Palladium hydrogenation catalyst and method to manufacture thereof
SUBSTANCE: palladium hydrogenation catalyst is described. It contains reduced palladium compound and modifier, where palladium bis-acetylacetonate is used as starting palladium compound and white phosphorus (Р4) is used as modifier, component ratio being as follows: palladium bis-acetylacetonate/phosphorus =1:0.1 to 1:1. Method to manufacture thereof is also described. The said method is based on reduction of the starting palladium compound with hydrogen in the presence of modifier. White phosphorus is used as modifier and is introduced prior to reduction of palladium (II) compound with hydrogen, palladium bis-acetylacetonate being used as starting compound, at optimum for catalyst system formation temperature of 80-90°С (353-363 К) and optimum for catalyst formation time of 25-30 minutes.
EFFECT: increase in catalyst activity, when catalytic process takes place under mild conditions.
2 cl, 5 tbl, 25 ex
The present invention relates to the field of catalytic chemistry, in particular the development of effective catalyst for the hydrogenation of unsaturated hydrocarbons (alkenes, alkynes), carbonyl and nitro compounds and method of its production, and can be used in fine organic synthesis.
A known method of obtaining a palladium catalyst in the hydrogenation of unsaturated compounds by reduction with hydrogen tetraamminepalladium (II) perchlorate and deposition restored nonvalence palladium on carbon material - nanocluster soot separate portions [RF Patent №2258561, B01J 23/44, B01J 21/18, B01J 37/18, B01J 37/03, 2005].
The disadvantage of the catalyst-analogue is a low catalytic activity in the hydrogenation of alkenes, which does not exceed 580 mol of ethylene/mol Pd·h (10 mol of ethylene/mol Pd·min) at a temperature of 25°and a hydrogen pressure of 1 ATM.
A method of obtaining a heterogeneous palladium catalyst hydrogenation by fixing tetrachloropalladate potassium (K2PdCl4) laminirovannom chlorotoluene copolymer of styrene and divinylbenzene with a particle size of the carrier of 0.075-0.12 mm, and subsequent reduction of the obtained metallopolymer with sodium borohydride [2039599 C1, B01J 37/00, B01J 23/44, 1995]. The disadvantage of the catalyst-analogue is low kata is itihasa activity in the hydrogenation of nitrobenzene, which does not exceed 30 mol of nitrobenzene/mol Pd·min (the reaction rate 14,42 ml of N2/min when loading a heterogeneous catalyst containing 1 wt.% Pd, 0.2 g; temperature, 45°and a hydrogen pressure of 1 ATM).
A method of obtaining palladium catalyst hydrogenation of acetylene compounds by interaction π-allylchloroformate with hydrazine in a molar ratio of hydrazine and π-allylchloroformate 1.5 to 2.5:1 [Ed. mon. The USSR 1100775 a, class 01J 37/16, 23/44, 1985].
The disadvantage of the catalyst-analogue is a low catalytic activity in the hydrogenation of alkynes, in particular phenylacetylene, which does not exceed 9800 ml phenylacetylene/g Pd·min (43 mol of phenylacetylene/mol Pd·min) at a temperature of 20°and a hydrogen pressure of 1 ATM and selectivity to styrene 95-96% at the time of absorption half of the calculated amount of hydrogen. The ratio of phenylacetylene:catalyst = 500.
Known homogeneous catalyst for the hydrogenation based on binuclear palladium complex of the composition [(But 2PH)Pd(μ-PBut 2)]2that with a selectivity of 98% hydrasuit cyclooctadiene-1,3 at 20°and a hydrogen pressure of 1 ATM in an environment THF. This catalyst exhibits catalytic activity only after first interacting with a molecular key is activated oxygen [I.S. Cho, Alper H. Selective Hydrogenation of Simple and Functionalized Conjugated Dienes Using a Binuclear Palladium Complex Catalyst Precursor. // Tetrahedron Letters. - 1995. - V.36, N 32. P.5674].
The disadvantage of the catalyst is a complex multistage synthesis source binuclear complex of palladium - [(But 2PH)Pd(μ-PBut 2)]2.
