The way to obtain tert-butylaniline
(57) Abstract:The invention relates to a method for producing tert-butylaniline that can be used as a selective reducing agent in aqueous and organic media. Describes how to obtain tert-butylaniline, including interaction of tert-butylamine with boranova the complex tetrahydrofuranyl or dimethylsulfide in the environment of the solvent, followed by separation of the final product, and the process is conducted at a molar ratio of bananowy complex: tert-butylamine, is equal to 1:0,95-1,2 respectively. The solvent may be tetrahydrofuran or dimethyl sulfide. 5 C. p. F.-ly. The invention relates to a technology for alkylamidoamines, in particular the production of tert-butylamine, which can be used as a selective reducing agent in aqueous and organic media.A method of obtaining aminoborane, in particular tert-butylaniline, including the interaction of alkali metal borohydride, acid and water in the presence of tert-butylamine (U.S. Pat. USA 3127448, 31.03.64).The known method is as follows. At 20oWith a mix of 9.5 ply 1.5 mol of water. Stirring is continued until cessation of hydrogen evolution, the mixture is filtered. The filtrate is evaporated to dryness in a vacuum. The solid residue is extracted with diethyl ether, receiving 19 g of tert-butylamine with a melting point 92-94oC. the product Yield is 43.8%.However, the known method of obtaining tert-butylamine has the following disadvantages:
low yield of finished product;
the low quality of the obtained tert-butylaniline, which was evaluated by its melting point 92-94oWith; it is known that more pure tert-butylamine has a melting point of from 93 to 97oWith that complies with the basic substance content not less than 97% (see Fluka, Chemical reagents for analytical work, 2001/2002);
use in reactions such starting components, as sodium borohydride and boron anhydride leads to the formation of large amounts of salt waste, which requires additional costs for their disposal.The closest analogue to the claimed invention in its technical essence and the achieved result is a method of obtaining aminoborane, including the interaction of sodium borohydride salt of the amine in the organic p is nborn (example 2). The reaction is carried out at room temperature or below between the amine salt, in particular the hydrochloride tert-butylamine and sodium borohydride in dimethoxyethane taken in approximately equal molar proportions. The duration of reaction of 0.5-1.5 hours. Upon completion of the reaction, the obtained solution is filtered, remove dimethoxyethane and receive tert-butylamine with a melting point 92-94oC. However, the example does not specify the output of the finished product. Although in another example, describing the receipt of dimethylaminoborane, output is 87%. It should be noted that in such syntheses yield depends on the nature of amines and their salts, as well as the solubility of reagents. In this method of obtaining aminoborane, in particular tert-butylaniline, as a solvent used dimethoxyethan, in which sodium borohydride is dissolved bad, so the yield of the target product cannot practically exceed 90%. The content of the basic substance in the final product is also not included, however, for the specified melting temperature (92-94o(C) the content of the basic substance is less than 97%.Furthermore, the presence of salt waste and the use of relatively expensive solvent - dimethoxyethane - conditions.To eliminate the above disadvantages of the task was to develop a new method of obtaining tert-butylaniline with a high content of basic substance, with high output and cost-effective when implemented in an industrial environment.The problem is solved developed method to obtain tert-butyl-aminoborane, including interaction of tert-butylamine with boron-containing compound in the environment of the solvent, followed by separation of the final product, the boron compounds are used bananowy complex - tetrahydrofuranyl or dimethylsulfide - and the process is conducted at a molar ratio of bananowy complex: tert-butylamine, is equal to 1: (0,95-1,2).When using tetrahydrofurane (THF-borane) as a solvent during the process is mainly used tetrahydrofuran. When using dimethylsulfide as a solvent during the