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WO2013048280A1 - Procédé de production sélective de n-méthyl-para-phénétidine - Google Patents

Procédé de production sélective de n-méthyl-para-phénétidine Download PDF

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Publication number
WO2013048280A1
WO2013048280A1 PCT/RU2011/000902 RU2011000902W WO2013048280A1 WO 2013048280 A1 WO2013048280 A1 WO 2013048280A1 RU 2011000902 W RU2011000902 W RU 2011000902W WO 2013048280 A1 WO2013048280 A1 WO 2013048280A1
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Prior art keywords
para
catalyst
methyl
phenetidine
alkylation
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Russian (ru)
Inventor
Александр Юрьевич ФРОЛОВ
Юрий Александрович ИВАНОВ
Николай Григорьевич БЕЛЯКОВ
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ZAKRITOYE AKTSIONERNOE OBSHESTVO "IFOHIM"
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ZAKRITOYE AKTSIONERNOE OBSHESTVO "IFOHIM"
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups

Definitions

  • the invention relates to chemical-technological processes, and in particular to methods for catalytic alkylation of aromatic amines and nitro compounds.
  • the invention relates to a method for producing ⁇ -methyl-para-phenethidine ( ⁇ -methyl-para-ethoxyaniline; ⁇ -methyl-para-aminophenetole) from para-phenetidine (para-aminophenetole; para-ethoxyaniline) or para-nitrophenetole (1-ethoxy- 4-nitrobenzene) and methanol in the presence of hydrogen or without hydrogen on a heterogeneous catalyst.
  • the proposed method allows the use of existing industrial plants used to obtain aniline and N-methylaniline.
  • ⁇ -methyl-para-phenethidine is currently used as an antiknock additive or additive to motor fuel [US Pat. 2 309 943, Russian Federation, IPC ⁇ 07 ⁇ 217 / 82, ⁇ 07 ⁇ 235 / 24, C10L1 / 223, C10L1 / 224.
  • N-methyl-para-phenethidine was obtained in two ways: from -methyl-Y-acetyl-para-phenethidine by boiling with sulfuric acid, adding sodium hydroxide and subsequent extraction with toluene, as well as according to the procedure described in [Weigant Hilgetag. Experimental Methods in Organic Chemistry.-Moscow: Chemistry, 1964.- 944 s], using dimethyl sulfate, sodium bicarbonate, sodium hydroxide or potassium with a yield of 50% of theoretical.
  • these production methods are preparatory in nature and unacceptable for the production of ⁇ -methyl-para-phenethidine under conditions of large-tonnage production.
  • the temperature of the process was determined by the boiling point of a solution of paraphenetidine in a specific aliphatic alcohol. In this way, N-amyl-para-phenethidine, ⁇ -decyl-para-phenethidine, N-cyclohexyl-para-phenethidine were obtained. The yield of target products was 85-95% of theoretical.
  • the method Since it is indicated that the method does not allow the reaction to shift toward monoalkylanilines, it is unacceptable for us, since if it is used to produce ⁇ -methyl-para-phenethidine, the situation will only worsen.
  • the catalyst used in the method has an acidic character, which can contribute to the hydrolysis of the ether group of para-phenetidine.
  • the total yield of aromatic amines is up to 99.5%, product productivity is up to 0.4-1.3 g / g h.
  • the method allows, depending from the ratio of reagents used, change the ratio of the resulting N-methyl-substituted and unsubstituted aromatic amines [US Pat. 2207335, Russian Federation, IPC 7 ⁇ 07 ⁇ 211 / 48, ⁇ 07 ⁇ 21 1/46, ⁇ 07 ⁇ 209 / 36.
  • a method of producing aromatic amines by reduction of the corresponding nitro compounds / Vinokurov V.A., Stytsenko V.D. et al., JSTs 2001111547/04, claimed 04/28/2001, publ. 06/27/2003].
