WO2004000777A1 - Procede de fabrication de composes carbonyles a partir d'hydrocarbures cycliques di- et polyenes et de leurs derives - Google Patents

Procede de fabrication de composes carbonyles a partir d'hydrocarbures cycliques di- et polyenes et de leurs derives Download PDF

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Publication number
WO2004000777A1
WO2004000777A1 PCT/RU2003/000063 RU0300063W WO2004000777A1 WO 2004000777 A1 WO2004000777 A1 WO 2004000777A1 RU 0300063 W RU0300063 W RU 0300063W WO 2004000777 A1 WO2004000777 A1 WO 2004000777A1
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Prior art keywords
reaction
goodbye
values
mixture
inert gas
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PCT/RU2003/000063
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English (en)
Russian (ru)
Inventor
Gennady Ivanovich Panov
Constantin Alexandrovich Dubkov
Evgeny Vladimirovich Starokon
Original Assignee
Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk filed Critical Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk
Priority to AU2003235532A priority Critical patent/AU2003235532A1/en
Publication of WO2004000777A1 publication Critical patent/WO2004000777A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties

Definitions

  • ⁇ a ⁇ b ⁇ nilnye s ⁇ edineniya ( ⁇ a ⁇ b ⁇ tsi ⁇ liches ⁇ ie ne ⁇ edelnye ⁇ e ⁇ ny and ⁇ a ⁇ zhe ⁇ a ⁇ b ⁇ tsi ⁇ liches ⁇ ie di- and ⁇ li ⁇ e ⁇ ny) yavlyayu ⁇ sya important ⁇ mezhu ⁇ chnymi vesches ⁇ vami for sin ⁇ eza ⁇ azn ⁇ b ⁇ azny ⁇ ⁇ ganiches ⁇ i ⁇ ⁇ du ⁇ v in ⁇ m including ag ⁇ imi ⁇ a ⁇ v and ⁇ a ⁇ matsev ⁇ iches ⁇ i ⁇ ⁇ e ⁇ a ⁇ a ⁇ v.
  • derivatives of 2-cyclohexen-1 are used in the quality of herbicides.
  • the corresponding cyclohexanedanes can be hydrated, catechol and rubber.
  • the reaction is carried out under conditions where the dihydrogen and pollenic hydrocarbons are in the form of a liquid phase in the presence of liquids
  • Excessive increase in temperature and / or pressure ⁇ 2 0 is undesirable, as it may reduce the selectivity due to the contribution of gas-rich oxidation.
  • Nitrous oxide or its mixture with inert gas is supplied, bringing the pressure to a predetermined value.
  • Nitrous nitrous oxide can be used in such a way that its pressure at the reaction rate is 0.01–200 atm. After this process, they cool and heat the reaction in the range of 20-300 ° ⁇ .
  • the response time is subject to the conditions for its use, and also the terms and conditions of the process, and may change for a few minutes. It is known that saturated carbohydrates and olefins can produce explosive mixtures with ⁇ 2 0 [ ⁇ . ⁇ réelle ⁇ réelle ⁇ réelle ⁇ , ⁇ . ⁇ jon ⁇ , V ⁇ transformer
  • Non-inert gas can play the flue gases of the reaction.
  • the proposed process may be carried out without solvents. However, with the use of the process and with the use of devices, some can be removed from the wide range of substances that are used in the process of synthesis. A product with a fairly high speed is available without a catalyst, although it can also be handled in a non-commercialized manner.
  • the proposed method for the receipt of carboxylic compounds does not offer a high number of original reagents.
  • the reserve of nitrogen may be used in its pure form, as well as with the addition of various gases that do not have an adverse effect on the performance of the process.
  • Original di- and polyenic cyclic hydrocarbons and their derivatives may also contain impurities of other compounds, if they are not connected.
  • Examples 1-6 describe experiments on the oxidation of 1,4-cyclohexadiene with nitrous oxide. The results of these examples are given in table 1.
  • Example 1 100 cm in size, made of stainless steel and equipped with a stirrer (Firmag), pour 25 cm 3 of 1,4-cyclohexadiene ( ⁇ êt ⁇ , 99%). They blow off nitrous oxide and then bring its pressure to 25 atm. They pressurize, heat up to 198 ° ⁇ , and withstand it at this temperature for 5 hours. After the end of the reaction, the process coolers cool the room temperature, measure the pressure and analyze the final composition of the gas and liquid fumes of the gas industry From the obtained data, they calculate the conversion of 1, 4-cyclohexadiene (X) and the selectivity of the reaction to the processed products (8:
  • C ⁇ is the concentration of the reaction product
  • C ⁇ 8 is the initial concentration of 1,4-cyclohexadiene.
  • the value of X may also be calculated by the difference between the initial and final concentrations of 1,4-cyclohexadiene:
  • the main reaction products are Z-cyclohexen-1-on, 2-cyclohexen-1-on, 1,4-cyclohexanedione and 1,3-cyclohexanedione.
  • the result of the experiment is the total selectivity of the carbohydrate compounds is 91.6%.
  • Example 2 is similar to Example 1 with an exception that the initial pressure of ⁇ 2 0 is set to 40 atm and the reaction is conducted at 160 ° C for 20 hours. ⁇ As a result of the experiment, the total selectivity of the vehicle connections is 91.1%.
  • Example 3 is analogous to Example 1, with the exception that the initial pressure of 0 2 0 sets 10 atm and the reaction takes 10 hours. ⁇ The result of the experiment is the total selectivity of the vehicle compounds of 91.7%.
