active phase - 2.5 µm/year

Example 8 (prototype)

In temperature-controlled static reactor, provided with a device for sampling, load 10 ml of Q (100 mmol) and 1 g of a catalyst comprising a phthalocyanine cobalt (2.5 µmol/g)supported on activated carbon Darco G-60 (DarcoG-60/2 mm Source). The reactor is rinsed with an inert gas (nitrogen, argon), and then include mixing. The reaction is carried out at 25°C for 1 hour. Completeness of the reaction is controlled by GLC. Determine the conversion rate of quadricyclane and selectivity of the overall process. The results are shown in the table.

Example 9

In temperature-controlled static reactor, provided with a device for sampling, load 10 ml of Q, 10 ml of dioxane and 1 g of catalyst SiO2(100am)/cm-CoPc(CH2NEt2)7. The reactor is rinsed with an inert gas (nitrogen, argon), and then include mixing. The reaction is performed at 0°C for 1 hour. Completeness of the reaction to trainout by GLC. Determine the conversion rate of quadricyclane and selectivity of the overall process. The results are shown in the table.

Example 10

The process is conducted according to example 9, but at a temperature of 25°C. the Results are shown in the table.

Example 11

The process is conducted according to example 9, but as tetrahydrofuran solvent used and the reaction is carried out at 40°C. the Results are shown in the table.

Example 12

The process is conducted according to example 9, but at a temperature of 60°C. the Results are shown in the table.

Example 13

The process is conducted according to example 10, but as the catalyst use SiO2(100am)/cm Source(CH2Cl)7. The results are shown in the table.

Example 14

The process is conducted according to example 13, but at a temperature of 60°C.

Example 15

The process is carried out in flow-through mode in the mass Q analogously to example 8 by using as a catalyst SiO2(100am)/5 m Source(CH2NEt2)7.

Example 16

The process is conducted according to example 15, but at a temperature of 25°C. the Results are shown in the table.

Example 17

The process is conducted according to example 15, but at a temperature of 40°C. the Results are shown in the table.

Example 18

The process is conducted according to example 15, but at a temperature of 60°C. the Results are shown in the table.

Example 19

The process is conducted according to example 16, but as the catalyst use SiO2(250am)/cm-CoPc(CH2 NEt2)7.

Example 20

The process is conducted according to example 19, but at a temperature of 40°C. the Results are shown in the table.

Example 21

The process is conducted according to example 19, but at a temperature of 60°C. the Results are shown in the table.

Example 22

The process is conducted according to example 16, but as the catalyst use SiO2(750am)/cm-CoPc(CH2NEt2)7.

Example 23

The process is conducted according to example 22, but at a temperature of 40°C. the Results are shown in the table.

Example 24

The process is conducted according to example 22, but at a temperature of 60°C. the Results are shown in the table.

Example 25

The process is conducted according to example 8, but as the catalyst use SiO2(750am)/cm-CoPc(CH2NEt2)5.

td align="left"> 73.5
Table
Conversion of Q and selectivity of isomerization reactions Q to NBD in the presence of catalysts
ExampleCatalystSolventTemperature, °CConversion of Q, %Selectivity, %
8 (prototype)DarcoG-60/2 mm Source-2599.9
9SiO2(100am)/cm-CoPc(CH2NEt2)7dioxane079.199.9
10SiO2(100am)/cm-CoPc(CH2NEt2)7dioxane259299.9
11SiO2(100am)/cm-CoPc(CH2NEt2)7THF4099.499.9
12SiO2(100am)/cm-CoPc(CH2NEt2)7dioxane6099.9,99.8
13SiO2(100am)/cm-CoPc(CH2Cl)7dioxane259099.9
14SiO2(100am)/cm-CoPc(CH2Cl)7dioxane60 98.899.6
15SiO2(100am)/5 m-CoPc(CH2NEt2)7-082.399.9
16SiO2(100am)/5 m-CoPc(CH2NEt2)7-2596.199.9
17SiO2(100am)/5 m-CoPc(CH2NEt2)7-4099.599.9
18SiO2(100am)/5 m-CoPc(CH2NEt2)7-6099.999.8
19SiO2(250am)/cm-CoPc(CH2NEt2)7-2595,799,9
20SiO2(250am)/cm-CoPc(CH2NEt2)7-40the 98.9 99,9
21SiO2(250am)/cm-CoPc(CH2NEt2)7-6099,899,8
22SiO2(750am)/cm-CoPc(CH2NEt2)7-25for 95.399,9
23SiO2(750am)/cm-CoPc(CH2NEt2)7-4097,999,9
24SiO2(750am)/cm-CoPc(CH2NEt2)7-6099,799,8
25SiO2(100am)/cm-CoPc(CH2NEt2)5-259699.9