  • ⁇ -methylaniline by alkylation of nitrobenzene with formaldehyde or a mixture thereof with methanol on copper oxide-containing catalysts at 220-260 ° C.
  • the molar ratio of nitrobenzene: alkylating agent is usually 1: (2.5-6.0), and the optimal molar ratio of formaldehyde to methanol in the alkylating agent is 1: 1, and formaldehyde can be used in the form of its aqueous solution in the presence of hydrogen with a molar the ratio of nitrobenzene to hydrogen 1: (3, 0-6.0) on copper oxide catalysts promoted with oxides of manganese, chromium, iron and cobalt, on a carrier - alumina.
  • the proposed method allows for the conversion of nitrobenzene to 100% and the yield of the target product - N-methylaniline 80-88%, to simplify and reduce the cost of technology, reduce energy consumption.
  • a significant drawback of the method is the use of an aqueous solution of formaldehyde, which necessitates the disposal of a large amount of additional water, which inevitably increases the cost of production, as well as the propensity of formaldehyde to polymerize.
  • ⁇ -methylaniline from nitrobenzene, methanol and hydrogen in the gas phase on a copper-containing catalyst comprising zinc and chromium compounds.
  • the process is carried out in two stages in two series-connected contact devices, in each of which nitrobenzene and methanol are supplied in a mixture or separately: nitrobenzene - to the first device, and methanol - to the second device, using layer-by-layer catalyst loading with the first contact device the creation of a "frontal layer", the temperature in which should not exceed 350 ° C, a volume of 10-50% of the total catalyst used in this contact apparatus, the following composition: copper oxide May 37-40. %, chromium oxide May 18-20. %, zinc oxide May 20.
  • a known method of producing ⁇ -methylaniline by reductive alkylation of nitrobenzene or its mixture with aniline methanol in the gas phase on an oxide copper-chromium catalyst In this case, reductive alkylation is carried out in medium of a mixture of hydrogen and carbon dioxide, taken in a molar ratio of about 3: 1, obtained by gas-phase condensation of methanol with water.
  • a mixture of hydrogen and carbon dioxide obtained in a separate contact apparatus is directed to reductive alkylation.
  • Known liquid-phase catalytic method for the alkylation of aromatic amines includes the alkylation of aromatic amines in the presence of hydrogen and lower alcohols at a temperature of 50-70 ° C on a heterogeneous catalyst.
  • a distinctive feature of the method is the alkylation of amines with formalin in a reactor with a reaction zone filled with a catalyst consisting of a block of highly porous cellular support based on alumina with a porosity of at least 70-95% and the active component is palladium with a mass content of 1.3-2%.
  • the method allows mainly to obtain monomethylaniline, to reduce the content of the active component - palladium in the catalyst, and also to reduce the reaction pressure and hydraulic resistance of the catalyst layer.
  • a known method of producing ⁇ -methylaniline by catalytic hydrogenation of nitrobenzene with hydrogen in the presence of methanol on copper-chromium catalyst is carried out sequentially in two reaction zones at 160-200 ° C in the first zone until nitrobenzene is completely converted and 210-240 ° C in the second zone to aniline conversion of at least 93% with a molar ratio of nitrobenzene: methanol: hydrogen 1 :( 2-4) :( 4-10).
  • the method allows to obtain the target product with a yield of more than 92%.
  • [Pat. 2223258, Russian Federation IPC 7 ⁇ 07 ⁇ 21 1/48, ⁇ 07 ⁇ 209 / 36 The method of obtaining ⁇ -methylaniline / Yu.D. Batrin, M.K. Starovoitov et al. -JYS! 2003100842/04, claimed 01/15/2003, publ. 02/10/2004].
  • Rj is a radical selected from H, CH3, C2H5, R.2 is a radical selected from H, CH3, C2H5, R-h is H or a radical CH 3, C 2 H 5 on the catalyst STC series at a temperature of 230-270 ° C, characterized in that, in order to save energy, add to the initial reaction mixture
  • R3 is H or a CH radical, C 2 H 5, whereby the required reactor temperature is maintained.