Known hydrogenation catalyst on the basis of the acetate complex of palladium (II) with tridentate P-, N-, O-containing ligand of the structure of [Pd(OAc)(PPh2(C6H4)CH=N-N=C(O)(CH3)], which hydrasuit unsaturated hydrocarbons under mild conditions (at a temperature of 40°and a hydrogen pressure of 1 ATM) [A. Bacchi, Carcelli M., M. Costa, A. Leporati, Leporati E., P. Pelagatti, Pelizzi S., G. Pelizzi Palladium (II) complexes containing a P, N-chelating ligand. Part II. Synthesis and characterization of complexes with different hydrazinic ligands. Catalytic activity in the hydrogenation of double and triple C-C bonds. // J Were Obtained. Chem. - 1997 - V.535. - P.107-120]. The disadvantage of this catalyst is the low catalytic activity in the hydrogenation of styrene and not more than 0.1 mol/g-al-Pd-min, and in the hydrogenation of Talana is 0.4 mol/g-al-Pd-min, as well as the complexity of the synthesis tridentate P-, N-, O-ligand.
The closest known solution of an analogous problem to the technical essence and the achieved effect is a method for the catalytic hydrogenation of unsaturated compounds by restoring the bis-acetate palladium hydrogen in benzene in the presence of triphenylphosphine p and a temperature of 20° C and a hydrogen pressure of 1 atmosphere for 1 h and a hydrogenation catalyst containing bis-acetate, palladium and modifying additive - triphenylphosphine, in which the ratio of Pd:P=1:1 [siksak A., Ungvary F., Kiss G. The formation of Catalytically active species by the reduction of palladium carboxylate phosphite systems: 1. Hydrogenation's // J. Mol. Catal. - 1983. - Vol.18, No. 2. - P.229]. The maximum specific activity of the catalytic system [Pd(OAc)2]3+3h3in the hydrogenation of ethynylbenzene (phenylacetylene) at 20°and the hydrogen pressure 1 excessive atmosphere is 4.8 mol/g-at Pd·min, in the hydrogenation of styrene and 0.2 mol/g-at Pd·min. Ratio of substrate: palladium = 1000.
Its disadvantages are the need for preliminary multi-stage synthesis of triphenylphosphine and low specific catalytic activity in hydrogenation as terminal alkynes (phenylacetylene)and alkenes (styrene).
The task of the invention is the creation of a palladium hydrogenation catalyst, which would have a large catalytic activity, could carry out a catalytic process under mild conditions (at room temperature and normal (atmospheric) pressure), as well as reduce the cost of implementation of the method.
This object is achieved in that the hydrogenation catalyst containing the recovered compound of palladium and modifying doba is ku, as the source of palladium compounds using bis-acetylacetonate, palladium, and as a modifying additive white phosphorus (P4) in the following ratio of components: bis-acetylacetonate palladium/phosphorus = 1:0.1 to 1:1.
This object is achieved in that in the method of producing catalytic hydrogenation, based on recovery of starting compound of palladium with hydrogen in the presence of the modifying additive, as modifying additives used white phosphorus, which is injected to the stage of recovery of the compounds of palladium (II) hydrogen, and as the parent compound of palladium bis-acetylacetonate, palladium, at the optimal temperature for the formation of catalytic systems 80-90° (353-363 K) and the optimal time of formation of the catalyst 25-30 minutes
A distinctive feature of the present invention is used as a modifying additive white phosphorus introduced into the reaction system to the stage of recovery of Pd(acac)2hydrogen, as well as the simplicity of its receipt.
The proposed method is efficient palladium catalyst for the hydrogenation of unsaturated, carbonyl and nitro compounds is as follows:
To a solution of bis-acetylacetonate palladium in DMF, placed in a thermostatted vessel type "duck"when room is the temperature in a stream of hydrogen add a solution of white phosphorus in benzene. The reaction mixture is stirred in hydrogen atmosphere at a temperature of 80-90° (353-363 K) for 15-30 min before the formation of the "solution" of black and brown. Then the reaction mixture is cooled to 30°and used in the hydrogenation.
Optimal conditions for the formation of the catalyst: the ratio of bis-acetylacetonate palladium:phosphorus = 0.2 and 0.3 (table 1); the temperature recovery of palladium (II) hydrogen 80-90° (353-363 K) (table 2), the recovery time is 25-30 min (table 3); the concentration of Pd(acac)2- 1 mmol/l (table 4).
Thus obtained catalyst allows gidrirovanii at a temperature of 30°C (303 K) styrene with activity 280 mol H2·(d) ATA Pd·min)-1; phenylacetylene consistently gidrirovanii to styrene with activity 157 mol H2·(d) ATA Pd·min)-1(if conversion phenylacetylene 90,0% selectivity to styrene is 95,3%) and then to ethylbenzene activity 118 mol H2·(d) ATA Pd·min)-1; nitrobenzene activity 128 mol H2·(d) ATA Pd·min)-1and 100%selectivity for aniline, benzaldehyde with activity 15 mol H2·(d) ATA Pd·min)-1and 100% selectivity for benzyl alcohol at 90% conversion (table 5).
