Organometallic complexes, the retrieval method, the catalyst hydroformylation on their basis and intermediate product

 

(57) Abstract:

Describes the ORGANOMETALLIC complexes of the formula I: [(Z+X-)mMLn]Y, where Z+denotes ion 1,2,4-triazole-5-ylidene formula (II), where1, R2and R4indicate a normal1-C4alkyl radical; R3denotes hydrogen, normal1-C4alkyl radical or phenyl; L denotes an ion or a neutral ligand; M is a metal selected from the group consisting of silver, mercury, Nickel, palladium or rhodium; n means an integer from 0 to 2; m represents an integer from 1 to 3; X-denotes a weakly coordinating anions and represents the counterions for ions 1,2,4-triazole-5-ylidene; Y denotes an anion that ensures the electrical neutrality of the metal complex, the method of production thereof, the catalyst hydroformylation on the basis of these complexes and the intermediate product of the formula (III). 4 C. and 4 h.p. f-crystals.

< / BR>

The present invention relates to novel ORGANOMETALLIC complexes containing cationic heterocyclic carbenes.

It also applies to ducational heterocyclic compounds-presests obtain the above ORGANOMETALLIC complexes.

Finally, the invention also includes the use of these complexes as catalysts for a range of chemical reactions.

ORGANOMETALLIC complexes containing heterocyclic carbenes have been already described earlier. Thus, in the patent EP-A-0721953 describes complexes containing nicotianae heterocyclic carbenes derived from imidazoline or pyrazoline and metal of groups 8, 9 and 10 of the Periodic classification of the elements. In the patent EP-A-0798041 describes complexes containing nicotianae heterocyclic carbenes derived from various compounds having 5, 6 or 7-membered cycles and containing one or more nitrogen atoms and/or sulfur and a metal selected from palladium, rhodium, Nickel, ruthenium and cobalt.

Such complexes are very stable compounds, which have, moreover, the advantage that they do not form when its toxic decomposition products. However, they have the drawback consisting in the fact that they cannot be used in an overly acidic environment, and complexes of metals with zero oxidation state is not soluble in water, which limits their applicability.

Thus, the present invention relates first of sigstat of General formula (I):

[(Z+X-)mMLn]Y (I)

in which Z+denotes ion 1,2,4-triazole-5-ylidene, in which at least a portion of atoms of the cycle of substituted hydrocarbon radicals;

L denotes an ion or a neutral ligand;

M denotes a metal selected from the transition elements of groups 1b, 2b, 3b, 4b, 5b, 6b, 7b and 8 of the periodic classification of elements, such as those published in the "Handbook of Chemistry and Physics, 51stEdition (1970-1971) by The Chemical Rubber Company;

X-denotes an organic or inorganic anion;

m denotes an integer from 1 to 6;

n denotes an integer from 0 to 5;

the sum of m and n is equal to or less than 6;

Y represents the anion or cation of this type, which ensures the electrical neutrality of the metal complex.

For convenience in the present text ORGANOMETALLIC or metal complexes referred to as compounds of formula (I), including the counterion y

Ions 1,2,4-triazole-5-ylidene Z+correspond to the General formula (II):

< / BR>
in which R1, R2, R3and R4identical or different, denote:

normal or branched alkyl radical or cycloalkyl radical,

aryl, alkoxy, the atom of hydrogen, a hydrophilic group such as a group:

THE SOOMA1, -SO3M1, -PO3M1, M1that represents inorganic or organic cationic residue selected from a proton, cations of alkali or alkaline earth metals, ammonium cations -- N(R)4in the formula where R, identical or different, denote a hydrogen atom or an alkyl radical with 1-4 carbon atoms;

N(R3)Yawhere R are identical or different, denote a hydrogen atom or an alkyl radical with 1-12 carbon atoms, a Yadenotes an inorganic or organic anion;

IT;

the aryl radical, arylalkyl or cycloalkyl, in a loop containing one or more substituents such as an alkyl radical, alkoxy radical, a halogen atom, a hydrophilic group, such as groups:

-COOM1, -SO3M1, RHO3M1, M1that represents inorganic or organic cationic residue selected from a proton, cations of alkali or alkaline earth metals, ammonium cations;

-N(R)4in the formula where R, identical or different, denote a hydrogen atom or an alkyl radical with 1-12 carbon atoms;

-N(R)3Yandwhere R, Odinak the organic or organic anion;

-HE;

R3denotes a hydrogen atom;

R1and/or R4can also each denote an organic ligand bound to the nitrogen atom ion 1,2,4-triazole-5-ylidene through alkalinity or Allenby radical, and the ligand may be a remnant of phosphite, phosphonite, phosphinate, phosphine, or a residue of aliphatic, cycloaliphatic, aromatic or heterocyclic tertiary amine serving as a ligand L to the metal M

The above organic ligands can be, for example, formed from phenyl - or alkylphosphines, substituted or not substituted above defined substituents, or phenyl or alkylphosphonium, substituted or not substituted above defined substituents, or phenyl or alkylphosphines, substituted or not substituted above defined substituents, or phenyl or alkylphosphines, substituted or not substituted above defined substituents.