  • Example 4 is similar to Example 1, in other words, that the reaction is carried out using a reagent as a source. For this, before starting the experiment, 10 ml of 1,4-cyclohexadiene and 20 ml of mesitylene are poured into the reaction.
  • Example 5 is analogous to Example 4 with the exception that the reaction is carried out at 250 ° C for 5 hours and as a result of the converter use a cyclohexane.
  • the reaction is carried out at 250 ° C for 5 hours and as a result of the converter use a cyclohexane.
  • 3- and 2-cyclohexen-1-ones are obtained in the approximate ratio of 1.5: 1, and also 1,4- and 1,3-cyclohexanedine in the case of 1: 8.
  • the aggregate selectivity for the carboxylic compounds is 95.6%.
  • Example 6 is similar to Example 4, except that the reaction is carried out in the case of 0.3 g less than 2 0 3 / 8SU 2 (2.8 wt.% Less than 2 0 3 ) and, as a result, the reactor is free. It is prepared by cooking 8You 2 products with CeC1 3 , it is dried at 110 ° ⁇ and it is heated at the temperature of 500 ° ⁇ for 2 hours. ⁇ The result of the experiment is the total selectivity of the storage compounds of 89.6%.
  • Example 7 is similar to Example 4 with the exception that the reaction is carried out in the form of 0.3 g of ⁇ / 8 ⁇ 0 2 (1 wt.% ⁇ ) and in the quality of the consumer uses benzyl. It is prepared by using 8U 2 steamers, which are dried at 3 ° C, dried at 110 ° ⁇ and heated at the temperature of 500 ° ⁇ for 2 hours. As a result of the experiment, the total selectivity of the vehicle compounds is 90.6%. Table 1 Acidification of 1,4-cyclohexadiene.
  • Example 9-12 This is, for example, comparative.
  • the experiment is carried out in a similar manner to Example 1, which, in the process, loads 3 ml of 1,4-cyclohexadiene. With such a load, the entire 1,4-cyclohexadiene under the reaction conditions is in the gas phase. As a result of its experience, its investment is less than 1%. This indicates that, given the given conditions, the reaction in the gas phase is practically not ideal.
  • Example 9 describes the oxidation of 1,3-cyclohexadiene with the use of a cyclohexane converter.
  • the experiment is carried out in a similar manner to Example 3 with the exception that, as a result of the original dietary cyclic hydrocarbon, 1,3-cyclohexadiene is obtained.
  • 1,3-cyclohexadiene is obtained.
  • the initial pressure ⁇ 2 0 is set to 10 atm. It is produced at 220 ° ⁇ for 5 hours.
  • the main product of the oxidation of 1,3-cyclohexadiene is 2-cyclohexen-1-one, which is converted to a 25.9% selectivity of 69% of 1,3-cyadi.
  • Example 10 is analogous to Example 9, which is an experience that lasts 3 hours and, as a result of inhibiting the use of polymerisation in the reaction mixture, adds 1 hydrate.
  • the conversion of 1,3-cyclohexadiene is 31.5%, with a selective 2-cyclohexen-1-formation of 35.3%.
  • EXAMPLE 11 Describes the oxidation of 3-methyl-1,4-cyclohexadiene using a solvent as a base. For this, in the case of the process and the room temperature, 10 ml of Z-methyl-1,4-cyclohexadiene and 20 ml of body are loaded. The initial pressure ⁇ 2 0 is set to 25 atm. It is produced at 220 ° ⁇ for 5 hours. As a result of the reaction, the conversion of 3-methyl-1,4-cyclohexadiene is 18.5% and the total selectivity is 94.3% for carboxylic compounds.
  • Example 12 describes the oxidation of 1, ⁇ -3,3-cyclohexene with the use of a cyclohexane converter. For this, in the case of the reactor and the indoor temperature, 10 g of 1, ⁇ -3,3-cyclohexene and 20 ml of cyclohexane are loaded. The initial pressure ⁇ 2 0 is set to 25 atm. It is produced at 220 ° ⁇ for 12 hours.
  • EXAMPLE 13 ⁇ Reactor and a room temperature load 25 ml of 1,5-cyclostadiene.
  • the initial pressure ⁇ 2 0 is set to 25 atm.
  • Example 14 is similar to Example 13, with the exception that the initial pressure ⁇ 2 0 sets 10 atm.
  • the result of the reaction of conversion of 1,5-cycle tadiene is 15.1% for the selectivity of 4-cycle of 87.8% and the total aggregate of 4.%
  • the aggregate selectivity of the corporeal compounds is 92.7%.
  • EXAMPLE 15 Describes the oxidation of 1,5-cyclostadiene using a recycle cycler. For this, in the process and in the room temperature, 15 ml of 1,5-cycloctadiene and 10 ml of cycloctane are loaded. ⁇ y ⁇ ⁇ v ⁇ dya ⁇ anal ⁇ gichn ⁇ ⁇ ime ⁇ u 1.
  • Examples 16-22 are given in table 3. These examples show the possibility of selective oxidation of 1,4-cyclohexadiene and 1,5- cyclic tadiene in carboxylic compounds using diluted nitrous oxide mixtures. 3 Table 3 shows the aggregate selectivity for corporeal compounds.
  • Example 21 is similar to example 17 with the exception that, in the sense of inert gas, instead of nitrogen, the mixture is used, in addition to the concentration of 24% of the mixture, the percentage of the charge is 100%.
  • Example 22 is analogous to example 20 with the exception that, in the sense of inert gas, instead of nitrogen, carbon dioxide is used, but at the same time there is a concentration of 24% of the excreted gas.
  • Examples 16–22 indicate the possibility of oxidizing di- and polynylic hydrocarbons to storage compounds with the addition of nitrogen, with a diluted gas.
  • Composition ⁇ 2 0 in inert gas may vary in broad terms, including the percentage of consumption of 25% or less, which is excluded

