Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
  • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
  • C07D333/56—Radicals substituted by oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings

Definitions

• the present invention relates to a process for preparing heterocyclic ketones of the formulae (I) and (la)
• R 1 is hydrogen or a C ⁇ -C 40 carbon-containing group
• R is hydrogen or a C C 4 o carbon-containing group, or R 1 and R 2 together form a cyclic ring system,
• R 3 is a C ⁇ -C 40 carbon-containing group
• X is an element of the 16th group of the Periodic Table or is a divalent nitrogen group
• R 4 is an electron-withdrawing radical which is selected from the group consisting of perhalogenated C C 0 carbon-containing radicals and C C 0 organosulfonyl groups.
• Substituted heterocyclic ketones are important starting products for preparing heterocyclic metallocene catalysts for the polymerization of ⁇ -olefins (J. Am. Chem. Soc, Vol. 123, No. 20, 4763-4773).
• chiral heterocyclic ansa-metallocenes are obtainable which have a high significance as a transition metal component of highly active catalysts in stereospecific olefin polymerization (WO 98/22486).
• Variation of the ligand system allows the catalyst properties of the metallocenes to be influenced in a targeted manner. This allows the polymer yield, the molecular weight distribution, the tacticity and the melting point of the polymers to be varied to a desired extent, as is also observed in the case of the related ansa-bisindenylmetallocenes (Chem. Rev. 2000, No. 4).
• Cyclopenta[b]thiophenes and cyclopenta[b]pyrroles are important ligand precursors for synthesizing the chiral heterocyclic ansa-metallocenes. Both cyclopenta[b]thiophenes and cyc!openta[b]pyrroles are generally prepared from the corresponding heterocyclic ketones.
• An example of a possibility of constructing a sulfur-containing cyclic ketosystem consists in the reaction of a substituted thiophene with methacrylic acid in the presence of super-polyphosphoric acid (J. Am. Chem. Soc, Vol. 123, No. 20, 4763-4773).
• heterocyclic ketones of the formulae (I) or (la) which comprises performing the reaction in a liquid reaction medium which comprises at least one strong organic acid and at least one water absorbent, where the strong organic acid has a higher acid strength than the carboxylic acid of the formula (III), by adding simultaneously the heterocyclic compound of the formula (II) together with the ⁇ , ⁇ -unsaturated carboxylic acid of the formula (III) or together with its anhydride of the formula (IV) to said liquid reaction medium.
• R 1 is hydrogen or a C**-C 40 carbon-containing group, for example a C* ⁇ -C 40 -alkyl radical, a C ⁇ -C** 0 - fluoroalkyl radical, a radical, a C 6 -C 0 -aryl radical, a C 2 -C 40 heteroaromatic radical, a C 6 -C* ⁇ o-fluoroaryl radical, a C 6 -C ⁇ 0 -aryloxy radical, a C 3 -C 1a -trialkylsilyl radical, a C 2 -C 2 o-alkenyl radical, a C 2 -C 20 -alkynyl radical, a C 7 -C 40 -arylalkyl radical or a C 8 -C 0 -arylalkenyl radical.
• a C* ⁇ -C 40 -alkyl radical for example a C* ⁇ -C 40 -alkyl radical, a C ⁇ -C** 0
• R 1 is preferably hydrogen, a cyclic, branched or unbranched C 1 -C 20 -, preferably C ⁇ -C 8 -aIkyl radical, a C 2 -C 12 -, preferably C -C 8 - ⁇ -alken-1-yl radical, a C 6 -C 2 -, preferably C 6 -C 14 -aryl radical or an arylalkyl radical having from 1 to 10, preferably from 1 to 4, carbon atoms in the alkyl radical and from 6 to 22, preferably from 6 to 10, carbon atoms in the aryl radical.
• R 1 radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclopentyl, n-hexyl, cyclohexyl, 5-hexen-1-yl, 7-octen-1-yl, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyi, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di-(tert-butyl)-phenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 1-naphthyl, 2-naphthyl, phenanthryl, p-isopropylphenyl,
• R 2 is hydrogen or a C* ⁇ -C 40 carbon-containing group, for example a C ⁇ -C 40 -alkyl radical, a C C ⁇ 0 - fluoroalkyl radical, a C C ⁇ 2 -alkoxy radical, a C 6 -C 40 -aryl radical, a C 2 -C 40 heteroaromatic radical, a C 3 -C 10 -fluoroaryl radical, a C 6 -C ⁇ 0 -aryloxy radical, a C 3 -C 8 -trialkylsilyl radical, a C 2 -C 2 o-alkenyl radical, a C 2 -C 20 -alkynyI radical, a C 7 -C 0 -arylalkyl radical or a C 8 -C 40 -arylalkenyl radical.
