A method of producing a catalyst for the oligomerization of styrene
(57) Abstract:The invention relates to the production of a catalyst for the oligomerization of styrene dimers, which are used as raw materials in organic synthesis and in the manufacture of synthetic rubbers, coolant, insulator oils as solvents polystyrene. The method consists of using a catalyst system comprising a palladium carboxylate of General formula Pd(OCOR)2where R - acetate, butyrate, valeriat, palmitate, stearate, benzoate, tertiary phosphines of General formula PR3where R is phenyl, artemether, parachlorophenyl, aromaticity, paradoxethereal, apirat boron TRIFLUORIDE of formula BF3OEt2. Spend the interaction of the components of the catalytic system In situ in the environment of the substrate without solvent, at a temperature of 333-C, atomic relations P: Pd = 1 - 3 and B: Pd = 5 - 10. The method allows to oligomerizate the styrene conversion of styrene oligomers to 1,45105the moles of styrene on the ATA Pd with selectivity for dimers to 89.7%. 5 table. The invention relates to the field of preparation of the catalyst for the oligomerization of styrene dimers, which are widely used as raw materials in organic synthesis and in the manufacture of synthetic cauterization for oligomerization of styrene-based compounds of divalent Nickel type 0,0'-diethyldithiophosphate Nickel and aluminiumchlorid type ethylaminoethanol, which will oligomerized styrene when the atomic ratio N1:A1=1:10 in white spirit at 308K with conversion of styrene only 4500 of moles of styrene per 1 g-at N1 .The closest known solution of an analogous problem to the technical essence and the achieved effect is a method of producing a catalyst for the oligomerization of styrene by reacting compounds of divalent palladium various compositions, including those containing carboxylate ligands, compounds of boron TRIFLUORIDE-substances containing complex anion of fluorine, for example, in the form of HBF4and with tertiary phosphines, for example, tributylphosphine . Such catalytic compositions are also characterized by relatively low conversion of styrene oligomers. Thus, ri oligomerization of styrene for 5 h at C under the action of the catalytic system Pd(OCOCH3)2+HBF4+P(n-Bu)3when the atomic ratio of Pd:B:P=1:2:1 conversion of styrene oligomers was 1104moles of styrene and 1 g-at Pd. Oligomers consisted mainly of dimers and trimers in the dimers 84%.To improve the efficiency of oligomerization of styrene is proposed in the following way: to use catalysts based on carboxylates of formula BF3OEt2.Distinctive features of the present invention is the use of catalytic systems on the basis of palladium carboxylates of General formula Pd(OCOR)2where OCOR-acetate, butyrate, valeriat, palmitate, stearate, benzoate, tertiary phosphines of General formula PR3where R is phenyl, artemether, parachlorophenyl, aromaticity, paradoxethereal and others, epirate boron TRIFLUORIDE of formula BF3OEt2.The method consists in the interaction of the carboxylate of palladium-tertiary phosphine and epirate boron TRIFLUORIDE in an environment of styrene at 298K for 30 minutes and Then the temperature change to the optimum.Optimal process conditions: temperature 333-C, preferably 343-K, the atomic ratio of P:Pd=1-3, preferably P:Pd=1-2, B:Pd=2-20, preferably B:Pd=5-10.Example 1. In a three-neck flask at 298K in argon atmosphere consistently make 300 ml (2.625 mol) of styrene, 0,0113 g (510-5mol) of bis-acetate, palladium and 0.0131 g (510-5mol) of triphenylphosphine, which are dissolved under stirring. Then by using the pipettor poured 0.046 ml (3,51004mol) epirate boron TRIFLUORIDE. Stirred for 30 min, then raise the temperature in the flask to K and conducting tifications installation. Allocate 179 g of styrene dimers (fraction 146-160oC/1 mm RT. Art.) and 19.7 g of the cubic residue. In accordance with the data of IR - and NMR1H-spectroscopy and gas chromatography-mass spectrometry fraction of dimers represented by a 1.3-diphenylbutane-1. VAT residue consists mainly of trimers.The conversion of styrene oligomers is 38200 mol of styrene and 1 g-at Pd.The selectivity of the oligomerization of styrene dimers is 90.1%, trimers - 9.9%.Examples 2-6. These examples illustrate the effect of the nature of the ligands with palladium on conversion of styrene oligomers. Oligomerization of styrene under conditions analogous to example 1. The data are given in table. 