WO2000041987A1 - Procede de preparation de cyclopentadienes substitues - Google Patents

Procede de preparation de cyclopentadienes substitues Download PDF

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Publication number
WO2000041987A1
WO2000041987A1 PCT/EP2000/000015 EP0000015W WO0041987A1 WO 2000041987 A1 WO2000041987 A1 WO 2000041987A1 EP 0000015 W EP0000015 W EP 0000015W WO 0041987 A1 WO0041987 A1 WO 0041987A1
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WO
WIPO (PCT)
Prior art keywords
acid
formula
compound
alkyl
substituted
Prior art date
Application number
PCT/EP2000/000015
Other languages
German (de)
English (en)
Inventor
Carsten Bingel
Original Assignee
Basell Polypropylen Gmbh
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.)
Filing date
Publication date
Priority claimed from DE19900732A external-priority patent/DE19900732A1/de
Priority claimed from DE19935885A external-priority patent/DE19935885A1/de
Application filed by Basell Polypropylen Gmbh filed Critical Basell Polypropylen Gmbh
Publication of WO2000041987A1 publication Critical patent/WO2000041987A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/08—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring
    • C07C13/15—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring with a cyclopentadiene ring
    • 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
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • 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

Definitions

  • the present invention relates to a process for the preparation of substituted, in particular 1,3-disubstituted, cyclopentadienes, which are prepared starting from substituted-cyclopent-2-en-1-ones.
  • Alkyl and aryl-substituted cyclopentadienes are used for the production of metallocene complexes ("Chemistry of Organozirconium and - hafnium compounds -", DJ Cardin, MF Läppert, CL Raston; 1986, Ellis Horwood Limited) such as, for example, metallocenes of titanium, zirconium, hafnium or lanthanoids used. These metallocenes are part of highly active catalyst systems for the production of polyolefins, in particular polyethylenes and copolymers of ethylene with other ⁇ -olefins (WO9504761).
  • R, R 1 are identical or different alkyl or aryl radicals and M is Li, MgCl, MgBr or Mgl.
  • a tertiary alcoholate is formed by the reaction with a Grignard compound or organolithium compound. After protonation and acid-catalyzed dehydration, 1,3-disubstituted cyclopentadiene is formed.
  • the reaction proceeding according to scheme (1) takes place without problems in the manner shown if R 1 is, for example, an aryl radical or tertiary butyl radical. From EP-A-0648722 it is known that when alkyl grigards such as
  • M is Li, MgCl, MgBr or Mgl
  • R, R 2 , R 3 may be the same or different alkyl or aryl radicals.
  • EP-A-0648722 a strong acid is used to dehydrate the tertiary alcohol, an endo / exo isomer ratio of about 1: 1 is obtained. Furthermore, EP-A-0648722 describes that at Using carboxylic acids in dehydration the ratio of endo / exo can be improved to 2.5: 1.
  • a disadvantage of the process described in EP-A-0648722 is that the conversion to the alcoholate is first carried out in diethyl ether / THF, and that the alcoholate is then added to an aqueous carboxylic acid solution.
  • the solvent diethyl ether should not be used on an industrial scale.
  • the use of two reactors, one for the alcoholate synthesis and one for the dehydration, is expensive.
  • the object was therefore to find a process for the preparation of substituted, in particular 1,3-disubstituted, cyclopentanes which avoids the disadvantages mentioned above and can be carried out without problems under technical conditions.
  • the present invention thus relates to a process for the preparation of substituted, in particular 1,3-disubstituted, cyclopentadienes comprising the steps:
  • R is a -C-C 0 hydrocarbon radical, preferably equal to alkyl or aryl and particularly preferably equal to methyl or phenyl, and
  • R 2 , R 3 are the same or different hydrogen or a -C ⁇ C 2 o hydrocarbon radical, preferably hydrogen, alkyl or aryl, particularly preferably hydrogen or a linear or branched Ci-C ⁇ alkyl radical, and
  • R 4 , R 5 , R 6 are identical or different hydrogen or a -C 20 hydrocarbon radical, preferably hydrogen, alkyl or aryl, particularly preferably hydrogen, and
  • M is Li, MgCl, MgBr or Mgl
  • step b) optionally separating the inert organic solvent from step a) and adding one or more water-immiscible organic solvents
  • step c) adding a strong, aqueous inorganic acid in order to achieve protonation and dehydration of the compound of the formula (III) formed in step a) to form the compounds of the formula (IVa) and (IVb).
  • a substituted, in particular a 3-position-substituted-cyclopent-2-en-l-one is first reacted with a Grignard compound or an organolithium compound MCHR 2 R 3 to give the tertiary alcoholate.
  • the alcoholate is then dehydrated in the same reactor by adding a strong inorganic acid in an aqueous two-phase system to an endo / exo isomer mixture, the desired endo content being at least 70% (based on the total amount of endo / exo).
  • the organic solvent phase must be practically immiscible with the aqueous acid phase in order to avoid acid-catalyzed isomerization from the endo isomer to the exo isomer.
