WO2012055754A2 - Procédé de préparation de dérivés de 1-méthylcyclopentane - Google Patents

Procédé de préparation de dérivés de 1-méthylcyclopentane Download PDF

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Publication number
WO2012055754A2
WO2012055754A2 PCT/EP2011/068328 EP2011068328W WO2012055754A2 WO 2012055754 A2 WO2012055754 A2 WO 2012055754A2 EP 2011068328 W EP2011068328 W EP 2011068328W WO 2012055754 A2 WO2012055754 A2 WO 2012055754A2
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WO
WIPO (PCT)
Prior art keywords
methylcyclopentene
stage
reaction
cyclohexene
product mixture
Prior art date
Application number
PCT/EP2011/068328
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German (de)
English (en)
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WO2012055754A3 (fr
Inventor
Andreas Lanver
Klaus Ebel
Rainer Klopsch
Werner Bertleff
Richard Dehn
Joaquim Henrique Teles
Helmut Kronemayer
Marcus Georg Schrems
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Basf Se
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Publication of WO2012055754A2 publication Critical patent/WO2012055754A2/fr
Publication of WO2012055754A3 publication Critical patent/WO2012055754A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/29—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of carbon atoms in a ring while maintaining the number of rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to a process for the preparation of 1-methylcyclopentene by thermal reaction of cyclohexanol or cyclohexene or mixtures of both
  • the present application relates to a process for the preparation of cyclopentane derivatives of the following formula I.
  • Product mixture of the 1st or 2nd stage can be attributed to the implementation of the 1st stage.
  • Cyclopentane derivatives of the above formula I are of importance as starting materials for chemical syntheses of various compounds.
  • From US Pat. No. 5,498,802 it is known to prepare 1-methyl-1-hydroxycyclopentane in three separate reaction steps, wherein in the first step cyclohexanol is dehydrated to cyclohexene, in the second step cyclohexene is isomerized to 1-methylcyclopentene and in the third step water is added to 1-methylcyclopentene is added in the presence of isopropanol as a solvent.
  • Example 1 of US 5,498,802 dissolved in methanol cyclohexanol is dehydrated at 250 ° C on silica to cyclohexene. At complete cyclohexanol conversion, a cyclohexene yield of 97.5% was achieved in the first step.
  • US 4,661,639 relates to a process for the preparation of cyclic alcohols by addition of water to cyclic olefins using modified aluminosilicate catalysts.
  • the following statements relate to the preparation of 1-methylcyclopentene as the end product.
  • Starting compound of the process for the preparation of 1-methylcyclopentene is cyclohexanol or cyclohexene or a mixture of the two.
  • the reaction is a gas phase reaction.
  • cyclohexene is a rearrangement to 1-methylcyclopentene; starting from cyclohexanol in the 1st stage, a dehydration to cyclohexene and then the subsequent rearrangement to 1-methylcyclopentene according to the following schematically illustrated reaction sequence:
  • Cyclohexene as the starting compound can also be obtained by separately pre-dehydration of cyclohexanol or any other method, e.g. by partial hydrogenation of benzene by the Asahi process.
  • Preferred starting compound is cyclohexanol or a mixture of cyclohexanol and cyclohexene, wherein the molar ratio of cyclohexanol to cyclohexene 1 to 0.1 to 0.1 to 1.
  • the reaction may be batchwise or, preferably, continuous, i. with continuous feed of the starting materials and continuous discharge of the products.
  • starting compounds therefore always includes in the following recycled compounds, eg, recycled by-products and recycled, unreacted starting compounds, as discussed in more detail below.
  • the reaction is preferably carried out in the gas phase in the presence of acidic catalysts.
  • the gas phase reaction can be carried out in reactors such as stirred reactors or tubular reactors.
  • the acidic catalysts can be arranged in the reactor as a fixed bed or fluidized bed. A necessary inertization of the catalysts may be carried out with a carrier gas, e.g. Nitrogen or argon.
  • a carrier gas e.g. Nitrogen or argon.
  • solid acid catalysts are e.g. SiO 2, Al 2 O 3, mixtures of SiO 2 and Al 2 O 3, aluminum silicates, ZrO 2, CO 2 or zeolites.
  • catalysts for the reaction of cyclohexanol or cyclohexene to 1-methylcyclopentene naturally occurring or synthetically prepared zeolites are also suitable.
  • the catalyst loading is preferably 0.05 to 3, preferably 0.1 to 2, particularly preferably 0.2 to 1 kg of starting compounds per liter of catalyst per hour.
  • the residence time is in particular from 1 to 50 seconds, preferably 5 to 15 seconds.
  • the reaction can be carried out at temperatures of 250 to 500, preferably 300 to 450, particularly preferably from 400 to 450 ° C.
  • the reaction pressure is not critical. It may, for example, be 0.1 to 10 bar, preferably 1 to 5 bar.
  • the product mixture obtained in the reaction contains, in addition to the desired product 1-methylcyclopentene, the following compounds: the by-products 3-methylcyclopentene and 4-methylcyclopentene (double bond isomers of 1-methylcyclopentene),
