Method of producing phenylethynyl derivatives of aromatic compounds
SUBSTANCE: method includes heating a mixture of components - 0.01 mol phenylacetylene, 0.01 mol iodobenzene (aryl iodide), 0.0006 g copper nanopowder and 0.002 g CuI at temperature of 110-120°C for 3 hours; after cooling, the reaction mass is poured into 100 ml cold water while stirring, followed by extraction with ethyl acetate, purification on a column with silica gel, elution with a solvent mixture with ratio of ethyl acetate to hexane of 1:6 and then distilling off the solvent to obtain pure products.
EFFECT: use of the present method enables to obtain end products with high output with considerable simplification of the process.
The invention relates to methods of organic synthesis, in particular to a method of synthesis phenylethynyl derivatives of aromatic compounds with the substitution of the iodine molecules in phenylacetylene, which are widely used in various fields, including in the manufacture of luminescent materials, and are used in chemistry, biology, and medicine.
Known methods of synthesis phenylethynyl derivatives of aromatic compounds with the substitution of the iodine molecules in phenylacetylene - this reaction with imprisonme occurs in the presence of base and palladium catalyst (Sonogashira) ().
Some patents have been used reaction type Sonogashira (benzodiazepine Derivative and drug containing, No. 2259360 EN, publ. 27.08.05; indole Derivatives containing an acetylene group, as PPAR activators, No. 2387639 EN, publ. 27.04.10; the Method of obtaining inhibitors of poly(ADP-ribose)polymerases, No. 2344138 EN, publ. 20.01.09; Triazolinone aminobenzophenone connection, No. 2394818 EN, publ. 20.07.2010). These reactions combination method Sonogashira preferably carried out using known catalytic mixtures of Pd(PPh3)4/CuI. B these systems were used amines as solvents, such as diethylamine, triethylamine, pyridine, etc. which, when evaporation is vzryvoopasnym and toxic.
A known method for the synthesis of phenylethynyl derivatives of aromatic compounds with the substitution of the iodine molecules in phenylacetylene (Catalytic Activity of Pd(II) Complexes with Triphenyl phosphito Ligands in the Sonogashira Reactionin Ionic Liquid Media, I.Błaszczyk A.M. Trzeciak J.J. Zio'łkowski, Catal. Lett. 2009, 133:262-266). When performing synthesis is necessary not only palladium, triethylamine, and the ionic liquid, and an inert atmosphere. To obtain a product in this way requires a complex installation, which is a disadvantage of the method.
A known method for the synthesis of phenylethynyl derivatives of aromatic compounds with the substitution of the iodine molecules in phenylacetylene (Tandem Sonogashira Coupling: An Efficient Tool for the Synthesis of Diarylalkynes. Zolta'n Nova'k, PE ter Nemes, and Andra's Kotschy. Organic Letters, 2004 Vol.6, No. 26, 4917-4920). But the synthesis should be carried out in two stages, first in the process is formed intermediate product between odensala and 2-methyl-3-butyn-2-I. Also the yields of target products is low and variable from 17 to 84%.
A known method for the synthesis of phenylethynyl derivatives of aromatic compounds with the substitution of the iodine molecules in phenylacetylene using CuI (Copper(I) Iodide Polyphosphine Adducts at Low Loading for Sonogashira Alkynylation of Demanding Halide Substrates: Ligand Exchange Study between Copper and Palladium, Matthieu Beaupérin, Andre Job, Hélène Cattey, Sylviane Royer, Philippe Meunierand Jean-Cyrille Hierso; Organometallics, 2010, 29(12), pp. 2815-2822), in this case it was used a very complex system of catalysts, as the CuI socialization si is the topic of [PdII(η3-allyl)Cl] 2that is the disadvantage of the method.