  • the presence of acidic compounds that are soluble in both the aqueous and organic phases should also be avoided. If the organic phase contains large proportions of a water-miscible solvent, the endo / exo ratio deteriorates.
  • a partial change of solvent for example by a water-miscible solvent such as tetrahydrofuran is partially distilled off, by a hydrocarbon such as an alkane or an aromatic or corresponding mixtures, such as pentane, hexane, isohexane, heptane, ® Exxsol DSP 100-120, toluene, Xylene, ethylbenzene, tetrahydronaphthalene, preferably heptane, is replaced and only then is the aqueous mineral acid added.
  • a hydrocarbon such as an alkane or an aromatic or corresponding mixtures, such as pentane, hexane, isohexane, heptane, ® Exxsol DSP 100-120, toluene, Xylene, ethylbenzene, tetrahydronaphthalene, preferably heptane, is replaced and only then is the aqueous mineral
  • the strong, aqueous inorganic acids used are preferably those whose pKa value is less than 4.
  • hydrochloric acid, sulfuric acid or phosphoric acid is used.
  • the substituted-2-cyclopentene-l-ones are known in part from the literature.
  • the preferred 3-substituted-2-cyclopenten-1-ones can be prepared from 1, -diketones, for example, by methods known from the literature (J. Chem. Soc. 1127 (1952); US Pat. No. 5,026,919; J. Org. Chem. 55: 311-315 (1990); Tetrahedron 39: 4127-4132 (1983)).
  • 3-Methyl- or 3-phenyl-2-cyclopenten-l-ones are preferred.
  • organometallic compounds R 2 R 3 CHM where R 2 , R 3 and M are as defined above, are commercially available or can be easily prepared by processes known from the literature (for example Grignard compounds: Organikum, 15th edition, VEB German Publishing House of Sciences, Berlin 1981, p. 623).
  • the reaction of the organometallic compound with the cyclopent-2-en-1-one can be in a ratio of 1: 1 to 1.5: 1, preferably 1.1 to 1.3: 1 in ether-containing solvents or solvent mixtures which are an ether but not diethyl ether , and contain a hydrocarbon, preferably tetrahydrofuran as ether and heptane or toluene as hydrocarbon, in a temperature range from -78 ° C to 110 ° C, preferably -10 ° C to 50 ° C.
  • the mixture is stirred for a further 0 to 5 h, preferably 1 to 3 h at a temperature of 0 ° C. to 110 ° C., preferably 20 ° C. to 50 ° C., before under reduced pressure, 800 mbar to 100 mbar, preferably 400 to 600 mbar, the ether, in particular tetrahydrofuran, is largely distilled off.
  • the distilled-off water-miscible solvent or the solvent component is replaced by a water-immiscible hydrocarbon, as described above, preferably n-heptane.
  • Mineral acid preferably hydrochloric acid, sulfuric acid or phosphoric acid, particularly preferably dilute sulfuric acid
  • the volume of the aqueous acid phase to the volume of the organic phase being 2: 1 to 0.5: 1.
  • the molar ratio of the protons to the organometallic compound used is 1: 1 to 4: 1, preferably 1.5: 1 to 2.5: 1.
  • the pH of the aqueous phase is less than 4, preferably less than 2.
  • the entire reaction procedure is characterized in that the various reaction steps, the possible production of an organometallic compound, for example the production of a Grignard compound, the reaction of the substituted cyclopent-2-en-l-one with the organometallic compound, the subsequent protonation of the tertiary alcoholate and the acid-catalyzed dehydration of the tertiary alcohol to the substituted cyclopentadiene, all of which are carried out in succession in the same reaction vessel.
  • an organometallic compound for example the production of a Grignard compound
  • the reaction of the substituted cyclopent-2-en-l-one with the organometallic compound the subsequent protonation of the tertiary alcoholate and the acid-catalyzed dehydration of the tertiary alcohol to the substituted cyclopentadiene, all of which are carried out in succession in the same reaction vessel.
  • the dehydration also produces the undesired exo isomer, the ratio endo / exo> 1.5: 1, preferably> 2: 1.
  • the endo / exo isomer mixture can be obtained by distillation under reduced pressure.
  • the content of the endo isomer can be determined by gas chromatography in order to calculate the amount of base required for deprotonating the substituted cyclopentadiene, such as, for example, butyllithium, methyllithium, phenyllithium, dibutylmagnesium, butylmagnesium chloride, sodium hydride or potassium hydride.
  • the substituted cyclopentadienyl alkali metal or alkaline earth metal salt prepared in this way can be prepared by known methods by reaction with the halides of titanium, zirconium, hafnium or the lanthanoids, preferably zirconium tetrachloride or the ether complexes of ZrCl 4 , for example ZrCl 4 * 2THF or ZrCl * DME, to be converted to the corresponding metallocene.
  • the mixture was stirred at 24 ° C for 2 hours. 30 ml of toluene were added. At 0 ° C to 25 ° C, 3 g of water and then 60 ml of 2 molar sulfuric acid were added dropwise with vigorous stirring, the temperature rising to 40 ° C. The mixture was then stirred at 60 ° C for 1 h. The phases were separated, the organic phase was washed with 40 ml of water and dried with 5 g of magnesium sulfate. The GC of the crude product shows an endo / exo ratio of 1: 1.4.