Example 26

Endurance testing of catalyst SiO2(100am)/cm-CoPc(CH2NEt2)7. The process is conducted as described in example 8 using a catalyst SiO2(100am)/cm-CoPc(CH2Nt 2)7at 25°C 10000 catalytic cycles. The conversion rate was 97.4%, the selectivity - 99.9%.

Example 27

Endurance testing of catalyst SiO2(100am)/cm-CoPc(CH2NEt2)7. The process is conducted as described in example 8 using a catalyst SiO2(100am)/cm-CoPc(CH2NEt2)7at 25°C 40000 catalytic cycles. The conversion amounted to 95.9%, the selectivity - 99.9%.

Example 28

Endurance testing of catalyst SiO2(100am)/cm-CoPc(CH2NEt2)7. The process is conducted as described in example 26 at a temperature of 60°C. the Conversion was 100%, the selectivity - 99.8%.

Example 29

Endurance testing of catalyst SiO2(100am)/cm-CoPc(CH2NEt2)7. The process is conducted as described in example 27 at 60°C. the Conversion was 99.9%, the selectivity - 99.9%.

These tables indicate that the isomerization Q to NBD in the presence of the proposed heterogeneous catalysts as conversion and selectivity superior to the process in the presence of the Source adsorbed on charcoal. The inventive catalysts provide high conversion and selectivity of isomerization Q NBD at various temperatures not only in solution but also in the mass of Q. the Results of examples 26 to 29 are indicative not only of a large catalytic activity, but also on high is some stability of the inventive heterogeneous catalysts. They have a constant profile activity for a long time.

1. A complex of cobalt with modified phtalocyanines ligand, covalently bound with silica, and having the following General formula:

where R is Cl, NHAlk, NAlk2;
n = 5-7, M - Co.

2. The way the valence isomerization of quadricyclane in norbornadiene in the presence of a heterogeneous catalyst, wherein quadricyclane subjected to isomerization at a temperature of 0-60°C in the presence of a catalyst complex according to claim 1.

3. The method according to claim 2, characterized in that the process is conducted in an indifferent solvent.



 

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1 cl, 4 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to method of polymerisation of raw material flow containing C5-C6 hydrocarbons, which includes: loading of hydrogen and raw material, containing at least, normal C5-C6 hydrocarbons into isomerisation zone and contacting of hydrogen and raw material with isomerisation catalyst in conditions that favour increase of degree of hydrocarbons branching in raw material flow and ensuring formation of outgoing flow from isomerisation zone, which contains, at least, butane, normal pentane, normal hexane, methylbutane, dimethylbutane, methylpentanes and hydrocarbons which have seven or more carbon atoms, isomerisation conditions including temperature from 40° to 235°C and pressure 70 kPa abs. to 7000 kPa abs; passing outgoing flow from isomerisation zone through deisohexanizer zone in order to divide it into four flows, flow outgoing from upper part of deisohexaniser zone, containing, at least, butane, first side flow from deisohexaniser zone, containing, at least, methylbutane and dimethylbutanes, second side flow from deisohexaniser zone, containing, at least, methylpentanes and normal hexane, and lower flow from deisohexaniser zone, containing, at least, hydrocarbons, consisting of seven and more carbon atoms; and supply of first side flow from deisohexaniser zone into zone of isomerizate stripping in order to separate upper flow from isomerisate desorber which contains, at least, butane, from product flow from zone of isomerisate stripping, containing methylbutane and dimethylbutanes.

EFFECT: application of claimed method allows to reduce capital outlays and reduce cost of energy supply due to excluding of column-stabiliser.

9 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a composition used for a C-C bonding reaction. The composition contains dibenzylidene acetone complexes of palladium (0) of formula Pdx(dba)y with the ratio y/x ranging from 1.5 to 3 and are insoluble in chlorine-containing hydrocarbon components in amount of up to 0.5 wt %. The invention also discloses use of the composition and a method of producing the composition.

EFFECT: invention enables to obtain dibenzylidene acetone complexes of palladium of high purity.

8 cl, 7 ex

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