Its advantage in comparison with the prototype is the higher specific catalytic activity in the hydrogenation.
Prima is 1: To a solution of 0,00304 g (1· 10-5mol) Pd(Acac)2in 9 ml of DMF, placed in otakuminopera, the hydrogen-filled vessel type "duck"add to 0.3·10-5mol of white phosphorus (P4) in 1 ml of benzene and stirred the reaction mixture for 25 min at 80°and the hydrogen pressure 1 excessive atmosphere. Received black-and-brown "solution" is cooled to 30°C (303 K) and experience in the hydrogenation of styrene. For this purpose through a Teflon tube with a rubber gasket in the syringe to inject 1 ml of styrene. The hydrogenation is carried out at intensive stirring, precluding the flow of process in the diffusion region. Control over the course of the process perform volumetric and GLC (a chromatograph Chrom-5, DIP, phase SE-30, the column length is 3.6 m, the temperature of thermostat 100°). The catalyst activity is 280 mol H2·(d) ATA Pd·min)-1that is, the quantitative conversion of styrene to ethylbenzene (table 1).
Examples 2-7: the Method is the same as in example 1. These examples illustrate the effect of the ratio P/Pd on the activity of the hydrogenation of styrene (table 1). The procedure for conducting experiments similar to example 1.
|The influence of the ratio P/Pd on the activity of the hydrogenation of styrene in the system Pd(acac)2 3< / br>WithPd=1 mmol/l, [substrate]/Pd=870, the solvent is DMF, T=30°C, PH2=1 ATM|
|Activity W, mol H2·(d) ATA Pd·min)-1||24||99||280||154||109||2||1|
Examples 8-11: these examples illustrate the effect of temperature recovery of Pd(Acac)2during the formation of the catalyst on the activity of the hydrogenation of styrene (table 2). The procedure for conducting experiments similar to example 1.
|The influence of the temperature of formation of the catalytic system Pd(acac)2+0,3 R on its activity in the hydrogenation of styrene|
WithPd=1 mmol/l, [substrate]/Pd=870, the solvent is DMF, T=30°C, PH2=1 ATM
|Activity W, mol H2·(d) ATA Pd·min)||0||0||290||137|
Examples 12-15: these examples illustrate the effect of the duration of the recovery process, Pd(Acac)2during the formation of the catalyst at optimum temperature (80° (C) on its activity in the hydrogenation of styrene (table 3). The procedure for conducting experiments similar to example 1.
|The influence of the duration of the process of formation of the catalytic system Pd(acac)2+0,3 P at 80°With activity in the hydrogenation of styrene WithPd=1 mmol/l, [substrate]/Pd=870, the solvent is DMF, T=30°C, PH2=1 ATM|
|Activity W, mol H2·(d) ATA Pd·min)-1||0||280||222||140|
Examples 16-21: these examples illustrate the effect of the concentration of the catalyst on its catalytic activity (table 4).
|The effect of the concentration of palladium on the activity of the hydrogenation stir the La in the system Pd(acac)
the solvent is DMF, T=30°C (303 K), PH2=1 ATM, the volume of styrene = 1 ml
|The Pd concentration, mmol/l||0,5||1,0||2,5||5,0||7,5||10,0|
|Activity W, mol H2·(d) ATA Pd·min)-1||191||280||164||33||34||33|
Examples 22-25: these examples illustrate the activity of the catalyst in the hydrogenation of various substrates (table 5). The procedure for conducting experiments similar to example 1.
|The activity of the catalytic system Pd(ASAS)2+0,3 PH3in the hydrogenation of various substrates WithPd=1 mmol/l, the solvent is DMF, the solution to 10 ml, T=30°C, PH2=1 ATM|
|Activity W, mol H2·(d) ATA Pd·min)-1||280||156||128||15|
|Quantity of substrate mmol||9,0||7,3||2,5||9,9|
|Output products||100% ethylbenzene||100% ethylbenzene||100% aniline||90% benzyl alcohol|
We offer palladium hydrogenation catalyst has high catalytic activity in the catalytic process under mild conditions (at room temperature and a hydrogen pressure of 1 barg. ATM).