A known method for the synthesis of phenylethynyl derivatives of aromatic compounds with the substitution of the iodine molecules in phenylacetylene type Sonogashira using Cu(I) (Copper-Catalyzed Synthesis of 1,3-Enynes. Craig G. Bates, Pranorm Saejueng, and D. Venkataraman. Organic Letters, 2004, Vol.6, No.9, 1441-1444). When this system was used Cu(I) as the main catalyst (for example [Cu(bipy)PPh3Br]), Cs2CO3, toluene, 110°C, 24 hours. It is also a complex system, which is a disadvantage of the method.
Object of the invention is to develop an effective method of obtaining phenylethynyl derivatives of aromatic compounds with the substitution of the iodine molecules in phenylacetylene using copper nanopowder.
The copper nanopowder prepared by a known method of electrical explosion of wire in an atmosphere of inert gas argon (jaworowski N.A., ALEXANDER Pustovalov, Lobanov GL, Zhuravkov S. p. study of the properties of aluminum powders obtained in argon with the addition of oxygen. // Izvestiya vuzov. Physics. 2012, T, No. 6/2, p.236-244). To obtain copper nanopowder was used to install UDP-4G, copper wire mark "MM" diameter 0,25 mm Length of exploding for one pulse of the wire piece is 105 mm, the charging voltage U=21 kV, the capacity of the capacitor Bank C=2,24 cf. The pressure of argon in the installation of 2.5 ATM. For electroexplosive nanopowders synthesis methodology is, through the metal wire is passed pulse current density (1010A/m2), resulting in the conductor vzryvoobrazno destroyed, the products of the explosion are condensed in the atmosphere of inert gas to form nano-sized particles. The powder obtained in this way has a value of specific surface area Sbeats=8m2/g, which corresponds to the average particle size of 84 nm (the size of the agglomerates is about 150-300 nm), and has high chemical activity. A dark-brown powder. The particle shape is spherical. Bulk density of about 5 g/cm3. The powder contains metallic copper (Cu), about 98% wt.; the rest of sorbed gases, copper oxide CuO is less than 1%, Cu2O less than 1% and H2O.
It is known that the nanopowder copper reacts with phenylacetylene in dimethylformamide (DMF), forming a yellow precipitate complex diphenylbutadiyne and copper. (Copper and Copper Oxides Nanopowders in the Oxidative Condensations of Phenylacetylene and tert-Butylacetylene. O.A. Kuznetsova, E.F. Khmara, V.I. Filyakova, M.A. Uimin, A.E. Ermakovb, S. Kaliev Rheec, and V.N. Charushin. Zhurnal Obshchei Khimii, 2007, Vol.77, No. 3, pp.439-443. Nanopowders based on copper and its oxides in oxidizing condensation phenylacetylene and tert-butylaniline, O. A. Kuznetsov, E. F. Khmara, C. I. Filatova, M. A. Uimin, A. E. Ermakov, S. Kaliev Rhee, C. N. Charushin. Journal of General chemistry. 2007, T, issue 3, s-443).(Synthesis and crystal structure of tetranuclear nickel(0) complex with 1,4-diphenylbutadiyne in the η2, η2-bridging mode. aekawa, M., Munakata, M., Kuroda-Sowa, T., and Hachiya, K., Inorg.Chim.Acta, 1995, vol.231, p.213.) (Synthesis and crystal structure of unsymmetrical trinuclearnickel(0) complexes with the 1,3-butadiynes in the monodentate and µ2-η2, η2-bridgin mode [Ni3(L)(cod)3] (L=tmsb and dpbd) out by Maekawa, M., Munakata, M., Kuroda-Sowa, T., and Hachiya, K., Polyhedron, 1995, vol.14, p.2879).
This means that in DMF in the presence of nanopowder copper phenylacetylene can timeresults. But before the formation diphenylbutadiyne appear radical particles of the type phenylacetylene [PhC≡C].
Prepare a mixture of two catalysts - Cu nanopowder and CuI, the nanopowder Cu reacts with phenylacetylene to form a radical particle phenylacetylene, and simultaneously CuI reacts with odensala (arriagada), thus activating it. In the two transitional particles react with each other forming diphenylacetylene.
