The way to obtain 1-phenyl-trans-3,4-dialkylphosphorous
The invention relates to a method for producing 1-phenyl-TRANS-3,4-dialkylphosphorous General formulawhere R = n-C4H9the h6H13n-C8H17that is in interaction-olefins with atelecommunications and metallic magnesium in the presence of a catalyst Cp2ZrCl2in an argon atmosphere in the environment of the solvent for 8 h followed by the addition at a temperature of -15oWith CuCl as catalyst and phenyldichlorophosphine, followed by stirring the reaction mass for 8-12 h at room temperature. These compounds may find application in thin organic synthesis, as plasticizers, flame-retardant impregnation for nitrate and cellulose acetates, in the manufacture of insecticides, serve as additives to improve the quality of gasoline and lubricating oils, are used as surfactants in textile industry. The technical result - individual 1-phenyl-TRANS-3,4-dialkylphosphorous with high Regio - and stereoselectively. table 1. Description text in facsimile form (see graphic part)and where R = n-C4H9the h6H13n-C8H17,characterized in that-olefins of General formulawhere R=n-C4H9the h6H13H-C8H17,subjected to interaction with atelecommunications (EtAlCl2) and metallic magnesium in a molar ratio: EtAlCl2:Mg equal to(20-22):(10-12):10, in the presence of a catalyst of zirconatetitanate (Cp2ZrCl2), taken in an amount of 3-7 mol.% with respect to the metal magnesium in an argon atmosphere at room temperature and atmospheric pressure in THF as solvent for 8 h followed by the addition at a temperature of -15°C catalyst odnoklasniki copper (CuCl), taken in an amount of 8-12 mol.% in relation to the original-olefin, and phenyldichlorophosphine PhPCl2in equimolar towards EtAlCl2the number and stirring the reaction mass for 8-12 h at room temperature.
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a catalytic system comprising metallocene compound of the formula: wherein CpI and CpII represent carboanions with the cyclopentanedienyl-containing structure wherein from to all hydrogen atoms can be substituted; D means a donor atom possessing at least one electron pair; A means an acceptor atom that in its state it has electronic hole and D and A are bound by the reversible coordination bond and wherein a donor group receives a positive (partial) charge and an acceptor group - a negative (partial) charge; M means a transient metal of III, IV, V or VI subgroup of Mendeleyev's periodic law; x means anionic equivalent or η-complex compound of transient metals of the formula: (IIIa) or, respectively, (IIIb) wherein η means the charged or electrically neutral system that can be condensed with unsaturated or saturated rings; D means a donor atom or A with a transient metal M chosen from this group is carried out either directly or through a spacer and D and A are bound by a coordination bond as given above; X means anionic equivalent; n value depends on charge of M metals, and η means a number 0, 1, 2, 3, 4. Donor-acceptor structure promotes to stability of catalyst being up to high temperatures, i. e. without significant decrease of the catalyst activity and provides preparing polyethylenes with enhanced molecular mass and increased boiling point value. Also, invention relates to a method for preparing alpha-olefins.
EFFECT: valuable properties of catalyst, improved polymerization method.
7 cl, 10 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to derivatives of urea. Method is carried out by oxidation of diphenylchlorophosphine with sulfuryl chloride at temperature 20-25°C in carbon tetrachloride medium. Formed diphenylphosphinic acid chloroanhydride is subjected for interaction with sodium cyanate in acetonitrile medium in the presence of anhydrous magnesium chloride as a catalyst at temperature 20-25°C followed by the addition reaction of formed diphenylphosphoryl isocyanate to n-alkylamines at temperature 20-25°C in acetonitrile medium used as a solvent. Invention provides simplifying method and synthesis of highly pure substance and decreasing energetic and economy consumptions. Synthesized compounds can be used in technology for treatment of radioactive waste in radiochemical manufacture.
EFFECT: improved method of synthesis.
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of 1,3-bis-(diethylphosphinomethyl)-benzene of the formula: Invention proposes two methods of synthesis. By the first method diethylphosphine is subjected for interaction with 1,3-bis-(dibromomethyl)-benzene and formed phosphonium salt is treated with potassium carbonate. By the second method diethylphosphine borane complex is subjected for interaction with 1,3-bis-(dibromomethyl)-benzene in mixture of toluene and alkali aqueous solution followed by treatment of formed 1,3-bis-(diethylphosphinomethyl)-benzene borane complex with fluoboric acid dimethyletherate and sodium hydrocarbonate solution. Compound can be used as a ligand for homogenous catalysts in hydrogenation, cross-linking, polymerization and carbonylation reactions. Proposed methods for synthesis of the end substance are simple in realization and don't require using components combustible in contact with air and complex procedures.
EFFECT: improved method of synthesis.