1. Palladium hydrogenation catalyst containing the recovered compound of palladium and modifying additive, characterized in that as the source of palladium compounds using bis-acetylacetonate, palladium, and as a modifying additive white phosphorus (R4) in the following ratio of components: bis-acetylacetonate palladium/phosphorus = 1:0.1 to 1:1.
2. A method of obtaining a palladium hydrogenation catalyst according to claim 1, based on recovery of starting compound of palladium with hydrogen in the presence of the modifying additive, characterized in that as modifying additives used white phosphorus, which is injected to the stage of recovery of the compounds of palladium (II) hydrogen, and as the parent compound of palladium bis-acetylacetonate, palladium, at the optimum t is mperature the formation of catalytic systems 80-90° (353-363 K) and the optimal time of formation of the catalyst 25-30 minutes
FIELD: industrial organic synthesis.
SUBSTANCE: alkylation of benzene with ethylene is carried out by supplying dried benzene feed, aluminum chloride-based catalytic complex, ethylene, recycled catalytic complex, and return benzene to alkylation reactor; separating resulting reaction medium from catalytic complex; neutralizing reaction medium with alkali; and flushing with water alkali; followed by rectification separation of reaction medium. According to invention, reaction components are preliminarily mixed in turbulent mode and fed into alkylation reactor also under turbulent conditions.
EFFECT: increased degree of benzene conversion.
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: invention relates to hydrotreatment of different petroleum fractions with high content of straight-chain paraffins to yield product with high content of isoparaffins. Catalyst is prepared on the base of crystalline elemento-alumino-phosphates having specified structure via (i) preparing aqueous reaction mixture containing aluminum source, concentrated phosphoric acid, and one or two sources of substituting element selected from magnesium, zinc, silicon, cobalt, manganese, nickel, chromium, and also organic structuring compound constituting di-n-pentylamine or mixture thereof with other di-n-alkylamines and having following composition (in molar parts): R/Al2O3 0.5-2.0, P2O5/Al2O3 0.8-1.2, MOx/Al2O3 0.05-1.5, and H2O/Al2O3 15-200 followed by (ii)crystallization of thus prepared mixture.
EFFECT: increased activity and selectivity of catalyst with regard to formation of desired reaction products and preserved catalyst activity regarding hydrogenation of aromatics.
4 cl, 1 dwg, 14 ex
FIELD: preparation of crystal elemento-alumo-phosphates, including alumo-phosphates of zeolite-like structure.
SUBSTANCE: alumo-phosphates are designated as ATO according to classification of Structural Commission of International Zeolite Association. Proposed method includes preparation of aqueous reaction mixture containing aluminum source, concentrated phosphoric acid and one or two sources of substituting element, as well as organic structure-forming compound in form of di-n-pentyl amine or mixture of di-n-pentyl amine with other di-n-pentyl amines having common composition expressed in terms of mole ratios: R/Al2O3=0.5-2.0; P2O5/Al2O3=0.8-1.2; MOx/Al2O3=0.1.5; H2O/Al2O3=15-200, where R is organic structure-forming compound; M is substituting element selected from beryllium, magnesium, zinc, chromium, gallium, iron, silicon, titanium, cobalt, manganese and cadmium; x=1, 3/2 or 2. Then, mixture thus prepared is subjected to crystallization, after which material is separated and dried.
EFFECT: possibility of obtaining pure-phase specimens without by-phases.
39 cl, 1 dwg, 7 tbl
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: invention relates to novel ruthenium catalysts, method for preparation thereof, and to employment thereof for catalytic hydrogenation of mono- and oligosaccharides in production of corresponding sugar alcohols. Ruthenium hydrogenation catalyst contains ruthenium supported by amorphous silica-based carrier, content of ruthenium being 0.2 to 7% of the weight of carrier, while carrier contains at least 90% silica and less than 10% of crystalline silicon dioxide phases. Catalyst is prepared by single or multiple treatment of carrier material with halogen-free solution of low-molecular weight ruthenium compound and subsequent drying of treated material at temperature not lower than 200°C immediately followed by reduction of dried material with hydrogen at 100 to 350°C. Herein disclosed is also a process for liquid-phase production of sugar alcohols (excepting sorbitol) via catalytic hydrogenation of corresponding mono- and oligosaccharides in presence of proposed catalysts.
EFFECT: increased activity and selectivity of catalysts.
