The way to obtain 1-ethyl-trans-3,4-dialkylanilines
(57) Abstract:The invention relates to methods of producing a cyclic boron compounds which may find application in the synthesis of TRANS-2,3-dialkyl-1,4-butandiol, substituted cyclic ketones, alcohols, esters, and other practically important compounds used in thin organic and ORGANOMETALLIC synthesis. The method consists in the interaction of olefins with ethylaminoethanol and magnesium in the presence of two-component catalyst consisting of zirconatetitanate and diisobutylaluminium in an argon atmosphere under normal conditions for 8 h, followed by addition of boron TRIFLUORIDE and stirring for 2 to 6 hours the solvent is tetrahydrofuran. The yield of the target products is 64 - 79%. table 1. The invention relates to methods for cyclic Bioorganicheskaya compounds, specifically, to a method for producing 1-ethyl-TRANS-3,4-dialkylanilines General formula (1):
< / BR>Offer Bioorganicheskaya compounds may find application in the synthesis of threo-2,3-dialkyl-1,4-butandiolov, substituted cyclic ketones, alcohols, esters, and other practically important"Organoboron compounds in organic synthesis", M., "Nauka", 1977, S. 331].The known method [B. M. Mikhailov, V. A. Dorokhov, DAN SSSR, 133, 119, (1960)] obtain 1-ethyl-C-methylrosaniline reaction of isoprene with 1,2-dereviana broadcast scheme
< / BR>By a known method cannot be obtained 1-ethyl-TRANS-3,4-dialkylanilines (1).The known method [R. Koster, G. Schomburg, Angew. Chem., 72. 567 (I960)] for 1-ethyl-3-methylrosanilinium reaction of isoprene with trialkylamine in the presence trialkylborane at a temperature of 140oC scheme
< / BR>The known method does not allow to obtain 1-ethyl-TRANS-3,4-dialkylanilines (1).Thus, in the literature there are no data on Regio - and stereoselective synthesis of 1-ethyl-TRANS-3,4-dialkyl - braziliano.We propose a new method Regio - and stereoselective synthesis of 1-ethyl-TRANS-3,4-dialkylanilines.The essence of the method lies in the interaction - olefins such as 1-hexene, 1-octene, 1-mission with ethylaminoethanol (Et-AlCl2) and metallic magnesium (powder), taken in a molar ratio of Mg : Et - AlCl2= (20-22) : 10 : (10-14), preferably 21:10:12, in the presence of two-component catalyst consisting of circoncision is igeria (i - Bu2AlH), taken in a molar ratio Cp2ZrCl2: Bui2AlH = 1 : (1-3), preferably 1:2, in an argon atmosphere at room temperature (22-23oC) and normal pressure for 8 hours, in tetrahydrofuran as a solvent, and then adding epirate boron TRIFLUORIDE (BF3Et2O) in equimolar number relative to Et - AlCl2and stirring for 2 to 6 hours, preferably 4 hours. The yield of the target products 64-79%. The reaction proceeds according to the scheme
< / BR>The reaction is accompanied by the release of MgCl2and AlF3as by-products.1-ethyl-TRANS-3,4-dialkylanilines are formed only with the involvement of Et - AlCl2and the catalytic system (Cp2ZrCl2+ i - Bu2AlH). In the presence of other aluminum compounds (e.g., i - Bu3Al, Et3Al, AlH3i - Bu2AlCl) or other catalysts (e.g., TiCl4, Zr(OBnu)4, Zr(ACAC)4, Zr(OPir)4, Ti(OBnu)4target products (1) are not formed.The conduct of a specified reaction in the presence of catalyst is more than 5 mol.% in relation to the magnesium does not lead to a significant increase in the yield of the target product. And reduced catalytically active sites in the reaction mass. Experiments were performed at room temperature (22-23oC). At a higher temperature (for example, 60oC) increases the amount of seal products, at a lower temperature (for example, 0oC) decreases the reaction rate. Changing the ratio of initial reagents in the direction of increasing the content of the olefin or EtAlCl2in relation to the magnesium does not lead to a significant increase in the yield of the target product. Reduction of the olefin or Et-AlCl2in relation to the magnesium reduces the yield of the target products.Significant differences of the proposed method:
1. The proposed method is based on the use of a - olefins, metal magnesium, Et - AlCl2and BF3OEt2in the presence of zirconium bearing catalyst. The reaction proceeds at room temperature (22-23oC). In the known method are used trialkylamines, isoprene and trialkylborane. The reaction proceeds at 140oC.The proposed method allows to obtain with high Regio - and stereoselectivity individual 1-ethyl-TRANS-3,4-dialkylanilines under mild conditions from available reagents.The method is illustrated by the following examples:
Example 1. In steklyannoj), 20 ml of dry THF, 21 mmol of 1-hexene, 12 mmol Et - AlCl2and a catalyst consisting of 0.3 mmol Cp2ZrCl2and 0.6 mmol i-Bu2AlH in 2 ml of dry THF, stirred for 8 hours at room temperature (22-23oC) add 12 mmol BF3Et2O, stirred for 4 hours. Get an individual 1-ethyl-TRANS-3,4-dialkylanilines. The yield of the target product was determined by oxidation of (1) known method [I] using alkaline hydrogen peroxide. In the oxidation of 1-ethyl-TRANS-3,4-dialkylanilines formed threo-2,3-di(n-butyl)-1,4-butanediol (2) according to the scheme:
< / BR>An NMR spectrum13C , M. D.) threo-2,3-di(n-butyl)-1,4-butanediol (2): 60.86 t (C1), 42.52 d (C2), 29.39 t (C3), 30.08 t (C4), 23.10 t (C5), 14.17 (C6).Other examples of the method shown in the table.The reaction was carried out at room temperature (22-23oC) in THF. In other solvents (ether, dioxane), the yield of the target products and the selectivity of the reaction are plummeting. In the aromatic (benzene, toluene) and aliphatic (hexane, cyclohexane) solvents the reaction is not. The temperature rise is impractical because it does not increase the yield of the target products. At lower temperatures snijaetsa-olefins interact with ethylaminoethanol (Et-AlCl2) and metallic magnesium, taken in a molar ratio of Mg : Et - AlCl2= (20 - 22) : 10 : (10 - 14), in the presence of two-component catalyst consisting of zirconatetitanate (Cp2ZrCl2), in the amount of 2 to 5 mol. % relative to magnesium, and diisobutylaluminium (i-Bu2AlH), taken in a molar ratio Cp2ZrCl2: i-Bu2AlH = 1 : (1 - 3), in an argon atmosphere under normal conditions in the presence of tetrahydrofuran as a solvent and then adding epirate boron TRIFLUORIDE (BF3Et2O) in equimolar number relative to Et-AlCl2and stirred for 2 to 6 hours
R2- alkylthiol containing 1-4 carbon atoms, possibly substituted by one or more substituents selected from halogen, hydroxyl, alkoxy, benzyloxy, and means phenylthio or mercapto;
R3- carboxyl, free or converted into a salt or an ester of linear or branched C1-C4-alkyl, or hydroxyalkyl;
R4- radical (CH2)m-SO2-X-R10where X is - NH-, NHCONH-, NHCO-O-; R10is hydrogen or C1-C3-alkyl, m = 0, 1;
the interaction of imidazole formula II
with the corresponding halogen derivatives - a compound of formula III
B is a boron atom;
X1and X2is hydroxyl or X1with X2form together with the boron atom to which they relate, zatem subjected to interaction with the compound of the formula V
X4is a halogen atom
H3CNNCH32C2B9H12which can be used as a component for electrochromic composition
FIELD: chemistry of organometallic compounds.
SUBSTANCE: invention relates to a method for preparing lithium complexes salts of the general formula (I): wherein each radical R3-R6 means hydrogen atom (H) or halogen atom (F, Cl or Br). Method involves mixing a) 3-, 4-, 5-, 6-substituted phenol of the formula (III): wherein R3-R6 have above given values with chlorosulfonic acid in acceptable solvent to yield compound of the formula (IV): ; b) intermediate product of the formula (IV) from the stage a) wherein R3-R6 have values given above is subjected for interaction with chlorotrimethylsilane to yield compound of the formula (II) given in the invention description and obtained product is filtered off and subjected for differential distillation; c) intermediate product (II) from the stage b) is subjected for interaction with tetramethanolate borate lithium (1-) in acceptable solvent and the end product (I) is isolated from it. Invention provides the development of a simple method for synthesis of lithium complex salts.
EFFECT: improved preparing method.
3 cl, 4 ex
FIELD: polymerization catalysts.