2 cl, 2 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
SUBSTANCE: invention concerns C1-symmetrical biophosphine ligands and respective catalysts and their application in asymmetrical syntheses, including enantioselective hydration of prochiral olefins for production of pharmaceutical compounds, including (S)-(+)-3-(aminomethyl)-5-methylhexane acid known as pregabaline and its structurally related compounds. The methods involve new prochiral catalysts or precatalysts for obtaining the catalysts, including chiral ligand, connected to rhodium by phosphor atoms, with chiral ligand structure represented by the formula 4 .
EFFECT: obtaining new catalysts for application in asymmetrical syntheses.
19 cl, 46 ex, 7 tbl,7 dwg
SUBSTANCE: invention concerns improved method of obtaining mevalonic acid derivatives of the general formula I or its pharmaceutically acceptable salt with base, or lactone, where -CH2-CH2- or -CH=CH-, R is heterocyclical residual of interaction of compound of the general formula IIa , where R1, R2, R3, R4 meanings are described in the invention, with compound of the general formula IIb: R-CH(=O) where R is cyclical residual. Obtained compound is recovered in the presence of recovery agent, preferably a compound of the formula IId , where M is Ru, Rh, Ir, Fe, Co, Ni, L1 - H, L2 - aryl, R5 is aliphatic residual, R8 and R9 are C6H5 or form cyclohexane ring or cyclohexane or cyclopentane ring combined with C atom, to which they are bound, with a number of further stages.
EFFECT: high product output.
4 cl, 1 ex
SUBSTANCE: method of tris-(hydroximethyl)phosphine preparation includes the interreaction of hydrogen phosphide with formaldehyde in water-medium in presence of the catalyst - salt of divalent cobalt or nickel activated with ammonia or primary organic amines at temperature 20-80°C; process is carried out at pressure 8-12 atm and ratio of catalyst, activator and formaldehyde equal to 1:(10-15):(4500-5000) respectively.
EFFECT: decrease of used catalyst and activator amounts; enhancing of end-product yield till 98-98,9%.
1 cl, 2 ex, 1 tbl
SUBSTANCE: invention relates to a method of producing tricyclohexylphosphine, used in synthesis of metal complex catalysts for the following reactions: metathesis, carbonylation, cross linking, polymerisation etc. The proposed method involves reacting red phosphorus with cyclohexyliodide and iodine, taken in molar ratio of 1:3:0.1 at temperature from 215 to 220°C in an inert atmosphere. The formed dimeric iodine complex of tricyclohexylphosphine is treated with pyridine or toluene with addition of 2 equivalents of pyridine in terms of red phosphorus and zinc powder.
EFFECT: design of a novel efficient and safe method of producing tricyclohexylphosphine.
1 cl, 3 ex
SUBSTANCE: present invention relates to organic electroluminescent devices based on compounds of formula
where Y, Z is selected from N, P, P=O, C=O, O, S, S=O and SO2; Ar1, Ar2, Ar3 are selected from benzene, naphthaline, anthracene, phenanthrene, pyridine, pyrene or thiophene, optionally substituted with R1; Ar4, Ar5, Ar6, Ar7 are selected from benzene, naphthaline, anthracene, phenanthrene, pyridine, pyrene, thiophene, triphenylamine, diphenyl-1-naphthylamine, diphenyl-2-naphthylamine, phenyldi(1-naphthyl)amine, phenyldi(2-naphthyl)amine or spirobifluorene, optionally substituted with R1; E is a single bond, N(R1), O, S or C(R1)2; R1 denotes H, F, CN, alkyl, where the CH2 can be substituted with -R2C=CR2 -, -C=C-, -O- or -S-, and H can be substituted with F, optionally substituted aryl or heteroaryl, where R1 can form a ring with each other; R2 denotes H, aliphatic or aromatic hydrocarbon; X1, X4, X2, X3 are selected from C(R1)2, C=O, C=NR1, O, S, S=O, SO2, N(R1), P(R1), P(=O)R1, C(R1)2-C(R1)2, C(R1)2-C(R1)2-C(R1)2, C(R1)2-O and C(R1)2-O-C(R1)2; n, o, p, q, r and t are equal to 0 or 1; s = 1.
EFFECT: obtaining novel compounds - emission layer dopants, and novel electroluminescent devices based on said compounds which emit a blue colour.
18 cl, 91 ex, 6 tbl
SUBSTANCE: present invention relates to ligands used in transition metal based catalysts for hydroformylation, isomerisation-hydroformylation, hydrocarboxylation, hydrocyanation, isomerisation-formylation, hydroaminomethylation and related reactions, of formula: , where i, j, k, l, m and n are H, R, Ar, substituted Ar, OR, OAr, COOEt, halogen, SO2R, SO3H, SO2NHR, POR2, POAr2 or NR2, where R is optionally substituted alkyl or aryl, Ar is aryl; X1-X4 are O or CH2; and Y1, Y'1 Y2, Y'2, Y3, Y'3, Y4, Y'4 are R, Ar, OR, OAr, pyrrole and substituted pyrrole are bonded through a carbon-carbon bond, CH2, NH, NR or O.