process is mainly used dimethyldisulfide. However, this does not preclude the use of other solvents, such as aromatic, aliphatic hydrocarbons, simple aliphatic and cyclic ethers, esters carbonex:tert-butylamine, equal to 1:(from 0.95 to 1.2). The deviation from the selected molar ratio bananowy complex: tert-butylamine less than 1:0,95 reduces the yield of the target product due to incomplete entry into the reaction boranova complex, in particular tetrahydrofurane or dimethylsulfide. In addition, when using recycle THF or dimethyl sulfide in the subsequent syntheses is the decline in the quality of the finished product due to the interaction of tert-butylamine with the products of decomposition of the unreacted THF-borane or dimethylsulfide respectively. The increase in the ratio over 1:1,2 is impractical because the indicators in the quality and yield of the finished product are not changed, this increases the time of the process and the energy consumption for cooling the reaction mixture, which increases the cost of the final product.Studies have shown that during the process at the desired molar ratio of the reactants, it is preferable to use a concentration of tetrahydrofurane from 0.01 to 2.9 M, in the case of dimethylsulfide is from 0.01 to 10.2 M Concentration of THF-borane, equal to 2.9 M, and the concentration of dimethylsulfide equal to 10.2 M are the maximum for the data of the second complex less than 0.01 M impractical because it gives no advantages in quality and yield of the final product, but increases the energy consumption for cooling of the reaction mixture and heating during distillation of tetrahydrofuran or dimethyl sulfide, and increases during the process.The temperature of the process ranges from minus 30 to plus 40oC, preferably from minus 20 to plus 30oC. carrying out the process at temperatures below minus 30oSince it is not economically feasible, because it does not increase the yield of tert-butylamine or improve its quality, but increases the cost of the final product due to the increase in energy consumption for cooling of the reaction mixture. Increasing the synthesis temperature above 40oWith leads to the decomposition of THF-borane or dimethylsulfide and interaction of tert-butylamine with the products of decomposition, which reduces the quality and yield of the finished product.In case of carrying out the process at temperatures below 10oAfter completion of dosing of the reagents, the reaction mass is preferably stand for stabilization at a temperature selected from a range from 10 to 60oC. thus obtain tert-butylamine with high stability - the main content is the new method allows to obtain tert-butylamine with a high content of the basic substance of 99.1-99.5% and the yield of the target product 93-96,6% of theory, however tert-butylamine has high stability.Below are examples of the proposed method.Example 1.Obtain tert-butylaniline carried out in a reactor equipped with a stirrer, a thermometer and a funnel for feeding tert-butylamine. Before loading the reactor is blown dry with nitrogen. Charged to the reactor 0.4 mol (200 ml) 2 M THF-borane containing 34.4 g THF-borane and 143,6 g of THF, and cooled it to minus 10oC. is poured Into the funnel 0.44 mol (46,3 ml) of tert-butylamine and submit it to the reactor at such a speed that the temperature of the reaction mixture was maintained below minus 10oC. After the filing of tert-butylamine reaction mass is heated to 20oC and maintained at this temperature with stirring until complete stabilization. Then the tetrahydrofuran is distilled off under reduced pressure. The output of tert-butylamine to 96.6% of theory, the basic substance content of 99.5%, the melting point of 97.5oC.Example 2.Obtain tert-butylaniline carried out in a reactor equipped with a stirrer, thermometer and funnel that feeds dimethylsulfide. Before loading the reactor is blown dry with nitrogen. In the reactor load of 1.05 mo is l (196 ml) 5.1 M of dimethylsulfide in dimethyl sulfide and submit it to the reactor with such speed, to the temperature of the reaction mixture was maintained below minus 10oC. After the filing of tert-butylamine reaction mass is heated to 20oC and maintained at this temperature with stirring until complete stabilization. The output of tert-butylamine after separation of the reaction mass to 96.6% of theory, the basic substance content of 99.5%, the melting temperature is 97.6oC.Example 3.Obtain tert-butylaniline carried out analogously to example 1. The temperature of the reaction mixture in the synthesis support about 20oC. the Molar ratio of THF-borane: TBA is 1:1,1. The THF concentration of 1 M boraneReceive tert-butylamine with a basic substance content of 99.4%; the yield of the final product 96%, melting point of 97.5oC.Thus, it was proved experimentally that the proposed new method allows