• a C ⁇ -C 40 -alkyl radical for example a C ⁇ -C 40 -alkyl radical, a C C ⁇ 0
• R 2 is preferably hydrogen, a cyclic, branched or unbranched C 1 -C 20 -, preferably C C 8 -alkyl radical, a C 6 -C 22 -, preferably C 6 -C 1 -aryl radical or an arylalkyl radical having from 1 to 10, preferably from 1 to 4, carbon atoms in the alkyl radical and from 6 to 22, preferably from 6 to 10, carbon atoms in the aryl radical.
• R 2 radicals are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, phenyl, 2-tolyl, 3-tolyl, 4-toiyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di-( tert- butyl)-phenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 1-naphthyl, 2-naphthyl, phenanthryl, p-
• R 1 and R 2 together may also form a cyclic ring system which may be either monocyclic or polycyclic and either saturated or unsaturated.
• the R 1 and R 2 radicals together are preferably a substituted or unsubstituted 1 ,3-butadiene-1 ,4-diyl group.
• the R 1 and R 2 radicals together are more preferably an unsubstituted 1 ,3-butadiene-1 ,4-diyl group or a singly or doubly terminally substituted 1 ,3-butadiene-1 ,4-diyl group where terminal substituents may have the same definition as R 2 .
• Preferred terminal radicals on the 1,3-butadiene-1 ,4-diyl group are methyl or phenyl.
• R 3 is a C C 40 carbon-containing group, for example a C ⁇ -C 0 -alkyl radical, a C C ⁇ 0 -fluoroalkyl radical, a C 6 -C 0 -aryl radical, a C 2 -C 0 heteroaromatic radical, a C 6 -C ⁇ 0 -fluoroaryl radical, a C 7 -C 0 - arylalkyl radical or a C 3 -C 18 -trialkylsilyl radical.
• a C ⁇ -C 0 -alkyl radical for example a C ⁇ -C 0 -alkyl radical, a C C ⁇ 0 -fluoroalkyl radical, a C 6 -C 0 -aryl radical, a C 2 -C 0 heteroaromatic radical, a C 6 -C ⁇ 0 -fluoroaryl radical, a C 7 -C 0 - arylalkyl radical or a
• R 3 is preferably a cyclic, branched or unbranched C 1 -C 2 0-, preferably C-*-C 8 -alkyl radical, a C 3 -C 22 -, preferably C 6 -C 4 -aryl radical, an arylalkyl radical having from 1 to 10, preferably from 1 to 4, carbon atoms in the alkyl radical and from 6 to 22, preferably from 6 to 10, carbon atoms in the aryl radical, or a C -C 24 heteroaromatic radical selected from the group consisting of substituted 2- or 3-thienyl radicals, substituted 2- or 3-furyl radicals or substituted pyrrol-2- or -3-yl radicals where the substituted five-membered heteroaromatic radicals bear no hydrogen atom in positions 2 and 5 and are identically or differently substituted in positions 1 , 3 and 4 or are unsubstituted, and where the substituents on the five-membered heteroaromatic radicals are identical or different C C 2 o
• X is an element of the 16th group of the Periodic Table, such as oxygen, sulfur, selenium or tellurium, preferably sulfur or selenium, in particular sulfur, or X is a divalent nitrogen group -(N-R 4 )-, where R 4 is an electron-withdrawing radical which is selected from the group consisting of perhalogenated C ⁇ -C 40 carbon-containing radicals, for example a perfluorinated C C o-alkyl radical or perfluorinated C 6 -C 22 -aryl radical, or a C r C 0 -organosulfonyl group, for example a C-
• R 4 is an electron-withdrawing radical which is selected from the group consisting of perhalogenated C ⁇ -C 40 carbon-containing radicals, for example a perfluorinated C C o-alkyl radical
• R 4 radicals examples include trifluoromethyl, n-nonafluorobutyl, pentafluorophenyl, heptafluoronaphthyl, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-tolylsulfonyl or trifluoromethylsulfonyl.
• X is extremely preferably sulfur.
• alkyl encompasses, unless further restricted, linear or singly or optionally also multiply branched saturated hydrocarbon radicals which may also be cyclic.
• alkenyl as used in the present context encompasses linear or singly or optionally also multiply branched hydrocarbon radicals having at least one, optionally also more than one, C-C double bonds which may be cumulated or conjugated. Preference is given to C 2 -C ⁇ 2 - ⁇ -alken-1-yi radicals such as vinyl, allyl, 3-buten-1-yl, 5-hexen-1-yl, 7-octen-1-yl and 9-decen-1-yl.
• aryl refers, unless further restricted, to aromatic and optionally also fused polyaromatic hydrocarbon radicals which may optionally be mono- or polysubstituted by linear or branched C C*
• substituted and unsubstituted aryl radicals are in particular phenyl, 2-methylphenyI, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert- butylphenyl, 4-methoxyphenyl, 1-naphthyl, 9-anthryl, 9-phenanthryl, 3,5-dimethylphenyl, 3,5-di- ferf-butylphenyl or 4-trifluoromethylphenyl.