1.Examples 7-10. These examples illustrate the effect of the nature of the tertiary phosphines on the conversion of styrene oligomers. Oligomerization of styrene under conditions analogous to example 1. The data are given in table. 2.Examples 11-16. These examples illustrate the effect of atomic relations B: Pd for conversion of styrene oligomers. The procedure for conducting experiments similar to example 1. The data presented in table. 3.Examples 17-19. These examples illustrate the effect of atomic relations P: Pd for conversion of styrene oligomers. The ratio of P:Pd varied from face experiments - 7 o'clock the Data given in table. 4.Examples 20-25. These examples illustrate the effect of process temperature on the conversion of styrene oligomers in the presence of the system Pd(OAc)2+2PPh3+7BF3OEt2. The ratio of the components and the duration of experiments similar to example 18. The data presented in table. 5.The described method allows to increase the conversion rate of styrene oligomers with 1104mol of styrene on the ATA Pd with selectivity for dimers 84% to 1.45105mol of styrene on the ATA Pd with selectivity for dimers to 89.7%. A method of producing a catalyst for the oligomerization of styrene by the interaction of the components of the catalyst of palladium carboxylate, tertiary phosphine and compounds of boron TRIFLUORIDE in an environment of styrene, wherein as catalyst components using a palladium carboxylate of General formula
where OCOR - acetate, butyrate, valeriat, palmitate, stearate, benzoate, a tertiary phosphine of General formula PR3where R is phenyl, artemether, parachlorophenyl, aromaticity, paradoxethereal, apirat boron TRIFLUORIDE of formula BF3Ot2,
and the process is carried out at a temperature of 333 - C, the atomic relations P : Pd = 1 - 3 and
FIELD: chemistry of metalloorganic compounds, chemical industry.
SUBSTANCE: invention relates to preparing compounds of tetrapyrazinoporphyrazine order, namely, to cobalt octasulfooctaphenyltetrapyrazinoporphyrazine of the formula:
that can be used as a catalyst in oxidation reactions of sulfur-containing compounds, in particular, cysteine and thioureas, and diethylamine also being both in acid and neutral media.
EFFECT: valuable properties of compound.
2 cl, 2 dwg, 4 ex
FIELD: chemistry, pharmacology.
SUBSTANCE: present invention relates to method for production of indolo-pyrrolo-carbazole derivative according to formula (I) , or its pharmaceutically acceptable salt, that have antitumour activity. Invention also relates to method for production of indole compound according to formula (XII) , or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, distinguished by conducting interreaction between compound with formula (XIII) , or its pharmaceutically acceptable salt, where R1 is definitely above, Ra and Rb are either separately C1-C7-alkyl, or together form C3-C6-alkylene group, and hydrogen gas at 1 to 5 atmospheres, in presence of hydrogenation catalyst (applied as novel catalyst as well), which consist of rhodium compound, metal compound, and optionally amine, in inert solvent at room temperature; the rhodium compound being 1 to 10% rhodium on carbon, aluminium oxide, calcium carbonate, or barium sulphate, and metal compound being nickel (II), iron (II), iron (III), cobalt (II), or cobalt (III). Method is also submitted for production of bis-indole compound by formula (VIII) , or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, Y is hydrogen, C1-C7-alkyl, phenyl, benzyloxymethyl, or C7-C12-aralkyl, consisting in reaction of indole compound by formula (XII), or its pharmaceutically acceptable salt, where R1 is protective hydroxy-group, with ethylmagnesium chloride, or butylmagnesium chloride, or magnesium compound by formula (X) RdMgRd, where Rd is butyl, in inert solvent, followed by conducting interreaction between product obtained and maleimide compound by formula (IX) , where X is halogen, and Y as above, in inert solvent.
EFFECT: improved method for indolo-pyrrolo-carbazole production.