In this case, ion 1,2,4-triazole-5-ylidene, defined above, substituted by the radicals R1and/or R4represents a bidentate or tridentate ligand.

L is ion ligand such as a halide, cyanide, or a neutral ligand, such as Oquendo metal, selected from the following group of metals: cobalt, iron, ruthenium, rhodium, palladium, osmium, indium, platinum, copper, silver, gold, zinc, cadmium, mercury.

These metals can have different oxidation States, including zero.

The anions X-are inorganic or organic anions, such as halides, but are selected preferably from the weakly coordinated anions in relation to the above metal M They form mainly counterions with respect to the ions of 1,2,4-triazole-5-ylidene.

As not limiting the scope of the invention examples of such weakly coordinated anions can be called triftormetilfullerenov, tetrafluoroborate, hexaflurophosphate, aluminum tetrachloride, tetrabromide aluminum, tetraploid aluminum, tetraiodide aluminum, gallium tetrachloride, tetrabromide gallium, tetraploid gallium, tetraiodide gallium.

The object of the present invention is also the use of ducation heterocyclic compounds as precursors upon receipt of ORGANOMETALLIC complexes of the General formula (I). Such ducation heterocyclic compounds correspond to the General formula (III):

- X-denotes an anion, such as the anions mentioned for the General formula (I).

Getting ducation heterocyclic complexes of the General formula (III) can be carried out using the reaction of compounds of formula XR2in which X and R2have the above values, with a triazole derivative having substituents XR2R1, R3and R4. The synthesis can also be carried out in several stages, each of which is derived triazole is reacted with a compound of the formula XR1, R3or XR4depending on what the Deputy is expected to be in the formula used for the reaction of triazole to obtain ducational heterocyclic compounds of the formula (III). This can be used reaction conditions, such as is described in the article by T. J. Curphey and K. S. Prasad, Journal of Org. Chem., 1972, 37, 2259.

Getting the ORGANOMETALLIC complexes of the formula (I) can be carried out by reaction ducational heterocyclic compounds of General formula (III) with a compound of the metal M in the presence of inorganic or organic bases. This may be associated anion compounds of the metal M or independently added to the reactions the AE necessary, an inorganic or organic base, in solution or in suspension of the compound (III). Of course, the order of input of various reagents may vary. The reaction can be conducted at room temperature or, mostly, at a temperature of from 25 to 150oC. Convenient to carry out the synthesis at the boiling temperature of the liquid in which the synthesis is carried out. The office complex of the formula (I) can be carried out using conventional chemical practice methods, for example filtration, centrifugation or extraction. The structure of the complexes of formula (I) and ducation heterocyclic compounds of the formula (III) is usually determined using nuclear magnetic resonance (NMR), infrared spectroscopy and x-ray diffraction. ORGANOMETALLIC complexes of the formula (I) can serve as catalysts in many chemical reactions.

Most of the ORGANOMETALLIC complexes of the formula (I), as well as ducation heterocyclic compounds of the formula (III), badly or not at all soluble in most nonpolar or polar organic solvents, such as alkanes, cycloalkanes, halogenoalkane, aromatic or alkylaromatic hydrocarbons and ethers. On the contrary, these compounds Rastislav (DMSO), the NITRILES (e.g. acetonitrile) and water. Thus, the ORGANOMETALLIC complexes of the present invention are soluble, in particular, NITRILES (e.g. acetonitrile), DMSO and water. These properties facilitate separation of such different compounds, in particular, using the extraction liquid/liquid. On the other hand, such properties allow the conduct of catalysis in biphasic medium.

As not limiting the scope of the invention examples of such reactions can be called hydrosilation of alkenes or alkynes, in particular, in the presence of complexes of ruthenium, hydrosilation of ketones in the presence of complexes of ruthenium or rhodium, the reaction of Hake in the presence of palladium complexes, hydrogenation of olefins, aldehydes, acids, enamides and reduction of compounds in the presence of complexes of ruthenium, rhodium, platinum or palladium, hydroformylation and hydrocarbonylation olefins in the presence of rhodium complexes, hidrotsianova olefins in the presence of complexes of Nickel, the synthesis of furan in the presence of complexes of ruthenium, the disproportionation of olefins in the presence of complexes of ruthenium and polymerization of acrylates in the presence of complexes of Nickel.