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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 permettant de préparer des cyclopentadiènes substitués, notamment des cyclopentadiènes 1,3-disubstitués, obtenus à partir de cyclopent-2-en-1-ones substituées.
PCT/EP2000/000015 1999-01-12 2000-01-04 Procede de preparation de cyclopentadienes substitues WO2000041987A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19900732A DE19900732A1 (de) 1999-01-12 1999-01-12 Verfahren zur Herstellung von 1,3-disubstituierten Cyclopentadienen
DE19900732.2 1999-01-12
DE19935885A DE19935885A1 (de) 1999-07-30 1999-07-30 Verfahren zur Herstellung von substituierten Cyclopentadienen
DE19935885.0 1999-07-30

Publications (1)

Publication Number Publication Date
WO2000041987A1 true WO2000041987A1 (fr) 2000-07-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/000015 WO2000041987A1 (fr) 1999-01-12 2000-01-04 Procede de preparation de cyclopentadienes substitues

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WO (1) WO2000041987A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1333017A2 (fr) * 2002-02-02 2003-08-06 MERCK PATENT GmbH Procédé pour la production d'alcènes
CN112723978A (zh) * 2020-12-28 2021-04-30 山东京博中聚新材料有限公司 一种四甲基环戊二烯的制备工艺

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0648722A1 (fr) * 1993-10-15 1995-04-19 Albemarle Corporation Procédé pour la préparation d'alkylcyclopentadiènes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0648722A1 (fr) * 1993-10-15 1995-04-19 Albemarle Corporation Procédé pour la préparation d'alkylcyclopentadiènes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1333017A2 (fr) * 2002-02-02 2003-08-06 MERCK PATENT GmbH Procédé pour la production d'alcènes
EP1333017A3 (fr) * 2002-02-02 2004-01-07 MERCK PATENT GmbH Procédé pour la production d'alcènes
CN112723978A (zh) * 2020-12-28 2021-04-30 山东京博中聚新材料有限公司 一种四甲基环戊二烯的制备工艺

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