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de fabrication de composés carbonyles. Le processus à breveter est fondé sur l'oxydation d'hydrocarbures cycliques di- et polyènes et de leurs dérivés qui produit des cétones carbocycliques insaturées correspondantes ainsi que des di- et polycétones, par du monoxyde de nitrogène ou par son mélange avec un gaz inerte. Le processus est réalisé à une température de 20 à 300 °C sous une pression de monoxyde d'azote entre 0,01 et 200 atm. Le processus permet d'assurer une sélectivité élevée vis-à-vis des produits visés, la protection contre les explosions et ouvre de bonnes perspectives en termes d'utilisation industrielle.
PCT/RU2003/000063 2002-06-25 2003-02-26 Procede de fabrication de composes carbonyles a partir d'hydrocarbures cycliques di- et polyenes et de leurs derives WO2004000777A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003235532A AU2003235532A1 (en) 2002-06-25 2003-02-26 Method for producing carbonyl compounds from di- and polyene cyclic hydrocarbons and the derivatives thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2002116991 2002-06-25
RU2002116991A RU2219160C1 (ru) 2002-06-25 2002-06-25 Способ получения карбонильных соединений из ди- и полиеновых циклических углеводородов и их производных

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WO2004000777A1 true WO2004000777A1 (fr) 2003-12-31