EXAMPLES SINT is sledovatelnot operations, described in J. Org. Chem., 1972, 37, R. 2259, 1H-1,2,4-methylthiazole twice was identified in (in positions 2 and 4 cycle) methyl ether of triftoratsetata in 1,2-dichloroethane at boiling and stirring.

The resulting brown precipitate is filtered off, then washed with 1,2-dichloroethane to yield a white powder. The obtained solid (IIIa) has a melting point of 160-162oC.

The connection has the following characteristics

NMR1H (DMSO-d6): 4,22 (s, 3H, CH3N) 4,50 (s, 6N, CH3N), 10,79 (s, 2H, Hcycle).

NMR13(N) (CD3SP): 38,67 (s, CH3N), 38,87 (s, 2CH3N), 120,35 (kV,1JCF=320, 1 Hz, CF3), 147,72 (s, 2Ccycle).

Example 2. Synthesis of compound (IIIb):

< / BR>
The synthesis is carried out in two stages. First of all put in position 4 of the isopropyl group (radical R4by adding the stoichiometric amount of 1H-1,2,4-methylthiazole to a solution of isopropyl ether triftoratsetata in 1,2-dichloroethane (boiling under stirring for 3 hours. Get a connection in the form of a yellow oil, having the following formula:

< / BR>
with the release of 91%.

To a solution of 5 g (18 mmol) of this compound in 20 ml of 1,2-dichloroethane add the 2.5 is wsysa brown precipitate is filtered off and then washed with 1,2-dichloroethane to yield a white powder.

The obtained solid (IIIb) has a melting point of 163-165oWith, and its number corresponds to a yield of 73% (based on an arbitrary intermediate connection.

The connection has the following characteristics:

NMR1H (CD3SP): 1,65 (d3JHH=to 6.58 Hz, 6N, CH3CH), 4,34 (s, 3H, CH3N) to 5.03 (Sept,3JHH=to 6.58 Hz, 1H, [CH3]2N), 10,22 (s, 2H, Hcycle.).

NMR13(CD3SP): 21,51 (s, CH3CH), 38,71 (s, CH3N), 58,88 (s, [CH3]2N), 120,35 (kV,1JCF=320, 1 Hz, CF3), 145,22 (s, 2Ccycle.).

Example 3. Synthesis of compound (IIIc):

< / BR>
The synthesis is carried out in two stages. First, the compound of the following formula:

< / BR>
receive according to the method described in J. Prakt. Chem., 1988, 330, 3, 325.

This compound is boiled in methyltrichlorosilane under stirring for 4 days. The resulting brown precipitate is filtered off and then washed with 1,2-dichloroethane to yield a white powder. The output obtained solids (IIIc) is 50% based on the compound used for the reaction in the second stage.

The product has the following characteristics:

NMR1H (CD3CN): 4,22 (s, 3H, CH3N), the 7.4-8.4V (implemented in two stages. At the beginning of a compound of the following formula:

< / BR>
receive according to the method described in J. Prakt. Chem., 1988, 330, 3, 325.

The compound obtained is boiled in 1,2-dichloroethane with 3 equivalents methyltrichlorosilane under stirring for 2 days. The resulting brown precipitate is filtered off and then washed with 1,2-dichloroethane to yield a white powder. The output obtained solids (IIId) is 69% (based on compound used for the reaction in the second stage, and the melting point of the product to 190.5-191,3oC.

The connection has the following characteristics:

NMR1H (CD3SP): 3.04 from (s, 3H, CH3), 4,19 (s, 3H, CH3N), and 7.8-8.1 (array, 10H, 1H phenyl), 10,51 (s, 1H, Hcycle.);

NMR13C (CD3SP): 12, 31 (CH3C), 38, 04 (s, CH3N), 126,70 (s, 2CH phenyl), 128,02 (s, phenyl), 128,49 (s, 2CH phenyl), 130,07 (s, phenyl), 131,56 (s, 2CH phenyl), 131,83 (s, 2CH phenyl), 134,04 (s, 1 CH phenyl), 135,88 (s, 1 CH phenyl), 120,35 (kV,1JCF=320, 1 Hz, CF3), 145, 58 (s, CHcycle.), 157,66 (C, Ccycle.CH3).

Paired spectrum TMR network for CH triazole cycle constant splitting1JCH=240 Hz.