EFFECT: obtaining novel efficient catalysts.
14 cl, 1 ex, 11 tbl
SUBSTANCE: invention refers to organic chemistry, namely, to method of production of functionally substituted fullerenes to be applied as complexing agents, sorbents, biologically active compounds, as well as for production of new materials with specified electronic, magnetic and optical properties. Substance of the method consists in production of 2,3-fullero-7-phenyl-7-phosphabicycklo[2.2.1]heptanes of formula (I) as resulted from reaction of fullerene C60 and phenylphospholane with catalyst Cp2TiCl2 added in toluol medium at temperature 140-160°C within 4-8 hours.
EFFECT: new method of selective production of functionally substituted fullerenes with end product yield 46-68%.
9 ex, 1 tbl
SUBSTANCE: present invention concerns the salts containing bis(trifluoromethyl)imide anions and saturated, partially or completely unsaturated heterocyclic cations, method of production and application thereof as ionic liquids.
EFFECT: production of new salts to be used as ionic liquids.
19 cl, 5 ex
SUBSTANCE: invention relates to ionic liquid used in electrical energy accumulation devices and as a solvent which contains a cation of general formula where X1, X2 and X3 denote N, O, S or C; R1-R11, X1, R1, R2 and R3, X2, R6, R7 and R8, X3, R9, R10 and R11 can form ring structures; the anion is selected from [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, [(RfSO2)3C]-, [(FSO2)3C]-, [ROSO3]-, [RC(O)O]-, [RfC(O)O]-, [CCl3C(O)O]-, [(CN)3C]-, [(CN)2CR]-, [(RO(O)C)2CR]-, [R2P(O)O]-, [RP(O)O2]2-, [(RO)2P(O)O]-, [(RO)P(O)O2]2-, [(RO)(R)P(O)O]-, [Rf2P(O)O]-, [RfP(O)O2]2-, [B(OR)4]-, [N(CN)2]-, [AlCl4]-, PF6 -, [RfPF5]-, BF4 -, [RfBF3]-, SO4 2-, HSO4-, NO3- I-, bis(oxalate)borate; R, R1-R11 are selected from hydrogehn, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl and heterocyclyl, halogen, CN- or NO2-; the carbon in R and R1-R11 can be substituted with O-, -Si(R')2-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N= -N=N-, -NH-, -NR'-, -N(R')2-, -PR'-, -P(O)R4 -P(O)R'-O-, -O-P(O)R'-O- and -P(R')2=N-; where R' denotes alkyl, fluoroalkyl, cycloalkyl, cycloalkenyl, cycloalkynyl, phenyl or heterocyclyl; Rf denotes a fluorine-containing substitute.
EFFECT: obtaining novel ionic liquids which are stable in liquid state in a wide temperature range.
14 cl, 76 ex, 3 dwg
SUBSTANCE: invention relates to a method of producing binuclear 3,4,5-triaryl-1,2-diphosphacyclopentadienide manganese complexes of general formula where Ar=C6H5, para-F-C6H4, para-Cl-C6H4. The method involves reacting a dimer of manganese tetracarbonyl bromide [MnBr(CO)4]2 with 1-trimethylstannyl-3,4,5-triaryl-1,2-diphosphacyclopenta-2,4-diene in molar ratio of 1:2 in pure tetrahydrofuran for 30 minutes at room temperature.
EFFECT: invention increases output of the product and reduces time and power costs.
SUBSTANCE: invention relates to chemistry of organometallic compounds, particularly to alkynyl phosphine gold-copper complexes which dissociate in a solution to form ions. The gold-copper alkynyl phosphine complexes are capable of forming covalent conjugates with proteins, thereby turning into a water-soluble form, exhibit luminescent properties and can be used as labels for fluorescence microscopy and in luminescent analysis.
EFFECT: improved properties of the compounds.
5 dwg, 4 tbl, 3 ex
SUBSTANCE: invention relates to a method of obtaining novel organophosphorous derivatives of formula 1 a-d
which can find application as ligands of metal-complex catalysts, intermediate reagents for fine organic and organometallic synthesis. The method consists in the interaction of skeletal hydrocarbons of a norbornene line with triethylaluminium (AlEt3) in the presence of the catalyst zirconocenedichloride (Cp2ZrCl2) in an argon atmosphere at a temperature of 15-25°C and atmospheric pressure for 12 hours without solvent with the addition at the second stage of toluene, benzene or hexane and PhPCl2 at a temperature of -10°C in the quantity of 1:1 relative to triethylaluminium with the following mixing of the reaction mass in an argon atmosphere at room temperature for 30 minutes.
EFFECT: obtaining novel organophosphorous derivatives.
2 cl, 1 ex, 1 tbl