  • the entire resulting amount of the 3- and 4-methylcyclopentene is recycled to the reaction.
  • the gaseous reaction is condensed. This can e.g. by adding an organic solvent such as toluene (quenching) done.
  • an organic solvent such as toluene (quenching) done.
  • the condensate consists of two liquid phases, one aqueous and one organic.
  • the two phases are separated.
  • the organic phase contains the above product mixture, in particular the desired product 1-methylcyclopentene.
  • the water phase is discharged.
  • the separation of the two liquid phases can be carried out by gravimetric phase separation. As phase separation vessels, for example, conventional standard apparatuses and standard methods are suitable. Alternatively, water can be separated from the condensed reaction product by an azeotropic distillation.
  • the organic phase containing generally unreacted cyclohexene (boiling point 83 ° C), 1-methylcyclopentene (boiling point 76 ° C), and the two isomers 3-methylcyclopentene and 4-methylcyclopentene (boiling points 65-66 ° C), can be worked up by distillation The above boiling points apply to atmospheric pressure; 1-methylcyclopentene can then be separated from this organic phase and used as the end product in the desired manner.
  • the entire residue of the organic phase which contains 3-methylcyclopentene and 4-methylcyclopentene and cyclohexene, is recycled to the reaction.
  • the cyclopentane derivatives of the formula I are prepared for the preparation of the cyclopentane derivatives of the formula I.
  • the process for the preparation of cyclopentane derivatives of the formula I is a two-stage process. In a 1st stage, the thermal conversion of cyclohexanol or cyclohexene to 1-methylcyclopentene; in the second stage the addition of compounds HX takes place.
  • X is a hydroxyl group, an alkoxy group, preferably a C1 to C10 alkoxy group or a chlorine atom.
  • X represents a hydroxyl group or an alkoxy group.
  • Suitable alkoxy groups are in particular alkoxy groups having 1 to 10 C atoms, particularly preferably having 1 to 5 C atoms.
  • X is particularly preferred for an alkoxy group, in particular a C 1 to C 5 alkoxy group, for example a methoxy group, ethoxy group, isopropoxy group, n-propoxy group, n-butoxy group or a pentoxy group.
  • X is a methoxy group.
  • 1-methylcyclopentene is produced in the first stage of the two-stage process. All statements above on the preparation of 1-methylcyclopentene apply here accordingly, unless otherwise stated below.
  • HX is preferably corresponding to water or preferably to a C 1 to C 10, in particular a C 1 to C 5, alcohol. Particularly preferred is methanol.
  • 1-methylcyclopentene is preferably reacted in the liquid phase in the presence of acidic catalysts with compounds HX to give cyclopentane derivatives of the formula I.
  • the reaction can be carried out at temperatures of, for example, 20 to 100.degree. C., preferably 50 to 90.degree. C., particularly preferably 40 to 90.degree.
  • the reaction pressure is not critical. It may, for example, be 0.1 to 10 bar, preferably 1 to 5 bar.
  • the molar ratio of 1-methylcyclopentene to compounds HX may be e.g. 1 to 10 to 10 to 1. In a preferred embodiment, HX is employed in molar excess; the molar ratio of 1-methylcyclopentene to the compounds HX is then in particular from 1: 1 to 1: 10, more preferably from 1: 2 to 1: 5.
  • solid acidic catalysts e.g. strong acid ion exchangers or zeolites used, as also mentioned in US 5,498,802.
  • the solid acidic catalysts can either be fixed in a reactor or are suspended in the liquid phase.
  • the catalyst loading may be, for example, 20 to 1, preferably 15 to 3, more preferably 5 to 3 kg of methylcyclopentenes per liter of catalyst per hour.
  • the residence time may be, for example, 5 minutes to two hours, more preferably 5 minutes to 2 hours, and preferably 10 minutes to 30 minutes.
  • HX H 2 O
  • the reaction in the second stage is preferably carried out in the presence of a polar organic solvent, for example secondary alcohols such as sec-butanol and isopropanol.
  • the solvent serves as a solubilizer between the water and the non-polar starting material 1-methylcyclopentene.
  • the reaction effluent from stage 2 contains the desired cyclopentane derivatives of the formula I, unconverted 1-methylcyclopentene, optionally its isomers as by-products and optionally unreacted HX and optionally solvent. If the acidic catalyst was suspended in the reaction mixture, it can be separated by filtration and recycled to synthesis step 2.
  • the workup of the reaction can be carried out by distillation.
  • fractional distillations can be carried out.
  • X in formula I is a C1 to C10 alkoxy group and in the second stage, the addition of the C1 to C10 alcohol corresponding to the 1-methylcyclopentene, in the second stage in a preferred embodiment, a reactive distillation carried out.
  • a reactive distillation carried out. In the reactive distillation, the reaction of the starting compounds in the
  • the starting materials here C1 to C10 alcohol, preferably methanol, and 1-methylcyclopentene, and optionally recycled by-products
  • the starting materials here C1 to C10 alcohol, preferably methanol, and 1-methylcyclopentene, and optionally recycled by-products