15 cl, 68 ex, 12 tbl
SUBSTANCE: method involves catalytic telomerisation of butadiene with diethylamine in the presence of a catalyst based on cationic complexes of palladium (II) of general formula [(acac)Pd(L)2]BF4 (where acac is an acetylacetonate ligand, L=PPh3, P'Pr3, P"Bu3 P(p-Tol)3 or (L)2=diphosphine ligands, selected from bis(diphenylphosphino)methane(dppm), bis(diphenylphosphino)propane(dppp), bis(diphenylphosphino)butane(dppb), bis(diphenylphosphino)ferrocene(dppf)). The process is carried out in a substrate medium, specifically diethylamine and butadiene, at temperature of 50-90°C. The method enables to obtain N,N-diethylocta-2,7-diene-1-amine with selectivity of 99.9% from the overall mixture of reaction products with high process output which reaches 4180 g of product per 1 g Pd. The catalysts used are more readily available compared to those previously used for the process.
EFFECT: improved method.
1 tbl, 1 ex
SUBSTANCE: invention relates to the field of organic chemistry, in particular to a method of obtaining alkylethers of 1- and 2-naphthalenecarboxylic acids, which are used in the synthesis of herbicides, plant growth hormones, dyes, photomaterials and polymers. The method of obtaining compounds of formula (1a-b) or (2a-b) in which R=CH3, C2H5, n-C3H7,consists in the fact that naphthalene is subjected to interaction with CCl4 and alcohol (methanol, ethanol, n-propanol) in the presence of metallic iron, activated HCl, and acetylacetone with the molar ratio of [Fe0(met.)]:[acetylacetone]:[naphthalene]:[CCl4]:[alcohol]=5-50:5:100:100-1000:100-1000, at a temperature of 130°C for 4-12 h in the argon atmosphere.
EFFECT: total output of alkyl ethers of 1- and 2-naphthalenecarboxylic acids reaches 75%.
1 tbl, 21 ex
SUBSTANCE: invention relates to a method of producing pentacyclo[8.4.0.03.7.04.14.06.11]tetradeca-8,12-diene of formula The method is characterised by catalytic dimerisation of 1,3,5-cycloheptatriene (CHT). The catalyst used is Ni(acac)2-Et2AlCl. The reaction is carried out with molar ratio CHT:Ni(acac)2:Et2AlCl=10:(0.1-0.3):4, in an argon atmosphere, at 20-100°C, in benzene for 8-48 hours.
EFFECT: method enables to obtain the end product separately.
7 ex, 1 tbl
SUBSTANCE: present invention relates to a method of preparing a catalyst complex of formula , where R1, R2, R3 and R4 are independently selected from a group consisting of hydrogen, C1-C20alkyl, C2-C20alkoxy group, halogen and amino group, where if R1 or R3 is an amino group, the amino group is optionally substituted with one or more fragments which are alkyl, if R2 or R4 is an amino group, the amino group is optionally substituted with one or more fragments which are C1-C20alkyl. The method includes a step of reacting a ruthenium catalyst precursor with one or two bidentate ligands of the Schiff base class in a nonpolar solvent and in the presence of a weak base, where the bidentate ligands of the Schiff base class are independently in amount of 1.0-3.0 equivalents relative to the amount of the catalyst precursor (formulae of the precursors and ligands are given in claim 1 of the invention). The invention also discloses a catalyst complex, a supported catalyst for metathesis of olefins and use thereof in olefin metathesis reactions.
EFFECT: invention enables to obtain a catalyst having high activity after activation, monomer stability and a simple and cheap method.
11 cl, 2 tbl
SUBSTANCE: invention relates to method of obtaining bis-(endo-bicyclo[4.2.1]none-2,4-dienes) of general formula (1), n = 0, 1, 2, 4. α,ω-diallenes of general formula interact with 1,3,5-cycloheptatriene (CHT) in presence of catalytic system TiCl4-Et2AlCl, with molar ratio α,ω-diallene:CHT:TiCl4:Et2AlCl = (9-11):20:(0.1-0.3):4, temperature 20-80°C, in benzene, for 10-48 h.
EFFECT: application of claimed invention makes it possible to obtain target compounds.
11 ex, 1 tbl