This object is achieved in that produce heating of the mixture components, 0.01 mol of phenylacetylene, 0.01 mol of odensala (aricidea), 0,0006 g copper nanopowder and 0.002 g CuI at a temperature of 110-120°C for 3 hours. After cooling the reaction mixture it is then poured into 100 ml of cold water with stirring, extracted with ethyl acetate. Then purified on a column of silica gel, elwira mixture solvent ethyl acetate : hexane in a ratio of 1:6. Next, the solvent is distilled off, getting friendly products. The mixture of reagents nano is orosco copper and CuI plays the role of catalyst, which reacts with the two substrates by the mechanism based on the reaction Sonogashira.
Thus, the proposed method allows to obtain phenylethynyl derivatives of aromatic compounds with the substitution of the iodine molecules in phenylacetylene using copper nanopowder. The method gives the yields of target products from 70 to 90%, significantly simplifies the process (see table).
|The method of obtaining phenylethynyl derivatives of aromatic compounds|
|Substrates||Products||Yield, % (time)||T C (p-l)/ %C %H|
|95 (0.5 hour)||248-250°C (AcOBu) %C 94,92 %H a 4.83|
|90 (1 hour)||188-190°C (Acoet) %C than 94.69 %H a 5.25|
|87 (2 hours)||155-156°C (AcOBu) %C 94,95 %H 4,75|
|85 (2 hours)||338-341°C (AcOBu) %C 94,90 %H is 4.93|
|87 (2 hours)||186-188°C (AcOBu) %C 90,82 %H 4,82 %O 4,32|
|82 (2.5 hour)||242-244°C (AcOBu) %C 94,92 %H 4,85|
|75 (3 hours)||253-254°C (Acoet)%C 94,91 %H 5,00|
|77 (3 hours)||136-137°C (Acoet) %C 94,82 %H 5,15|
|72 (3 hours)||176-178°C (Acoet) %C 94,96 %H 4,95|
|70 (3 hours)||62-63°C (Eton) %C 94.34 %H 5.66|
The method of obtaining phenylethynyl derivatives of aromatic compounds, comprising heating a mixture of components, 0.01 mol of phenylacetylene, 0.01 mol of odensala (arriagada), 0,0006 g copper nanopowder and 0.002 g CuI at a temperature of 110-120°C for 3 hours, after cooling the reaction mixture it is then poured into 100 ml of cold water with stirring, extracted with ethyl acetate, and then purified on a column of silica gel, elwira mixture solvent ethyl acetate : hexane in a ratio of 1:6, then the solvent is distilled off, getting friendly products.
SUBSTANCE: invention relates to novel individual diarylalkanes, to method of preventing treatment of diseases and states, associated with tyrosinases, method of preventing treatment of diseases and states, associated with overproduction or uneven distribution of melamine, method of inhibiting tyrosinase activity and method of melamine synthesis suppression, in which claimed diarylalkanes, as well as compositions for local application based on novel diarylalkanes, are applied.
EFFECT: increased efficiency of composition application.
30 cl, 5 tbl, 14 dwg, 18 ex
SUBSTANCE: invention relates to versions of a novel method of producing a (E)-stilbene derivative of formula
used to produce polyhydroxystilbenes, particularly resveratrol or piceatannol, which exhibit antioxidant effect, novel intermediate compounds of formula , , and
used in said methods, as well as use of the compound of formula
(III), (IV) or (VII) as an intermediate compound in the synthesis of the (E)-stilbene derivative of formula (VI) or polyhydroxystilbene. Values of substitutes R1, R1', R2', R, A, Ar, R' are given in the claim.
EFFECT: improved properties of the compound.