  • methanol is used as a hydrogen source for nitrobenzene reduction at a molar ratio of nitrobenzene: methanol 1: 4-10.
  • SUBSTITUTE SHEET (RULE 26) 170-300 ° C and a catalyst temperature of 350-450 ° C in a two-stage reactor by catalytic reduction of nitrobenzene, followed by alkylation of aniline with methanol without isolation of aniline in its commercial form at atmospheric pressure on a copper oxide catalyst, including zinc and chromium compounds.
  • This method is characterized in that the process is carried out in a two-stage reactor, the second stage of which is a cavity adiabatic contact apparatus filled with a granular catalyst.
  • a known catalytic method for the production of secondary cyclic amines by reacting the corresponding primary cyclic amine with low boiling alcohols consists in carrying out reactions in the presence of a catalytic mixture of metallic copper, aluminum oxide and other metal oxides, in connection with which, cyclic amines can be produced cost-effectively.
  • This invention is proposed for the production of ⁇ -methylaniline from aniline and methanol using a stoichiometric excess of alcohol, which greatly increases the conversion of aniline to ⁇ -methylaniline and completely inhibits the formation of ⁇ , ⁇ -dimethylaniline. As a result, a sufficiently pure product is obtained by applying distillation to remove unreacted alcohol and water formed during the reaction.
  • the inter-regeneration run of the catalyst is 250 hours. [Pat. 2580284, USA. The production of secondary aromatic amines / Thomas Jay Deal and others - publ. 12/25/1951].
  • the catalyst contains a large amount of acidic aluminum oxide; therefore, when using this method to obtain itz department desk-methyl-para-phenethidine, hydrolysis of the ester group is very likely.
  • a known method for the production of secondary alkylaromatic amines by direct alkylation of primary aromatic amines with primary aliphatic alcohols is achieved by the use of distillation or crystallization from an appropriate solution.
  • unbranched aliphatic alcohols as an alkylating agent
  • the yield of the target product reaches from 70 to 90%
  • the yield of the target product is 40-50%.
  • Raney nickel is used as an alkylation catalyst. [Pat. 2813124, USA.
  • the disadvantage is the low yield of the secondary amine.
  • a catalyst consisting of copper and chromium and the corresponding formula: Cr » Me » Me, where Me is Cu, Zn, Fe OR Ni, Me is Ba, Ca, Mg OR Mn, Cr.
  • the metal content in the catalyst Cr from 20 to 80% of the mass, Me 1 from 20 to 80% of the mass, Me2 from 0 to 5% of the mass.
  • the yield of ⁇ -methylaniline is 95%. [Pat. 3819709, USA.
  • the disadvantage is the very high pressure during the process.
  • An improved process for the continuous production of ⁇ -alkylarylanilines by reaction between arylamines and monohydric saturated alcohols and / or dialkylethers in the gas phase at a temperature of from 180 to 450 ° C. in the presence of a carrier that contains phosphoric acid.
  • the improvement consists in the use of silicic acid having an internal surface area of from 50 to 500 m / g and containing from 0.1 to 20% by weight of phosphoric acid, as well as the continuous supply of phosphoric acid and / or alkyl phosphate to the catalyst throughout the process .
  • the yield of ⁇ -monoalkylanilines and ⁇ , ⁇ -dialkylanilines is 95-98%. [Pat. 3957874, USA. Continuous production of ⁇ -alkylarylamines / Tony Dokner and others - publ. 05/18/1976].
  • a known method of producing ⁇ -alkylated aromatic amines by co-heating aromatic amines with lower aliphatic alcohols in the presence of phosphoric acid from 0.01 to 1.0 mol, calculated on equivalent nitrogen at a temperature of 150-280 ° C. Subsequently, the resulting liquid phase is separated with the release of ⁇ -alkylated aromatic amine. The duration of the process is from 30 to 130 hours, depending on the starting reagents.