SUBSTANCE: invention relates to novel organometallic compounds and to olefin polymerization catalytic systems including such organometallic compounds, and also to a method for polymerization of olefins conduct in presence of said catalytic system. Novel organometallic compound is prepared by bringing into contact (i) compound of general formula I: (I), where Ra, Rb, Rc, and Rd, identical or different, represent hydrocarbon groups; and (ii) Lewis acid of general formula MtR
EFFECT: enabled preparation of novel olefin polymerization cocatalysts, which reduce use of excess cocatalyst relative to alkylalumoxanes, do not lead to undesired by-products after activation of metallocene, and form stable catalytic compositions.
14 cl, 1 tbl, 32 ex
FIELD: chemistry of organophosphorus compounds.
SUBSTANCE: invention relates to compounds with the bond C-P, namely to phosphorus-boron-containing methacrylate that can be used as inhibitor of combustion of polyvinyl alcohol-base film materials. Invention describes phosphorus-boron-containing methacrylate of the following formula: wherein n = 4-8. Polyvinyl alcohol films modified with indicated phosphorus-boron-containing methacrylate shows the enhanced refractoriness, rupture strength up to 206 kgf/cm2, water absorption up to 240% and relative elongation up to 12%.
EFFECT: valuable properties of substance.
1 tbl, 2 ex
FIELD: chemistry of complex compounds.
SUBSTANCE: invention relates to new derivatives of boranocarbonate of the formula (I): wherein X1 means -H; X3 and X2 mean similar or different substitutes that are taken among the group consisting of -H, -NHxRy at x + y = 3, or -R wherein R means substitute that is bound with nitrogen or boron atom through carbon atom, respectively, and represents methyl or ethyl group; Y means group -OH, -OH2, -OR or -NHR wherein R means substitute that is bound with nitrogen or oxygen atom through carbon atom, respectively, and represents methyl or ethyl group; or their salts. Invention provides using prepared compounds as source of carbon monoxide (CO) and as a reducing agent in preparing carbonyl metal complexes in an aqueous solution. Also, invention involves a method for preparing borane carbonate and a method for reducing with using H3BCO as a reducing agent.
EFFECT: improved method for preparing.
20 cl, 14 ex
FIELD: organic synthesis.
SUBSTANCE: invention relates to organoboron compounds technology, in particular to aminoboranes and, more specifically, to trimethylaminoborane, which can be used as reducing and hydroboronizing agents as well as in color photography, in magnetic film manufacture, and as fuel additive to decrease amount of deposits in combustion chamber. Method comprises reaction of trimethylamine with gaseous diborane in organic solvent at reduced temperature. Solvent is selected from aliphatic, cycloaliphatic, and aromatic hydrocarbons with melting temperature not higher than -20°C. Reaction is conducted at temperature from -30°C to 0°C, preferably from -15 to -5°C, at trimethylamine-to-solvent volume ratio 1:(1/5-3.5).Proposed method simplifies preparation procedure owing to eliminated laborious solvent removing vacuum distillation stage and stage wherein of aqueous alkali metal hydroxide is introduced to stabilize aminoborane. Yield of desired product, characterized by high purity, achieves 95-98.6%, which is essentially higher than, for example yield (86%) of morpholinoborane regarded as prototype compound in a known process.
EFFECT: enhanced economical efficiency of process.
3 cl, 4 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to technology for preparing organoboron compounds, in particular, to the improved method for preparing 9-borabicyclo[3.3.1]nonane. Method for preparing 9-borabicyclo[3.3.1]nonane is carried out by interaction of diborane with 1,5-cyclooctadiene in 1,4-dioxane medium at simultaneous feeding diborane and 1,5-cyclooctadiene at the rate necessary for maintaining the molar ratio 1,5-cyclooctadiene : diborane = (1.9-2.04):1.0, respectively, during all through reaction. The process is carried out in the volume ratio 1,4-dioxane : 1,5-cyclooctadiene = (2.2-4.0):1.0 and at temperature 11-25°C. In preparing 9-borabicyclo[3.3.1]nonane the reaction mass is kept at temperature 65-102°C. The invention provides simplifying technology in preparing 9-borabicyclo[3.3.1]nonane due to exclusion the preliminary preparing borane complex and additional recrystallization of 9-borabicyclo[3.3.1]nonane, enhancing yield of the end product up to 91.0-93.5% of the high quality (the content of basic substance is 99.1-99.9%, melting point is 152-156°C), and possibility for creating the wasteless manufacturing. Method for preparing 9-borabicyclo[3.3.1]nonane shows technological simplicity in its realization and economy profit in its realization in industrial scale.