Example 5. Synthesis of compounds (A):

< / BR>
The synthesis is carried out in two LASS="ptx2">

The compound obtained is boiled in 1,2-dichloroethane with 3 equivalents methyltrichlorosilane under stirring for 2 days. The resulting brown precipitate is filtered off and then washed with 1,2-dichloroethane to yield a white powder. The output obtained solids (E) is 71% based on the compound used for the reaction in the second stage, and the melting point of the product 180oC.

The connection has the following characteristics:

NMR1H (CD3CN): 4, 08 (s, 3H, CH3N), 4, 20 (s, 3H, CH3N), 4, 46 (s, 3H, CH3N), and 7.8-8.1 (array, 10H, 5H phenyl), 10,16 (s, 1H, Hcycle.);

NMR13(CD3CN): 37, 88 (s, CH3N), 38,36 (s, CH3N), 39,42 (s, CH3N), 130,78 (s, phenyl), 131,97 (s, 2CH phenyl), 132,15 (s, 2CH phenyl), 137,35 (s, CH phenyl), 131, 83 (s, 2CH phenyl), 120,35 (kV,1JCF=320, 1 Hz, CF3), 147, 35 (s, CHcycle.), 156, 48 (C, Ccycle.).

Example 6. Synthesis of compound (IIIf)

< / BR>
The synthesis is carried out in two stages. First, the compound of the following formula:

< / BR>
receive according to the method described in J. Prakt. Chem., 1988, 330, 3, 325.

The compound obtained is boiled in 1,2-dichloroethane with 3 equivalents methyltrichlorosilane under stirring for 2 day is. The output obtained solids (IIIf) is 95% based on the compound used for the reaction in the second stage, and the melting point of the product 194,4oC.

The connection has the following characteristics:

NMR1H (Acetone d6): at 3.35 (s, 3H, CH3C) to 4.46 (s, 3H, CH3N), 4,69 (s, 3H, CH3N), of 4.77 (s, 3H, CH3N), 10,77 (S, 1H, Hcycle.);

NMR13(Acetone d6): 10,53 (s, CH3C), 35, 91 (s, CH3N), 36,26 (s, CH3N), 37,99 (s, CH3N), 120,35 (kV,1JCF= 320,1 Hz, CF3), 145,35 (s, CHcycle.), 157,31 (C, Ccycle.CH3).

EXAMPLES OF THE SYNTHESIS OF ORGANOMETALLIC COMPLEXES OF THE FORMULA (I)

Example 7. Synthesis of compound (Ia) with Ad(I):

< / BR>
To a suspension of 1 g obtained in example 1 ducational compounds (IIIa) in 20 ml of tetrahydrofuran, add 0.4 g (2.4 mmol) of silver acetate. The mixture is boiled for 2 hours under stirring. Formed is not miscible with THF brown oil was washed several times with 10 ml THF. After evaporation of the solvent receive sensitive to light solid brown color (yield 82% and per ducation compound (IIIa)).

The resulting complex has the following characteristics:

NMR1 NMR13(CD3CN) IS 37.2 (NCH3), 38,5 (NCH3), AND 38.6 (NCH3), 121, 1million (kV,1JCF=320,1 Hz, CF3), 144,8 (CH), 189,2 (Garden).

Example 8. Synthesis of compound (Ib) with Nd (II):

< / BR>
To a suspension of 0.43 g obtained in example 5 ducational compound (IIIe) in 20 ml of tetrahydrofuran added 0.16 g of the diacetate of mercury (previously dried in vacuum for 12 h at 50o(C) and 1 ml of dimethyl sulfoxide. The mixture is stirred for 24 hours at room temperature. Formed brown precipitate, soluble only in very polar rastvoritelyakh. The obtained solid is washed several times with THF to remove traces of acetic acid. The resulting complex is recrystallized by slow diffusion of ether into a methanol solution of the complex. The recrystallized complex (Ib) has a melting point of 85.4-87oC. Yield: 86% (based on ducation compound (IIIe).

The resulting complex has the following characteristics:

NMR1N (CD3OD): 4, 70 (s, N, NCH3,4JH-Hg=12,8), the 4.29 (s, 6N, CH3N4JH-Hg=8,5 Hz), 7,9-8,2 (array, 10H, H of phenyl);

NMR13(CD3OD): 38,79 (CH3N-NCH3), 41,75 (NCH3), 121, 1million (kV, 1the structure of the complex was also established using x-ray diffraction.

Example 9. Synthesis of compound (1C) with Ni(II)

< / BR>
To a suspension 0,442 g of the diacetate of Nickel and 0.75 g of sodium iodide in 50 ml of THF added 2.4 g obtained in example 5 ducational compound (IIIe). The mixture is boiled for 2 hours under stirring. The formed colored precipitate is filtered off and washed several times with THF. The resulting complex is recrystallized from a mixture of acetone/ether at -30oC. the Recrystallized complex (1C) has a red color and a melting point 310,7oC (decomposition: crystals blacken). The yield is 85% (based on ducation connection (E).