16 cl, 4 tbl, 7 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: invention relates to catalyst for aromatization of alkanes, to a method of preparation thereof, and to aromatization of alkanes having from two to six carbon atoms in the molecule. Hydrocarbon aromatization method consists in that (a) C2-C6-alkane is brought into contact with at least one catalyst containing platinum supported by aluminum/silicon/germanium zeolite; and (b) aromatization product is isolated. Synthesis of above catalyst comprises following steps: (a) providing aluminum/silicon/germanium zeolite; (b) depositing platinum onto zeolite; (c) calcining zeolite. Hydrocarbon aromatization catalyst contains microporous aluminum/silicon/germanium zeolite and platinum deposited thereon. Invention further describes a method for preliminary treatment of hydrocarbon aromatization catalyst comprising following steps: (a) providing aluminum/silicon/germanium zeolite whereon platinum is deposited; (b) treating zeolite with hydrogen; (c) treating zeolite with sulfur compound; and (d) retreating zeolite with hydrogen.
EFFECT: increased and stabilized catalyst activity.
26 cl, 1 dwg, 5 tbl, 4 cl
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: invention is dealing with development of effective catalyst for hydrogenation of unsaturated hydrocarbons (alkenes, alkynes) and a method for preparation thereof, which could be used in fine organic synthesis. Catalyst contains palladium compound and a modifying additive, the former being palladium bis-acetylacetonate and the latter phosphine (PH3) at molar ratio ranging from 1:0.1 to 1:1, respectively. Preparation of catalyst is based on reduction of palladium compound with hydrogen in presence of phosphine, which is introduced before reduction of palladium bis-acetylacetonate at catalytic system formation temperature: 70-80°C. Optimal time for molding of catalyst is 10-15 min.
EFFECT: increased catalytic activity when carrying out catalytic process under mild conditions (at room temperature and atmospheric pressure) and reduced catalyst preparation expenses.
2 cl, 5 tbl, 24 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention relates to preparation of supported Fischer-Tropsch catalysts and comprises treatment of supported Fischer-Tropsch catalyst precursor in the first step, which precursor is in pre-reduced state in the form of particles. Precursor contains cobalt-impregnated catalyst support and reducible labilized cobalt oxide in fired state selected from compounds depicted by formulas including CoOaHb, wherein a=1.7 and b>0, and monometallic hydrocalcite-type compounds Coii 0,74Coiii 0,26(OH)2,01(NO)0,21(CO)0,02×0,6H2O. Cobalt oxide is reduced with reducing gas, which is pure hydrogen, at the first volumetric velocity of supplied gas SV1 and first heating velocity HR1 to form partially reduced catalyst precursor. Resulting precursor is activated, in the second step, with reducing gas, which is pure hydrogen, at the second volumetric velocity of supplied gas SV2 and second heating velocity HR2, so that SV2<SV1 and/or HR2≥HR1 provided that, when SV2=SV1, then HR2≠HR1 and, HR2=HR1, then SV2≠SV1.
EFFECT: achieved maximum catalytic activity.
12 cl, 3 dwg, 5 tbl, 5 ex
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: invention provides copper and silica-based catalyst containing 22.5-53.0% copper. Catalyst is prepared by reductive thermal decomposition of copper silicate in hydrogen flow at 380-450°C. catalyst is used in dihydroxyalkane production processes carried out at 180-200°C.
EFFECT: increased activity and selectivity of catalyst.
3 cl, 1 tbl, 8 ex
FIELD: hydrocarbon conversion processes.
SUBSTANCE: process consists in catalytic decomposition of hydrocarbon-containing gas at elevated temperature and pressure 1 to 40 atm, catalyst being reduced ferromagnetic cured product isolated by magnetic separation from ashes produced in coal combustion process at power stations. The catalytic product represents spinel-type product containing 18 to 90% iron oxides with balancing amounts of aluminum, magnesium, titanium, and silicon oxides. Prior to be used, catalyst is subjected to hydrodynamic and granulometric classification.
EFFECT: reduced total expenses due to use of substantially inexpensive catalyst capable of being repetitively used after regeneration, which does not deteriorate properties of original product.