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2438570A (en) * 2005-03-02 2007-11-28 Noel Alfred Warner Process and plant for gas-based direct steelmaking
US7649119B2 (en) 2006-06-29 2010-01-19 Basf Se Method for the production of cyclic ketones
US7692045B2 (en) 2004-09-23 2010-04-06 Basf Aktiengesellschaft Method for purifying and concentrating dinitrogen monoxide
US7714172B2 (en) 2006-06-29 2010-05-11 Basf Se Method for the production of cyclic ketones
WO2010076182A1 (fr) 2008-12-30 2010-07-08 Basf Se Procédé de production de cétones par réaction d'oléfines 1,1-disubstituées avec du n2o
US7754172B2 (en) 2005-11-22 2010-07-13 Basf Aktiengesellschaft Method for isolating N2O
US7803971B2 (en) 2004-09-23 2010-09-28 Basf Akiengesellschaft Method for the production of cyclopentanone
WO2012066296A2 (fr) 2010-11-19 2012-05-24 Invista Technologies S.A.R. L. Oxyde de diazote-contenant des liquides ioniques en tant que réactifs chimiques
US8404901B2 (en) 2008-04-02 2013-03-26 Basf Se Process for purifying dinitrogen monoxide
US8449655B2 (en) 2006-12-11 2013-05-28 Basf Aktiengesellschaft Process for isolating N2O
US8461392B2 (en) 2008-08-29 2013-06-11 Basf Se Process for preparing cyclic ketones
US8808430B2 (en) 2008-04-02 2014-08-19 Basf Se Process for purifying N2O

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103313956A (zh) * 2010-12-15 2013-09-18 沙特***石油公司 使用气态氧化剂的烃原料流的脱硫

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB790607A (en) * 1955-10-11 1958-02-12 Hoffmann La Roche A process for the manufacture of a cyclic ketone and the conversion thereof into its monoketals and into a keto-alcohol and esters of same
GB1418590A (en) * 1972-11-16 1975-12-24 Firmenich & Cie Preparation of alicyclic diketones
RU2074164C1 (ru) * 1994-04-12 1997-02-27 Институт катализа им.Г.К.Борескова СО РАН Способ получения фенола или его производных
US5756861A (en) * 1994-04-12 1998-05-26 Monsanto Company Method for production for phenol and its derivatives

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB790607A (en) * 1955-10-11 1958-02-12 Hoffmann La Roche A process for the manufacture of a cyclic ketone and the conversion thereof into its monoketals and into a keto-alcohol and esters of same
GB1418590A (en) * 1972-11-16 1975-12-24 Firmenich & Cie Preparation of alicyclic diketones
RU2074164C1 (ru) * 1994-04-12 1997-02-27 Институт катализа им.Г.К.Борескова СО РАН Способ получения фенола или его производных
US5756861A (en) * 1994-04-12 1998-05-26 Monsanto Company Method for production for phenol and its derivatives

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7692045B2 (en) 2004-09-23 2010-04-06 Basf Aktiengesellschaft Method for purifying and concentrating dinitrogen monoxide
US7803971B2 (en) 2004-09-23 2010-09-28 Basf Akiengesellschaft Method for the production of cyclopentanone
GB2438570B (en) * 2005-03-02 2011-01-26 Noel Alfred Warner Process and plant for gas-based direct steelmaking
GB2438570A (en) * 2005-03-02 2007-11-28 Noel Alfred Warner Process and plant for gas-based direct steelmaking
US7754172B2 (en) 2005-11-22 2010-07-13 Basf Aktiengesellschaft Method for isolating N2O
US7714172B2 (en) 2006-06-29 2010-05-11 Basf Se Method for the production of cyclic ketones
US7649119B2 (en) 2006-06-29 2010-01-19 Basf Se Method for the production of cyclic ketones
US8449655B2 (en) 2006-12-11 2013-05-28 Basf Aktiengesellschaft Process for isolating N2O
US8404901B2 (en) 2008-04-02 2013-03-26 Basf Se Process for purifying dinitrogen monoxide
US8808430B2 (en) 2008-04-02 2014-08-19 Basf Se Process for purifying N2O
US8461392B2 (en) 2008-08-29 2013-06-11 Basf Se Process for preparing cyclic ketones
WO2010076182A1 (fr) 2008-12-30 2010-07-08 Basf Se Procédé de production de cétones par réaction d'oléfines 1,1-disubstituées avec du n2o
US8420866B2 (en) 2008-12-30 2013-04-16 Basf Se Process for preparing ketones by reacting 1,1-disubstituted olefins with N2O
WO2012066296A2 (fr) 2010-11-19 2012-05-24 Invista Technologies S.A.R. L. Oxyde de diazote-contenant des liquides ioniques en tant que réactifs chimiques

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Publication number Publication date
RU2002116991A (ru) 2004-01-10
RU2219160C1 (ru) 2003-12-20
AU2003235532A1 (en) 2004-01-06

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