The resulting complex has the following characteristics:

NMR1H (Acetone-d6): 7,8-8,0 (broadened, 10H, H of phenyl), 4,88-4,84 (2s, 6H, NCH3), 4,54-4,49 (2s, 6H, CH3N), 4,42-to 4.41 (2s, 6H, CH3N);

NMR13C (CD3OD): 37,0 (CH3N) 37,9 (CH3N) 38,4 (CH3N), 121, 1million (kV,1JCF= 320,1 Hz, CF3), 130, 5-130, 8-134, 8 (With phenyl), 153,4 (C-Ph), 188,2 (C-Ni).

The structure of the complex was also established using x-ray diffraction.

Example 10. Synthesis of compound (Id) with Ni(II)

< / BR>
To a suspension 0,090 g of the diacetate of Nickel and 0.15 g of sodium iodide in 25 ml of THF added 0,425 g obtained in example 6 is litrovuyu and washed several times with THF. The resulting complex is recrystallized from a mixture of acetone/ether at -30oC. the Recrystallized complex (Id) has a red color and a melting point 300-305oC (decomposition: crystals blacken). The output is 79% (based on ducation compound (IIIf).

The resulting complex has the following characteristics:

NMR1H (Acetone-d6): 4,88-4,84 (2C, 6N, NCH3), 4,54-4,49 (2C, 6N, CH3N), 4,42-to 4.41 (2C, 6N, CH3N) 2,63 (s, 6N,-CH3);

NMR 13(CD3OD): 13,86 (SP3), 36,1 (CH3N) 37,6 (CH3N) 38,5 (CH3N), 121, 1million (kV,1JCF=320,1 Hz, CF3), 154,8 (- IU), 187,6 (C-Ni).

The structure of the complex was also established using x-ray diffraction.

Example 11. Synthesis of compound (Ie) with Ni(II)

< / BR>
To a suspension 0,200 g of the diacetate of Nickel and 0.34 g of sodium iodide in 30 ml of THF added 0.935 g obtained in example 1 ducational compounds (IIIa). The mixture is boiled for 2 hours under stirring. The formed colored precipitate is filtered off and washed several times with THF. The resulting complex is recrystallized by slow diffusion of ether into a solution of the complex in acetonitrile and then from a mixture of acetone/EPE is whiteone compound (IIIa).

The resulting complex has the following characteristics:

NMR1H (Acetone-d6): to 4.38-4.35 the (2s, 6N, CH3N), 4,68 with 4.65 (2C, 6N, CH3N), 4,99-4,96 (2C, 6N, NCH3), to 9.32 (s, 2H, CH).

Example 12. Synthesis of compound (If) with Pd(II)

< / BR>
To a suspension 0,112 g of palladium diacetate and 0.30 g of sodium iodide in 60 ml of THF added 0,472 g obtained in example 5 ducational connection (E). The mixture is boiled for 2 hours under stirring. The formed colored precipitate is filtered off and washed several times with ether. The resulting complex is recrystallized from a mixture of acetone/ether at -30oC. the Recrystallized complex (If) is a yellow crystals with a melting point 211-213oC (decomposition: the crystals turn brown). In the reaction all triftormetilfullerenov anions are replaced with jodijaniayj. The output is 51% per ducation compound (IIIe).

The resulting complex has the following characteristics:

NMR1H (DMSO-d6): a 7.8-8.1 (ukrop., 10H, H of phenyl), 4,49-4,53 (2C, 6N, N3), is 4.21 (s, 6N, CH3N), 4,10-4,13 (2C, 6N, CH3N);

NMR13(DMSO-d6); 37,2 (CH3N), TO 38.3 (CH3N), AND 39.9 (CH3N), to 130.1-130,9-134,5 (phenyl), 152,4 (C-Ph), of 174.5 (C-Pd).

Cadinene (Ig) with Pd(II):

< / BR>
To a suspension 0,112 g of palladium diacetate and 0.30 g of sodium iodide in 60 ml of THF added 0,425 g obtained in example 6 ducational compound (IIIf). The mixture is boiled for 2 hours under stirring. The formed colored precipitate is filtered off and washed several times with ether. The resulting complex is recrystallized from a mixture of acetone/ether at -30oC. the Recrystallized complex (1g) has a red color and a melting point 206-212oC (decomposition: the crystals turn brown). In the reaction all triftormetilfullerenov anions were replaced by iodide anions. The yield is 60% per ducation compound (IIIf).