  • a known method of producing ⁇ -alkylated aromatic amines by carrying out the reaction between an aliphatic alcohol having from 1 to 6 carbon atoms and an aromatic amine having 1 hydrogen atom, bonded to nitrogen in the amino group.
  • the reaction proceeds in the vapor phase at a temperature of 250-450 ° C in the presence of a catalyst consisting of alumina treated with hydrofluoric acid, with a yield of monoalkylamines of about 80%, with a conversion of the starting amines of about 60%.
  • tertiary amines were formed with a yield of about 10%.
  • Aromatic amines that can be alkylated according to the conditions described in this patent are: aniline, o-, m-, or p-toluidine, o-, m-, or p-xylidine, o-, m-, or p- anisidine and others. In this way, monoethyl-m-toluidine (48-92%) and diethyl-m-toluidine (8-22%) were obtained.
  • the advantage of this method is the possibility of using relatively low temperatures for the reaction, and very significant drawbacks in mass production are the high cost of aldehydes and ketones and their tendency to polymerization.
  • the patent does not indicate such important process characteristics as the load of the reaction mixture on the catalyst and the inter-regeneration run time of the catalyst. However, in this case, this is not necessary, since it is already evident from the composition of the obtained catalysis that the method is not very suitable for industrial use because of the great difficulties in separating the catalysis of this composition into components. [Pat. 4029707, USA. Production of ⁇ -alkylated aromatic amines / Charles W. Hargis. - publ. 06/14/1977].
  • a known method of producing ⁇ -alkylated aromatic amines by carrying out the reaction between aliphatic or cycloaliphatic alcohols and aromatic amines at elevated temperature and elevated pressure in the presence of catalysts. The reaction is carried out in the presence of phosphorus oxyhalides. The temperature at which the alkylation process takes place is 200-400 ° C, the pressure is 3-20 MPa. The yield of the target products for--alkylanilines is 43-46%, for ⁇ , ⁇ -dialkylanilines 3-8%. The remaining amount is the unreacted aromatic amine. [Pat. 4268458, USA. Process for the production of ⁇ -alkylated aromatic amines / Werner Schulte-Hermann, Heinz Hemmerich. - publ. 05/19/1981].
  • a known method for producing para-substituted aromatic amines by conducting a para-substitution reaction of an aromatic carbamic acid ester with an aromatic amine in the presence of aliphatic or cycloaliphatic alcohols. The reaction is carried out at a temperature of 100-260 ° C, at reduced or atmospheric pressure.
  • the para-substitution reaction according to the above method, the following compounds were obtained: 4-tert-pentylaniline (83% of theory) and 4-tert-butylaniline (80% of theory). [Pat. 4359584, USA. Production of p-substituted aromatic amines / Franz Merger, Gerhard Nestler. - publ. November 16, 1982].
  • a known method of producing ⁇ -alkyl and ⁇ , ⁇ -dialkylaniline by carrying out the alkylation of aniline with alcohols, preferably with methanol or ethanol, in the presence of a ZSM-5 catalyst The use of the modified ZSM-5 catalyst enhances the selectivity for N-alkylation, while at the same time, the formation of undesirable by-products such as toluidines is suppressed.
  • the molar ratio of silicon oxide to alumina in the catalyst is from 20: 1 to 700: 1, more preferably a ratio of from 30: 1 to 200: 1.
  • the aluminosilicate can be modified using alkaline, alkaline earth or transition metal ions, preferably cesium, potassium, magnesium and iron.
  • the reagents are contacted in the presence of a catalyst at a temperature of from 300 to 500 ° C, at a pressure of from 1 to 3 atm. and when the molar ratio of alcohol to aniline is from 1 to 6.
  • the feed rate is from 0.2 to 4 g of raw material / g of catalyst / hour.