  • the reaction takes place to the cyclopentane derivative of the formula I (preferably 1-methyl-1-methoxycyclopentane).
  • the readily volatile starting compounds are condensed at the top of the column and returned to the column (stream 2).
  • the less volatile cyclopentane derivative of the formula I preferably 1-methyl-1-methoxycyclopentane
  • less volatile by-products accumulate in the bottom of the column and can be withdrawn (stream 3).
  • the distillation apparatus may preferably contain conventional internals for promoting the separation by distillation (packing or column bottoms) and the acid catalyst, for example as a fixed bed or fluidized bed (see internals A and B in Fig. 1).
  • the second stage process may be carried out batchwise or continuously; Preferably, the process is carried out continuously in the 2nd stage.
  • An essential feature of the two-stage process according to the invention for the preparation of cyclopentane derivatives is that 3-methylcyclopentene and 4-methylcyclopentene, and optionally unreacted starting compounds are recycled in the product mixture of the 1st or 2nd stage in the implementation of the 1st stage.
  • 1-methylcyclopentene is separated as described above from the product mixture of the 1st stage and fed to the 2nd stage, while 3-methylcyclopentene and 4-methylcyclopentene and preferably also the unreacted cyclohexene are recycled to the reaction of the 1st stage ,
  • the entire organic residue is recycled after separation of the 1-methylcyclopentene.
  • the product mixture contains water from the dehydration of cyclohexanol to cyclohexene. Water is obtained as a separate aqueous phase and can be easily separated from the organic phase as described above. The aqueous phase is discarded and not recycled to the 1st stage reaction.
  • a return in addition to the return in the 1st stage, a return can also be carried out in the 2nd stage.
  • unreacted starting materials of the second stage that is, 1-methylcyclopentene and unused HX, are attributed to the second stage reaction.
  • the product mixture of the 1st stage is condensed and the organic phase without separation of the by-products 3-methylcyclopentene and 4-methylcyclopentene and without separation of the unreacted starting compounds (cyclohexene) supplied to the further reaction in the 2nd stage.
  • an aqueous phase is obtained in the condensation of the product mixture due to the (use) of cyclohexanol, this is preferably separated and discarded, as far as no water is needed in step 2.
  • HX H 2 O
  • the aqueous phase is also fed to the second stage.
  • the product mixture obtained in the 2nd stage accordingly contains the desired cyclopentane derivative of the formula I
  • stage 1 3-methylcyclopentene and 4-methylcyclopentene unreacted starting materials from stage 1: cyclohexene
  • further water is preferably added in the second stage.
  • an addition of 1 to 100 mol, in particular 10 to 80 mol of water per 1 mol of 1-methylcyclopentene is preferred.
  • the desired 1-Methylcyclopentanderivat be separated by fractional distillation as high boilers of the above compounds and, if necessary, again purified by distillation.
  • unreacted HX in particular water and alkanols, are separated from the product mixture of the second stage and are not recycled to the first stage.
  • stage 1 (examples 1 to 3) and stage 2
  • Example 6 shows that the reactions take place with high selectivity.
  • Example 5 shows the recycling of the unwanted by-products upon recycling
  • Example 14 shows that the presence of 3-methylcyclopentene, 4-methylcyclopentene and cyclohexene in the second stage does not lead to new by-products.
  • Temperature measurement was filled with a catalyst amount of about 300ml.
  • the educt (1) was fed continuously in trickle mode.
  • In the bottom of the glass reactor was condensed in a 1 L flask with attached condenser with toluene as the quench liquid. Nitrogen was used as the carrier gas.
  • From the biphasic mixture the aqueous phase was separated in a separating funnel. The organic phase was analyzed by GC.
  • the starting material used was the following mixture: compounds 3 (11 GC-FI%), 4 (56 GC-FI%), 5 (24 GC-FI%). At a temperature of 400 ° C, a
  • an ion exchanger (Amberlyst type) was charged as a catalyst.
  • the mixture consisting of 1-methylcyclopentene, isopropanol (iPrOH) and water was fed from a storage tank via a membrane pump at a constant internal volume.
  • the product mixture was analyzed by GC. The yields and conversions were calculated from GC% by weight results.
  • composition of the product mixture :
  • the temperature is set at 85 ° C.
  • the two reactants methylcyclopentene and methanol then boil and condense on the reflux condenser. Then, the condensed mixture enters the reaction zone with the ion exchanger and reacts to the product 1-methoxy-1-methylcyclopentane. Since the boiling point is above 85 ° C, the product can be enriched in the sump to near full conversion.
  • composition of the product mixture :
  • a mixture consisting of the compounds 3 and 7 was fractionally distilled at a pressure between 1 bar and 100 mbar.
  • the apparatus used was a 1 liter flask with a 20 cm column with 3 mm V2A Raschig rings.