The resulting complex has the following characteristics:

NMR1H (DMSO-d6): to 4.41-4,40 (2C, 6N, NC3), the 4.29 (s, 6N, CH3N), 4,16-4,15 (2C, 6N, CH3N) 2,95 (6N,-CH3).

Example 14. Synthesis of compound (Ih) with Ni(0)

< / BR>
Method of synthesis AND

1 ml of tetracarbonyl Nickel diluted in 40 ml anhydrous and obezhirennogo acetonitrile. To the resulting solution was added 360 μl of pyridine and 660 μl of triethylamine. A solution of 2.0 g obtained in example 6 ducational compound (IIIf) in 60 ml anhydrous and obezhirennogo of acetonitrile are added dropwise the Oia total solution continue stirring for another 1 hour. The volume of the reaction solution is then reduced by two-thirds by evaporation of the solvent in vacuo, then add 200 ml obezhirennogo ether. Thereafter, a precipitate of the complex (Ih), which is filtered off and washed several times with ether. The resulting complex is recrystallized from a mixture of acetone/ether at -30oC. Complex (Ih) is a yellow crystals, melting point which cannot be determined accurately (decomposition: the crystals turn brown). Output is 26% per ducation compound (IIIf).

The resulting complex has the following characteristics:

NMR1H (DMSO-d6): 4,00 (s, 6N, N3), 3,99 (s, 6N, CH3N) of 3.78 (s, 6N, CH3N) 2,72(6N,-CH3).

In the infrared spectrum has bands at 1982 cm-1and 1906 cm-1(WITH).

The structure of the complex also established using x-ray diffraction.

Using elemental analysis found:

- 28,99% (theory 28,89%)

- 3,36% N (theory 3,63%)

- KZT 12.39% N (theory 12.62% stake).

Synthesis method IN

To a solution of 0.2 g obtained in example 10 ORGANOMETALLIC complex (Id) in 10 ml anhydrous and obezhirennogo of acetonitrile, add 150 is A. The reaction begins at the moment when you start mixing. The solution becomes yellow, then it is filtered with a straw, and then treated the same way as in the method (adding ether to precipitate ORGANOMETALLIC complex). The output is 48% in the calculation used for the reaction of the ORGANOMETALLIC complex (Id). Produce the same tests and get the same features as in method A. the results are the same.

Example 15. Synthesis of compound (Ij) with Rh(I)

< / BR>
To a suspension 0,456 g obtained in example 6 ducational compound (IIIf) and 0.16 g of NaI in 40 ml of THF add a solution 0,277 g acetylacetonate dicarbonate in 10 ml of THF. Stirred for 2 days at 50oC. After evaporation of the solvent and several washings with ether get a solid brown color. The output is 70% per ducation compound (IIIf).

The resulting complex has the following characteristics:

NMR1H (DMSO-d6): 4,47 (s, 3H, NCH3), 4,28 (s, 3H, CH3N) 4,20 (s, 3H, CH3N), 2,96 (s, 3H,-CH3);

NMR13(DMSO-d6): 10,5 (s,-CH3), 35,2 (s, NCH3), 36,8 (s, CH3N) 37,9 (c, CH3N), to 154.2 (s,-CH3), USD 183.0 (d1J (Rh-C)=82,9 Hz, CO), 188, 1 (l,
< / BR>
To a suspension of 0.16 g obtained in example 1 ducational compounds (IIIa) in 10 ml THF add a solution 0,200 g acetylacetonate dicarbonate in 10 ml of THF. The mixture is stirred for 15 hours at 50oC. the Resulting brown solid residue washed several times with ether. The output of the complex (Ik) is 67% (based on ducation compound (IIIa).

The resulting complex has the following characteristics:

NMR1H (DMSO-d6): 4,20 (s, 3H, NCH3), 4,22 (s, 3H, CH3N), 4,25 (s, 3H, CH3N) to 9.66 (s, 1H, CH);

NMR13(DMSO-d6): 38,6 (s, NCH3), 38,7 (s, NCH3), 39,1 (s, CH3N) 37,9 (s, CH3N), 121, 1million (kV,1JCF=320,1 Hz, CF3), 145,5 (s, CH), 186,1 (d1J(Rh-C)=76 Hz, CO), 187,9 (d1J(Rh-C)=43, 3 Hz, With carbene).

The IR spectrum has bands at 2029 (and) cm-1and 1985 (cf) cm-1(WITH).