  • ⁇ -methylaniline (51-89%) and ⁇ , ⁇ -dimethylaniline (9-40%) were obtained, depending on the type used catalyst.
  • the known method of gres collapse-alkylation of anilines by conducting in the vapor phase the reaction of anilines with lower alcohols or dialkyl ethers at elevated temperatures and in the presence of pentasilic type zeolite catalysts containing protons and having an S1O2 / AI2O3 ratio of at least 60.
  • the temperature at which the reaction proceeds is 220-370 ° C.
  • a gas-phase process which includes the step of reacting a primary aromatic amine (aniline or substituted aniline) with an alcohol having from 1 to 5 carbon atoms or with ether under conditions of ⁇ court founded ⁇ -alkylation using gallosilicate.
  • the reaction proceeds at a temperature of from 200 to 500 ° C and atmospheric pressure.
  • ⁇ -methylaniline is obtained.
  • the selectivity of the alkylation process is from 40 to 90%, depending on the catalyst used and the process conditions. [Pat. 5159115, USA. Catalytic gas-phase process of ⁇ -alkylation of aromatic primary amines / Peter G. Pappas et al. - publ. 10/27/1992].
  • the aim of the invention is to provide the possibility of obtaining ⁇ -methyl-para-phenethidine with a purity of not less than 98% and a high yield, allowing you to organize highly profitable, multi-tonnage production.
  • BASF Cu-E403TR catalyst produced by composition: copper chromite 67-71%), copper 11-15%, copper oxide 8-21%, graphite 0-4%, chromium oxide (3+) 0-3%; BASF production catalyst Cu-0203T 1/8 composition: copper oxide 75-100%, chromium oxide (3+) 0.1-1%; BASF production catalyst Cu-E406TR composition: Cu-36%, Cr-31%, Ba-6%.
  • Example 1 In a quartz tube with an inner diameter of 45 mm, 100 ml of copper-chromium catalyst and 100 ml of inert material (broken quartz, ceramic Rashig rings) used to improve the evaporation of the reagents were loaded. Nitrogen was passed through the tube at a rate of 200 ml / min and heated with an electric heater to a temperature of 200 ° C. At this temperature, catalyst recovery was started by feeding a 5% aqueous solution of methanol into the tube so that the temperature in the catalyst layer did not rise above 300 ° C. After completion of the recovery (the cessation of heat generation and a drop in temperature in the catalyst layer to 200 ° C) for another 1 hour, pure methanol vapor was passed through a quartz tube.
  • inert material broken quartz, ceramic Rashig rings
  • Methanol was replaced with a mixture consisting of 1 molar part of para-nitrophenetole and 5 molar parts of methanol, which was supplied at a rate of 0.125 - 0.3 L / h and the synthesis of irri special fit-methyl-para-phenetidine was carried out.
  • Contact gases were cooled in a glass ball cooler and collected in a collector.
  • the condensate was divided into aqueous and organic layers in a phase separator.
  • the organic layer was analyzed by GLC.
  • the contacting process was conducted continuously until the appearance in the organic layer 5-% para-nitrophenetol catalysis. Then the flow of the reaction mixture was stopped and the installation was switched to the catalyst regeneration mode.
  • the collected organic layer was separated in a batch distillation unit, intermediate products and methanol were returned for contacting.
  • Commodity ⁇ -methyl-para-phenethidine was obtained with a concentration of 98%.
  • Example 2 As in example 1, but instead of para-nitrophenetol, para-phenetidine was used.
  • the load of the mixture on the catalyst is 0.3-0.4 l / h.
  • the catalyst in the oil layer contains 0-8% para-phenetidine, 90-95% N-methyl-phenethidine and 1-5% ⁇ , ⁇ -dimethyl-para-anisidine. Received ⁇ -methyl-para-phenethidine with a yield of 85-90%).
  • Example 3 As in example 1, the process was conducted in a stream of nitrogen.