EFFECT: improved preparing method.
4 cl, 4 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to technology for preparing organoboron compounds, in particular, pinacol borane (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) representing a monofunctional hydride-borating agent for alkenes and alkynes and for Suzuki's cross-coupling reaction also. Method is carried out by interaction of pinacol (2,2,3,3-tetramethylethylene glycol, 2,3-dimethyl, 2,3-butanediol) with borane reagent in the presence of a solvent and the following isolation of the end product. Gaseous diborane is used as a borane reagent and the process is carried out in diethyl ether medium at range of temperatures 5-36°C, and the process is carried out in the mole ratio of reagents pinacol : diborane = 1:(0.45-0.55), respectively; or the method is carried out by interaction of pinacol with borane reagent and the following isolation of the end product wherein gaseous diborane is used as a borane reagent, and the process is carried out in pinacol melt at temperature ranges 40-80°C. The process is carried in the mole ratio of reagents pinacol : diborane = 1:(0.45-0.55), respectively. Method provides preparing pinacol borane with high yield 90-95% and high purity 99.5-99.8%. Method shows technological simplicity and economy profit in realization in the industrial scale.
EFFECT: improved preparing method.
3 cl, 4 ex
FIELD: organic chemistry, pharmaceuticals.
SUBSTANCE: disclosed method for production of [R-(R*,R*)}]-2-(4-fluoriphenyl)-β,δ-dihydroxy-5-(1-methyl)-3-phenyl-4-[(phenylamino)-carbonyl]-1H-heptanoic acid semi-calcium salt (atorvastatin) of formula XII includes reaction of preprepared compound of formula Xa with compound of formula IV in solvent mixture selected from group containing xylene, cyclohexane, methyl-tert-butyl ether, diisopropyl ether, acetonitrile, in presence of catalyst selected from group containing pivalic acid, trifluotomethylsulfonic acid, methanesulfonic acid or p-toluenesulfonic acid to form intermediate of formula XIa , followed by hydrolysis of formula XIa and calcium salt production to form target product of formula XII. Claimed compound represents enzyme hydroxymethylglutaryl-CoA reductase inhibitor, and thereby is useful as hypolipidemic and hypocholesteronemic agents.
EFFECT: new method for atorvastatin synthesis.
7 cl, 2 dwg, 9 ex
FIELD: polymer materials.
SUBSTANCE: invention provides luminescent material showing semiconductor properties and being product of complex polymerization in glow discharge, which is formed as a supported polymer layer located either between electrodes or on any of electrodes. Starting pyrromethene complex is difluoroborate complex of 1,3,5,7,8-pentamethyl-2,6-diethylpyrromethene (Pyrromethene 567). Method of preparing luminescent semiconductor polymer material comprises glow-discharge polymerization for 2 to 120 min of Pyrromethene 567 vapors at temperature preferably 250-350°C, pressure 10-1 to 10-2 Pa, and discharge power 0.5-3 W. Resulting luminescent polymer is characterized by thickness preferably 0.001-10 μm, conductivity 1·10-10 to 5·10-10 Ohm-1cm-1 (20°C), luminescence emission maximum in the region of 540-585 nm at band halfwidth 55-75 nm. Polymer is obtained with quantum yield 0.6-0.8 and is designed for creation of film light-emitting devices.
EFFECT: improved performance characteristics of material.
13 cl, 3 ex
FIELD: physical analytical methods.
SUBSTANCE: invention relates to bioanalytical methods involving dye-labeled indicators. Bioanalytical method without separation is provided directed to measure analyte obtained from biological liquid or suspension, wherein are used: analyte microparticles as first biospecific reagent; and second biospecific reagent labeled with biphotonic fluorescent dye based on dipyrromethene boron difluoride containing at least one water solubility imparting group selected from ammonium salt and sulfonic or carboxylic acid alkali metal salt and at least one chemically active group selected from carboxylic acid, reactive carboxylic acid ester, carboxylic acid anhydride, maleimide, amine and isothiocyanate. In the method of invention, laser is focused onto reaction suspension and biphotonically excited fluorescence from individual microparticles (randomly flowing or oriented by pressure provided by emission of exciting laser through focal volume of laser beam).
EFFECT: increased efficiency of bioanalyses.
5 cl, 5 dwg, 5 tbl, 25 ex