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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 préparation de 1-méthylcyclopentène par transformation thermique de cyclohexanol ou de cyclohexène ou de mélanges de ces deux composés en 1-méthylcyclopentène, caractérisé en ce que les sous-produits obtenus 3-méthylcyclopentène et 4-méthylcyclopentène (isomères à liaison double de 1-méthylcyclopentène) sont renvoyés dans la transformation.
PCT/EP2011/068328 2010-10-25 2011-10-20 Procédé de préparation de dérivés de 1-méthylcyclopentane WO2012055754A2 (fr)

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EP10188692 2010-10-25
EP10188692.7 2010-10-25

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WO2012055754A2 true WO2012055754A2 (fr) 2012-05-03
WO2012055754A3 WO2012055754A3 (fr) 2012-08-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8993819B2 (en) 2011-07-12 2015-03-31 Basf Se Process for preparing cycloheptene
US9193862B2 (en) 2012-02-22 2015-11-24 Basf Se Blends for composite materials

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4661639A (en) 1984-05-25 1987-04-28 Asahi Kasei Kogyo Kabushiki Kaisha Process for producing cyclic alcohol
US5498802A (en) 1995-02-28 1996-03-12 Hoechst Celanese Corporation Process for preparing omega-halo-ketones

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2333903A (en) * 1939-06-05 1943-11-09 Universal Oil Prod Co Treatment of hydrocarbons
US2485966A (en) * 1947-09-29 1949-10-25 Shell Dev Methylcyclopentene production

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4661639A (en) 1984-05-25 1987-04-28 Asahi Kasei Kogyo Kabushiki Kaisha Process for producing cyclic alcohol
US5498802A (en) 1995-02-28 1996-03-12 Hoechst Celanese Corporation Process for preparing omega-halo-ketones

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NEFTEKHIMIYA, vol. 31, no. 3, 1991, pages 386 - 390

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8993819B2 (en) 2011-07-12 2015-03-31 Basf Se Process for preparing cycloheptene
US9193862B2 (en) 2012-02-22 2015-11-24 Basf Se Blends for composite materials

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