  • Example 4 As in example 1, the process was conducted in a stream of hydrogen.
  • Example 5 As in example 2, the process was conducted in a stream of nitrogen.
  • Example 6 As in example 2, the process was conducted in a stream of hydrogen, with a ratio of 1 molar part of para-phenetidine and 2 molar parts of methanol.
  • Example 7. As in example 1, 3, 4, but in the presence of triethylamine in a molar ratio to para-nitrophenetole of 0.1: 1. Received ⁇ -methyl-para-phenethidine with a yield of up to 92%.
  • Example 8 As in example 2, 5, 6, but in the presence of triethylamine in a molar ratio to para-phenethidine of 0.1: 1. Received ⁇ -methyl-para-phenethidine with a yield of up to 96%.
  • BASF Cu-E403TR catalyst produced by composition: copper chromite 67-71%, copper 1 1-15%, copper oxide 8-21%, graphite 0-4%, chromium oxide (3+) 0-3%;
  • BASF production catalyst Cu-0203T 1/8 composition copper oxide 75-100%, chromium oxide (3+) 0.1-1%;
  • BASF production catalyst Cu-E406 TR composition Cu-36%, Cr-31%, Ba-6%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Le procédé de production de N-méthyl-para-phénétidine fait partie des processus technologiques et chimiques et plus particulièrement des procédés d'alkylation catalytique d'amines aromatiques et des compositions azotées. Le procédé porte sur un procédé de production de N-méthyl-para-phénétidine (N-méthyl-para-éthoxy-aniline) ; N-méthyl-para-aminophénétol) à partir de para-phénétidine (para-aminophénétol; para-éthoxy-aniline) ou de para-nitrophénétol (1-éthoxy-4-nitrobenzol) et de méthanol en présence d'hydrogène ou sans hydrogène sur une base de catalyseur hétérogène. Le procédé de l'invention permet d'utiliser les installations industrielles existantes utilisées pour la production d'aniline et de N-méthylaniline. Le but visé par l'invention est la possibilité de produire du N-méthyl-para-phénétidine possédant une pureté d'au moins 98 % et un rendement élevé, ce qui permet d'organiser une production hautement rentable de l'ordre de plusieurs tonnes.
PCT/RU2011/000902 2011-09-28 2011-11-15 Procédé de production sélective de n-méthyl-para-phénétidine Ceased WO2013048280A1 (fr)

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WO2018048319A1 (fr) * 2016-09-12 2018-03-15 Общество с ограниченной ответственностью "ИФОТОП" Procédé de production de n-méthyl-para-phénétidine

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2207335C2 (ru) * 2001-04-28 2003-06-27 Российский государственный университет нефти и газа им. И.М.Губкина Способ получения ароматических аминов восстановлением соответствующих нитросоединений
RU2309944C1 (ru) * 2006-04-12 2007-11-10 Общество с ограниченной ответственностью "ИФОХИМ" Производные пара-метоксианилинов, повышающие стойкость углеводородных топлив к детонации, и топливная композиция (варианты)

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* Cited by examiner, † Cited by third party
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RU2309943C1 (ru) * 2006-03-16 2007-11-10 Общество с ограниченной ответственностью "ИФОХИМ" Применение производных пара-этоксианилинов, повышающих стойкость углеводородных топлив к детонации, и топливная композиция (варианты)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2207335C2 (ru) * 2001-04-28 2003-06-27 Российский государственный университет нефти и газа им. И.М.Губкина Способ получения ароматических аминов восстановлением соответствующих нитросоединений
RU2309944C1 (ru) * 2006-04-12 2007-11-10 Общество с ограниченной ответственностью "ИФОХИМ" Производные пара-метоксианилинов, повышающие стойкость углеводородных топлив к детонации, и топливная композиция (варианты)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"«Sovetskaya Entsyklopediya»", KHIMICHESKAYA ENTSIKLOPEDIYA, 1988, pages 265 *

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