26 cl, 1 dwg, 32 ex
SUBSTANCE: method involves: transformation of 1-(4-hydroxy-3-propylphenyl)propane-1-on under effect of trifluoromethane sulphone anhydrite (Tf2O) in the presence of triethylamine (NEt3) into its derivative 4-propyionyl-2-n-propylphenyl ether of trifluoromethane sulphonic acid, with further concentration by Suzuki reaction type with 2-ethyl-5-metoxyphenylboronic acid in the presence of K2CO3, PdCl2(PPh3)2 or Pd(PPh3)4 in catalytic amount, obtaining 1-(2'-ethyl-5'-metoxy-2-propylbiphenyl-4-yl)propane-1-on; demethylation of 1-(2'-ethyl-5'-metoxy-2-propylbiphenyl-4-yl)propane-1-on by heating in the absence of solvent with pyridine salt excess, obtaining 1-(2'-ethyl-5'-hydroxy-2-propylbiphenyl-4-yl)propane-1-on; transformation of 1-(2'-ethyl-5'-hydroxy-2-propylbiphenyl-4-yl)propane-1-on into 6-ethyl-4'-(1-ethyl-1-hydroxypropyl)-2'-propylbiphenyl-3-ol by reaction with ethylmagnesium bromide or ethyllithium, and condensation of 6-ethyl-4'-(1-ethyl-1-hydroxy-propyl)-2'-propylbiphenyl-3-ol with dimethyl ether of 4-bromomethylphthalic acid, with further recovery reaction by lithium borohydride in situ. Claimed method allows for obtainment of target product with high output. Also invention refers to novel 6-ethyl-4'-(1-ethyl-1-hydroxypropyl)-2'-propylbiphenyl-3-ol compound used as intermediary product in the claimed method.
EFFECT: possible application in medicine.
17 cl, 1 dwg, 1 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention provides improved process for production of a fluorine-containing compound useful as starting material for manufacture of a variety of fluoropolymers with high output when performing short process and using inexpensive and easily accessible chemicals. Process comprises: (i) interaction of indicated below compound 1 with indicated below compound 2 to form indicated below desired compound 3, which is a compound, wherein content of fluorine is at least 30 wt % and which has hydrogen atom or multiple bond capable of being fluorinated; and (ii) liquid-phase fluorination of compound 3 to give indicated below compound 4 followed by (iii) cleaving group EF in compound 4 to produce compound 5 and compound 6: E1-RA-E1 (1), E2-RB (2), RB-E-RA-E-RB (3),
RBF-EF-RAF-EF-RBF (4), EF1-RAF-EF1 (5),
and RBF-EF2 (6), where RAF represents fluorine-containing bivalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether oxygen atoms; RA represents group, which is the same as group RAF or bivalent organic group capable of being converted into group RAF using fluorination reaction; RBF represents fluorine-containing polyvalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether or carbonyl oxygen atoms; RB represents group, which is the same as group RBF or polyvalent organic group capable of being converted into group RBF using fluorination reaction; E1 and E2 are such that, when group E1 is -CH2OH or Q1-CH2OH group, then group E2 is -COX or -SO2X group and, when group E2 is -CH2OH or -Q2-CH2OH group, then group E1 is -COX or -SO2X group, where X is halogen atom and Q1 and Q2 may be identical or different and represent -CH(CH3)- or -CH2CH2- group; E represents group -CH2OCO-, -CH2OSO2-, -Q1-CH2OCO-, -Q2-CH2OCO-, -Q1-CH2OSO2-, or -Q2-CH2OSO2-; EF represents group, which is the same as group E or group obtained by fluorination if group E on conditions that at least one group RAF, RBF, or EF is a group formed by fluorination reaction and groups EF1 and EF2 are groups formed by cleaving group EF. Invention also relates to novel fluorine-containing compounds of formulas 3-12, 3-13, 3-14, 3-15, 3-16, 4-12, 4-13, 4-14, 4-15, 4-16, 5-16, which are indicated in description.
EFFECT: increased resource of raw materials for production of fluoropolymers.
8 cl, 23 ex
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for preparing biologically active compounds, in particular, resveratrol of the formula (I): from Siberian cedar bark as a vegetable raw. Method involves extraction of Siberian cedar bark firstly with petroleum ether, 3 times for 3 h, at temperature 70-80°C for separation of terpene compounds followed by extraction of stilbene compounds by successive extraction with methyl-tert.-butyl ester and ethanol under the same conditions. Stilbene compounds are purified by column chromatography on silica gel followed by deglycosylation of prepared sum of stilbene glycosides by using lithium thioethylate at temperature 150°C in argon flow and the following O-demethylation of prepared resveratrol monomethyl ester by effect with boron tribromide in argon flow. Invention provides using available raw and high yield of the end product.