2 cl, 6 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: catalytic system of hydrocarbon feedstock hydrofining is activated by circulating hydrogen-containing gas or mixture thereof with starting feedstock through layer-by-layer loaded catalysts in presulfided or in presulfided and oxide form at elevated temperature and pressure. Hydrogen is injected into circulating hydrogen-containing gas or mixture thereof with starting feedstock portionwise, starting concentration of hydrogen in circulating hydrogen-containing gas not exceeding 50 vol %. Starting feedstock consumption is effected stepwise: from no more than 40% of the working temperature to completely moistening catalytic system and then gradually raising feedstock consumption to working value at a hourly rate of 15-20% of the working value. Simultaneously, process temperature is raised gradually from ambient value to 300-340°C. Circulating factor of hydrogen-containing gas achieves 200-600 nm3/m3. Addition of each portion of hydrogen is performed after concentration of hydrogen in circulating hydrogen-containing gas drops to level of 2-10 vol % and circulation of hydrogen-containing gas through catalysts loaded into reactor begins at ambient temperature and further temperature is stepwise raised. Starting feedstock, which is straight-run gasoline or middle distillate fractions, begins being fed onto catalytic system at 80-120°C.
EFFECT: enabled prevention and/or suppression of overheating in catalyst bed.
5 cl, 6 tbl, 12 ex
FIELD: petrochemical processes.
SUBSTANCE: feedstock is brought into contact with preliminarily activated zeolite-containing catalyst, namely mordenite-supported Pt, at 250-300°C, pressure 1.5-3.5 MPa, hydrogen-containing gas-to-feedstock ratio 300-1000 nm3/m3, and feed flow rate 1.0-4.0 h-1. Preliminary activation of zeolite-containing isomerization catalyst is conducted in two successive steps: drying catalyst in inert gas flow; reducing catalyst in hydrogen-containing gas flow; and supplying feedstock and setting steady-state isomerization process. Drying of zeolite-containing catalyst in inert gas flow is effected under conditions of gradually raised temperature from 120°C at temperature raise rate 10-15°C/h and ageing for 2-5 h at 120°C to 350°C followed by ageing at this temperature, whereupon temperature is lowered to 130°C. Reduction of zeolite-containing catalyst in hydrogen-containing gas flow is effected at gradually raised temperature to 220-350°C at temperature rise rate 15-25°C/h and ageing for 2-6 h at 220-350°C, whereupon temperature is lowered to 180°C. Initial feedstock is supplied at 180°C in circulating hydrogen-containing gas flow, aged for 4 h at 180°C and then gradually heated to 250°C at heating rate 5°C/h, after which further heated at heating rate 5°C a day to achieve process characteristics meeting product quality requirements.
EFFECT: increased catalyst activity, selectivity, and working stability.
2 cl, 2 tbl, 17 ex
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: palladium-containing hydrogenation catalyst, which can be used to control rate of autocatalytic hydrogenation reactions, is prepared by hydrogen-mediated reduction of bivalent palladium from starting compound into zero-valence palladium and precipitation of reduced zero-valence palladium on carbon material, wherein said starting material is tetraaqua-palladium(II) perchlorate and said carbon material is nano-cluster carbon black. Reduction of palladium from starting compound and precipitation of zero-valence palladium on carbon material are accomplished by separate portions.
EFFECT: increased catalytic activity, enabled catalyst preparation under milder conditions, and reduced preparation cost.
1 dwg, 1 tbl, 12 ex
FIELD: organic synthesis and catalysts.
SUBSTANCE: invention relates to improved method of telomerization of diene with conjugated double bonds, wherein said diene interacts with a compound having active hydrogen atom and selected from group, consisting of alkanols, hydroxyaromatic compounds, carboxylic acids, and water, in presence of telomerization catalyst based on VIII group metal source and bidentate ligand. The latter is depicted by general formula (I): R1R2M1-R-M2R3R4, wherein M1 and M2 independently represent P; R1, R2, R3, and R4 independently represent monovalent aliphatic group or R1, R2, and M1 jointly and/or R3, R4, and M2 jointly independently represent cycloaliphatic group with 5-12 carbon atoms in cycle, wherefrom one atom is M1 or M2; and R represents (i) bivalent organic bridge group, which is unsubstituted alkylene group or alkylene group substituted by lower alkyl groups optionally incorporating oxygen as heteroatom, or (ii) group containing two benzene rings bound to each other or to alkylene groups, which in turn are linked to M1 and M2. Invention also relates to novel bidentate ligands, which can be utilized in the method of invention and having following general formulas: R1R2M1-V-M2R3R4 (II) and Q1Q2M1-Q5-Ar1-Q6-M2Q3Q4 (III). Invention further relates to improved method for production of 1-octene involving 1,3-butadiene telomerization step to form 1-substituted 2,7-octadiene.
EFFECT: expanded synthetic possibilities in conjugated dienes area.
10 cl, 1 dwg, 1 tbl, 10 ex