to obtain stable tert-butylamine with high technical and economic indicators compared to the prototype (the content of the basic substance in the target product to 99.1-99.5% pure, melting point of 97.5-98oWith the release of the final product 93-96,6%);
to simplify the process by eliminating time-consuming stage of the technology.Sources of information
1. U.S. patent 3127448, 31.03.64.2. Flucka. Chemical reagents for analytical work 2001/2002.3. The Japan Patent 81158792, 07.12.81. 1. The way to obtain tert-butylaniline, including interaction of tert-butylamine with boron-containing compound in the environment of the solvent, followed by separation of the final product, characterized in that boron compounds are used bananowy complex - tetrahydrofuran-borane or dimethyl sulfide-borane and the process is conducted at a molar ratio of bananowy complex: tert-butylamine, is equal to 1:0,95-1,2 respectively.2. The method according to p. 1, characterized in that as boranova complex using tetrahydrofuran-borane with a concentration of 0.01 to 2.9 M3. The method according to p. 1, characterized in that as boranova complex use of dimethyl sulfide-borane with a concentration of 0.01-10,2 M4. The method according to PP.1 and 2, characterized in that the solvent used tetrahydrofuran.5. The method according to PP.1, 3, characterized in that the solvent used dimethyldisulfide.6. The method according to PP.1-5, characterized in that the process is carried out at a temperature from minus 20 to plus 30C.
where BAS, BAS', BAS"- bioactive ingredients, which may be identical or different; Su and Su' - complexes phenylboric acid; L, L', L" - linkers; n = 0 or 1, three methods for their production, intermediate products used in their synthesis and representing phenylboronic complexing reagents and phenylboronic cross-linking reagents, the method of selection of the desired cell population, as well as set or system containing bioconjugate And, to scroll to the desired population of cells
< / BR>where n is 0 or 1;
m is 0 or 1;
p is 0;
X represents oxygen or sulfur;
Y represents CH, N or NO;
W represents oxygen or H2;
And represents N or C(R2);
G represents N or C(R3);
D represents N or C(R4)
provided that not more than one of A, G and D represents nitrogen, but at least one of Y, a, G, and D represents nitrogen or NO;
R1represents hydrogen or C1-C4-alkyl;
R2, R3and R4are independently hydrogen, halogen, C1-C4-alkyl, C2-C4alkenyl,2-C4-quinil, aryl, heteroaryl, including five - or six-membered aromatic ring with 1 or 2 nitrogen atoms, as well as furyl or morpholyl, HE OS1-C4-alkyl, CO2R1, -CN, -NO2, -NR5R6or R2and R3or R3and R4accordingly, together with part a and G or G and D southwest a hydrogen, WITH1-C4-alkyl, C(O)R7C(O)OTHER8WITH(O)OR9, SO2R10, -NR5R6, (CH3)3Si and phenyl, or may together represent (CH2)jQ(CH2)kwhere Q represents a bond; j is 2 and k is 0 to 2;
R7, R8, R9, R10and R11are independently C1-C4-alkyl, NH2, aryl or its enantiomer,
and their pharmaceutically acceptable salts, and methods for their preparation, intermediate compounds and pharmaceutical compositions, which has an activating effect against nicotine7-acetylcholine receptors and can be used for the treatment and prevention of psychotic disorders and disorders of the type of lower intellectual
< / BR>or their salts, where in the formula Ia W represents N or C-CO-R, where R denotes HE OC1-C6alkyl or NR3R4where R3and R4- N or C1-C6alkyl, or formula Ib Az denotes imidazopyridine and in both formulas Ia and Ib R1represents C1-C4alkyl, R2denotes phenyl fragment or 2,5-cyclohexadiene-3,4-ridin-1 silt fragment
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