EFFECT: improved preparing method.
SUBSTANCE: invention relates to method of obtaining 1-alkynyl adamantanes from derivatives of adamantine and acetylene compounds with catalysis with Lewis acid, taken in equimolar amounts. Method is characterised by the following: as initial components used are 1-adamantanol and 1-alkene or 1-trimethylsilylalkene, which are heated at temperature of 1,2-dichloroethane boiling in presence of 5 molar percent of gallium triflate as Lewis acid until initial compounds are fully consumed.
EFFECT: application of claimed method makes it possible to obtain target compound from commercially available initial compounds with good output of target product.
1 cl, 1 tbl, 10 ex
SUBSTANCE: invention relates to a method for synthesis of 1,2,6,7-bis-(9H, 10H-anthracene-9,10-diiyl)pyrene 1 by reacting an in situ generated aryne derivative of pyrene with anthracene in an argon atmosphere
The present invention provides a method for synthesis of said compound, which can be used as a monomolecular optical sensor for detecting nitroaromatic compounds.
EFFECT: improved method.
1 ex, 1 tbl
FIELD: process engineering.
SUBSTANCE: invention relates for treatment of gas and gas condensate for pipeline transportation. Proposed method comprises catalytic treatment of hydrocarbon gas at higher temperature. It differs from known processes in that catalytic treatment is used for the mix of stabilisation gas and wide fractions of light hydrocarbons produced by separation of the mix of catalytic treatment product with gas condensate deposit borehole products to separation gas and condensate followed by dehydration, demineralisation and stabilisation to produce stable gas condensate and stabilisation gas. Note here that separation gas is subjected to drying and gas-gasoline processing to obtain dry stripped gas and wide fraction of light hydrocarbons.
EFFECT: higher yield of prepared gas and stable gas condensate, no wastes or semis.
1 cl, 1 ex
SUBSTANCE: invention relates to a method for synthesis of 2,3,6,7,10,11-tris-(9H, 10H-anthracene-9,10-diiyl)triphenylene 1 - a monomolecular optical sensor for detecting nitroaromatic compounds by reacting an in situ generated arine derivative of triphenylene with anthracene in an argon atmosphere .
EFFECT: use of the present method enables to obtain the desired compound with output of 69%.
1 cl, 1 ex, 1 tbl
SUBSTANCE: invention relates to apparatus for liquid-phase synthesis of isoprene from material which contains isobutylene and formaldehyde and/or substances which are sources thereof, for example, trimethyl carbinol and 4,4-dimethyl-1,3-dioxane, in the presence of an aqueous solution of an acid catalyst. The apparatus is a reactor system consisting of a shell-and-tube reactor which is heated by steam through the inter-tube space and is connected in series to a hollow vertical reactor, possibly fitted with a pump for forced circulation of the reaction mass between reactors, wherein there are distribution devices in the reactors for feeding material. The apparatus is also characterised by that it has at least three reaction zones defined by points of feeding material. In the hollow reactor, there are distribution devices for the entire stream of reaction mass above the points of feeding material, wherein the distance between a point of feeding material and a distribution device of the entire stream is at least 0.1 m, preferably 0.5-2.0 m.
EFFECT: use of the present apparatus enables more flexible control of the process of synthesis of isoprene with reduced formation of by-products and also increases efficiency of using the reaction volume, thus reducing capital and operating costs.
5 cl, 1 dwg
SUBSTANCE: invention relates to a method of producing 1,4-disubstituted [1.1.1b.1.1] pentipticenes , R = C=C-Ar; thienyl-2. The method involves reaction of pentipticene quinone with lithium derivatives of hetarenes and acetylenes, followed by aromatisation with a reducing agent. The method is characterised by that the reducing agent used is zinc dust in acetic acid.