• heteromatic radical refers to aromatic hydrocarbon radicals in which one or more carbon atoms are replaced by nitrogen, phosphorus, oxygen or sulfur atoms or combinations thereof. These may optionally be mono- or polysubstituted by linear or branched C C 18 -alkyl, C 2 -C* ⁇ o-alkenyl or C 6 -C** 0 -aryl.
• Preferred examples include thienyl, furyl, pyrrolyl, pyridyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, pyrimidinyl, pyrazinyl and the like, and also methyl, ethyl, propyl, isopropyl and tert-butyl radical-substituted derivatives thereof.
• R 3 being methyl and X being sulfur and R 1 and R 2 each being as defined above.
• the process according to the invention is notable in that the reaction is performed in a liquid reaction medium which comprises at least one strong organic acid and at least one water absorbent, where the strong organic acid has a higher acid strength than the carboxylic acid of the formula (III), by adding simultaneously the heterocyclic compound of the formula (II) together with the , ⁇ -unsaturated carboxylic acid of the formula (III) or together with its anhydride of the formula (IV) to said liquid reaction medium. Preference is given to adding a preformed mixture of the reaction components to the liquid reaction medium.
• the strong organic acids which may be used in the process according to the invention have a higher acid strength than the carboxylic acids of the formula (III).
• preferred strong organic acids include perhalogenated carboxylic acids, for example trichloroacetic acid, trifluoroacetic acid or perfluoropropionic acid, or C ⁇ -C., 8 -alkylsulfonic acids which may also be halogenated. Preference is given to using *-C 8 -, in particular C C -alkylsulfonic acids in the process according to the invention.
• Preferred examples are methanesulfonic acid, trifluoromethanesulfonic acid and ethanesulfonic acid, in particular methanesulfonic acid.
• the water absorbent should be capable of binding water of reaction in the acid reaction medium physically, for example in the case of a molecular sieve, or chemically, for example in the case of phosphorus pentoxide. Preference is given to using phosphorus pentoxide as the water absorbent in the process according to the invention.
• the liquid reaction medium may also comprise inert solvents, for example alkanes or halogenated alkanes.
• alkanes examples include pentane, hexane, heptane and dodecane
• suitable halogenated alkanes include methylene chloride and 1 ,2-dichloroethane.
• the starting compounds of the formulae (II), (III) and (IV) are not to be regarded as components of the above-described liquid reaction medium.
• the molar ratio of the heterocyclic compound of the formula (II) to the ⁇ , ⁇ -unsaturated carboxylic acid of the formula (III) is typically in the range from 5 : 1 to 1 : 100. Preference is given to the ratio being in the range from 2 : 1 to 1 : 3, in particular in the range from 1.1 : 1 to 1 : 1.5.
• the anhydride of the formula (IV) is used instead of the ⁇ , ⁇ -unsaturated carboxylic acid of the formula (III), it should be noted that one mole of anhydride of the formula (IV) corresponds to two moles of carboxylic acid of the formula (III) in the process according to the invention:
• the mass ratio of the heterocyclic compound of the formula (II) to the liquid reaction medium in the process according to the invention is typically in the range from 1 : 2 to 1 : 1000, preferably in the range from 1 : 3 to 1 : 50, more preferably in the range from 1 : 5 to 1 : 35.
• the mass ratio of the water absorbent to the strong organic acid is preferably in the range from 1 : 99 to 25 : 75.
• the mass ratio is in particular between 5 : 95 and 15 : 85.
• the reaction temperature in the process according to the invention is typically in the range from 20 to 200°C, preferably in the range from 50 to 110°C, in particular in the range from 60 to 90°C. At a reaction temperature of 20°C, a very low conversion was observed, at only 60°C a satisfactory conversion and, at 110°C, the maximum of the conversion to the desired reaction product was exceeded.
• the process according to the invention is typically carried out under atmospheric pressure. However, it may in principle also be carried out under reduced or elevated pressure. It is important merely that the reaction partners are present together in the liquid reaction medium under the reaction conditions, in order to be able to react with each other in an optimum manner.
• the process according to the invention is notable for good yields, high space-time yields and simple isolation and workup of the reaction products from the reaction mixture.
• Mass spectra were measured using a Hewlett Packard 6890 instrument which was equipped with a 5973 mass analyzer (El, 70 eV).
• Super-PPA super-polyphosphoric acid
• phosphorus pentoxide was prepared typically by completely dissolving 164.3 g of phosphorus pentoxide in 975.7 g of commercially obtainable polyphosphoric acid (Aldrich) at 140°C with stirring.
• Eaton's reagent was used as commercially obtained (Aldrich; 7.5% by weight of phosphorus pentoxide in methanesulfonic acid).
• Table 1 shows a comparison of examples 1 to 5 and comparative examples A to E

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Pyridine Compounds (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2002
  • 2002-12-19 DE DE10260095A patent/DE10260095A1/de not_active Withdrawn
• 2003
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