Example 17. Catalysis of hydroformylation styrene compound (Ij) with Rh(I)

The reaction hydroformylation styrene is carried out in 100-ml reactor made of stainless steel with double sheath, allowing the implementation of heating by means of circulating oil, with adjustable thermostat temperature. Cover reactor equipped with an inlet valve or a thief to transfer fluids with a syringe. Inside of the autoclave is Teflon cavity with a magnetized rod serving for mixing of the reacting substances.

Obtained in example 15 complex (Ij) with Rh(I) (40 mg) is loaded into Teflon cavity together with 100 mg of triphenylphosphine (5 equivalents per catalyst). The autoclave is pressurized and rinsed three times with argon. After that load 15 ml of tetrahydrofuran, 5 ml of styrene and 60 mg of triethylamine (4 equivalents per catalyst) and set the pressure carbon monoxide (15 bar) and hydrogen (15 bar). The contents of the autoclave are heated at 60oWith under stirring with a magnetic stirrer. After 4 hours of reaction at this temperature, the autoclave was quickly cooled in a mixture of acetone with liquid nitrogen and within 1 hour relieve pressure. A sample of the reaction mixture analyzed by gas chromatography.

Get the following results:

the degree of conversion of styrene: 95%

the selectivity to aldehydes: 97%

- the ratio of branched aldehyde/linear aldehyde: 95/5

the frequency of turnover of the catalyst: 75 h-1(calculated as average of the response time using the same for all products of the coefficient of the output signal of the gas chromatography).

After 3 hours of reaction at 80oWith the autoclave was quickly cooled in a mixture of acetone with liquid nitrogen and within 1 hour relieve pressure. A sample of the reaction mixture analyzed by gas chromatography.

Get the following results:

the degree of conversion of styrene: 96%

the selectivity to aldehydes: 100%

- the ratio of branched aldehyde/linear aldehyde: 25/75

the frequency of turnover of the catalyst: 79 h-1(calculated as average of the response time using the same for all products of the coefficient of the output signal of the gas chromatography).

1. ORGANOMETALLIC complexes of the General formula I

[(Z+X-)mMLn]Y

in which Z+denotes ion 1,2,4-triazole-5-ylidene formula II

< / BR>
where R1, R2and R4indicate a normal C1-C4 alkyl radical;

R3denotes hydrogen, normal C1-C4 alkyl radical or phenyl;

L denotes an ion or a neutral ligand;

M represents a metal selected from the group consisting of silver, mercury, Nickel, palladium or rhodium, n means an integer from 0 to 2, m represents an integer from 1 to 3;

X-denotes the weakly coordinated the ensuring the electrical neutrality of the metal complex.

2. ORGANOMETALLIC complexes under item 1, characterized in that L is ion ligand selected from halides, or a neutral ligand selected from carbon monoxide or phosphine.

3. ORGANOMETALLIC complexes under item 1, characterized in that the weakly coordinated anion X-is triftormetilfullerenov.

4. The method of obtaining the ORGANOMETALLIC complexes of the General formula I, characterized in that ducation heterocyclic compounds of General formula III

< / BR>
in which R1, R2, R3and R4have the meanings given above for ions 1,2,4-triazole-5-ylidene formula II;

X-denotes an anion, such as the anions mentioned for the General formula I,

enter into reaction with a compound of the metal M in the form of a solution or suspension at room temperature or, preferably, at a temperature of from 25 to 150oC.

5. The method according to p. 4, characterized in that the reaction is carried out in the presence of an organic or inorganic base at a temperature of from 25 to 150oC.

6. The catalyst hydroformylation, characterized in that it contains the ORGANOMETALLIC complexes according to one of paragraphs.1-3.

7. Ducation g of the hydrated C1-C4 alkyl radical;

R3denotes hydrogen, normal C1-C4 alkyl radical or phenyl;

L denotes an ion or a neutral ligand;

M represents a metal selected from the group consisting of silver, mercury, Nickel, palladium or rhodium, n means an integer from 0 to 2, m represents an integer from 1 to 3;

X-denotes a weakly coordinating anions and represent counterions for ions 1,2,4-triazole-5-ylidene;

Y denotes an anion that ensures the electrical neutrality of the metal complex.