EFFECT: use of the present method enables to increase output of the end product; the method is also simple and environmentally friendly and does not require use of expensive catalysts.
1 cl, 2 ex, 3 tbl
SUBSTANCE: invention relates to a method of processing methyldihydropyran and/or by-products of synthesis of isoprene from isobutylene and formaldehyde via thermocatalytic decomposition thereof over an aluminosilicate-containing catalyst with preheating (or without) of the starting material in the presence of water vapour followed by condensation of the obtained contact gas to form aqueous and oil layers. Reaction products - isoprene, isobutylene and formaldehyde - are then extracted from said layers. The method is characterised by that an isoprene fraction containing 3-25 wt % isobutylene dimers is added to the contact gas at temperature 35-90°C, with weight ratio of the isoprene fraction to the contact gas equal to (0.02-0.15):1.
EFFECT: use of the present method enables to considerably improve the quality of waste water from the process and reduce loss of the end products without reducing selectivity of the process and without increasing deposition of coke on the catalyst.
1 cl, 4 ex, 1 tbl
SUBSTANCE: invention relates to an compound of general formula (1), where each of R1-R8, R10 and R13 represent a hydrogen atom; each of R9 and R14 represents a group selected from a hydrogen atom, a tert-butyl group, a phenyl group and a naphthyl group, wherein the phenyl group contains at least one substitute selected from a methyl group, a tert-butyl group and a phenyl group, or is unsubstituted; one of R11 and R12 represents a hydrogen atom, and the other of R11 and R12 represents a group selected from a naphthyl group, a phenanthrenyl group, an anthracenyl group, a perylenyl group, a chrysenyl group, a benzo-s-phenanthrenyl group, a fluorenyl group, a fluoranthenyl group, a benzofluoranthenyl group and a naphthofluoranthenyl group, wherein the naphthyl group contains a phenyl group as a substitute or is unsubstituted, the anthracenyl group contains a phenyl group as a substitute or is unsubstituted, the chrysenyl group contains a phenyl group as a substitute or is unsubstituted, the fluorenyl group contains a methyl group as a substitute, the fluoranthenyl group contains at least one substitute selected from a tert-butyl group and a phenyl group, or is unsubstituted, and the benzofluoranthenyl group contains at least one substitute selected from a phenyl group, a phenyl group substituted with a methyl group, and a phenyl group substituted with a tert-butyl group, or is unsubstituted The invention also relates to an organic light-emitting device and a display device using said substance.
EFFECT: light-emitting organic devices using said compound demonstrate high colour purity, emission efficiency and long service life
4 cl, 6 tbl, 9 ex, 1 dwg
SUBSTANCE: invention relates to a method of producing isoprene, involving liquid-phase condensation of isobutylene in form of an isobutylene-containing C4 fraction with aqueous formaldehyde solution in the presence of an acid catalyst at high temperature and pressure to form 4,4-dimethyl-1,3-dioxane and a mixture of high-boiling by-products, followed by liquid-phase decomposition of the obtained 4,4-dimethyl-1,3-dioxane to isoprene in the presence of trimethyl carbinol and/or isobutylene and an aqueous solution of an acid catalyst at high temperature and pressure. The method is characterised by that 4,4-dimethyl-1,3-dioxane and a mixture of high-boiling by-products are separated from the condensation products by fractionation, where said mixture is then distilled on a vacuum fractionation column with collection of distillate in amount of 10-50 wt % from the column feed, followed by feeding the collected distillate for liquid-phase decomposition to isoprene in the presence of trimethyl carbinol and/or isobutylene and aqueous solution of the acid catalyst at temperature 150-200°C, pressure 0.6-1.7 MPa together with 4,4-dimethyl-1,3-dioxane and/or in a separate reactor.
EFFECT: method simplifies the process by eliminating gum formation and increases output of isoprene from the same amount of raw material.
3 cl, 4 ex, 1 tbl