8. Connection on p. 7, characterized in that the weakly coordinated ion X-is triftormetilfullerenov.

 

Same patents:

The invention relates to organic and analytical chemistry, specifically to the substance obtained by chemical means, (5-nitrophenolic-8-thio, 4-carboxyphenyl) mercury formulas

as an analytical reagent for photocolorimetric determination of sulfhydryl compounds (thiols, hydrogen sulfide)

-olefin (options)" target="_blank">

The invention relates to catalysts used for Homo - and copolymerization of ethylene and other olefin hydrocarbons

The invention relates to the use of aquaheat as transport systems for the effective transfer of metals and various organic ligands through the cell membrane

,,,-tetramethylcyclotetrasiloxane and methods for their production" target="_blank">

The invention relates to chemistry and chemical technology, and more specifically to the synthesis of a new breed of macroheterocyclic compounds, tetrasauropus chlorine, namely,,,-tetramethylcyclotetrasiloxane

The invention relates to a method for Organoelement compounds, which can be used as additives to lubricating oils

-aminophenylacetate nickel, palladium and copper, and the method of production thereof" target="_blank">

The invention relates to organic chemistry, specifically to new chemical compounds - performancemanagement N,N'-ethylenebis-beta-aminophenylacetate Nickel, palladium and copper, which can be used as organic filters and photostabilization for organic liquids and polymers

< / BR>
and the way they are received, characterized in that the initial reaction of fluorinated diketones carried out in benzene in the presence of a catalyst - epirate boron TRIFLUORIDE with removal of water by azeotropic distillation

The invention relates to the refining, and in particular to methods of allocation of residual oil fractions vanadyl-(EAP) and nigelbotterill (TM) products Parametrierung which have catalytic properties [1 and 2]

There is a method of allocation VP of oil or fractions by extraction with dimethylformamide [3]

The disadvantage of this method is the sharp decrease in the efficiency of extraction of the EAP in the transition from oil of low and medium density to high-viscosity heavy oil and residual fractions, which are more suitable raw material source for the selection of the EAP because of the much higher content compared with oils of low and medium density

The invention relates to new derivatives of (1-(-oxyethyl)-2-methyl-5-intorimidazole) has antibacterial, antitrichomonas, fungicidal and immunostimulatory activity

The invention relates to the field of organic chemistry - synthesis of amino acids, namely, to obtain optically pure-amino acids through the metal complexes with asymmetric reagents

,,,-tetramethylcyclotetrasiloxane and methods for their production" target="_blank">

The invention relates to chemistry and chemical technology, and more specifically to the synthesis of a new breed of macroheterocyclic compounds, tetrasauropus chlorine, namely,,,-tetramethylcyclotetrasiloxane
The invention relates to improvements in the field of compounds of precious metals, and more specifically to improvements in the field of ruthenium compounds and methods for their preparation

The invention relates to the field of inorganic chemistry, namely the chemistry of platinum group metals, more specifically to a method for the rhodium carboxylates (II), widely used in the preparation of catalysts for industrial organic synthesis

The invention relates to new chemical substances with the General formula M'nM(H-1GluTrp)mn2Oh, where M' is a cation of an alkali metal, M is a cation d-metal or alkaline-earth metal, GluTrp - anion glutamylation, n is the number of atoms of alkali metal, m is the number of water molecules

The invention relates to a new stable complex compound containing macrocyclic tetradentate ligand having the structure of formula I, where R1and R2have the same or different values are related or unrelated, and each is selected from the group consisting of hydrogen, halogen, methyl, CF3and, if they are connected, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, are spatial and confirmation difficult, so that the oxidative degradation of complex metal compound is limited, when the complex is in the presence of an oxidizing environment, Z represents a stable to oxidation atom, which metallocomplexes selected from nitrogen and oxygen, X represents an oxidation resistant functional group selected from O or NRswhere Rsrepresents a methyl, phenyl, hydroxyl, auxillou group, CF3or CH2CF3, R3, R4, R5represent fragments of connecting adjacent Z atoms containing structure described in the claims

The invention relates to a new stable complex compound containing macrocyclic tetradentate ligand having the structure of formula I, where R1and R2have the same or different values are related or unrelated, and each is selected from the group consisting of hydrogen, halogen, methyl, CF3and, if they are connected, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, are spatial and confirmation difficult, so that the oxidative degradation of complex metal compound is limited, when the complex is in the presence of an oxidizing environment, Z represents a stable to oxidation atom, which metallocomplexes selected from nitrogen and oxygen, X represents an oxidation resistant functional group selected from O or NRswhere Rsrepresents a methyl, phenyl, hydroxyl, auxillou group, CF3or CH2CF3, R3, R4, R5represent fragments of connecting adjacent Z atoms containing structure described in the claims

- cyclodextrin and method of suppressing tumor growth" target="_blank">

The invention relates to organic chemistry, and medicine, and it applies to substances used in combination with ascorbic acid for the treatment of malignant neoplasms (binary catalytic "dark" therapy of malignant tumors) and method of suppressing tumor growth
The invention relates to methods for dilaceration chelates of iron and can be used, for example, in agriculture as a protective means and in veterinary medicine
Up!