WO2012005694A1 - Dihydroindènes et composés associés - Google Patents

Dihydroindènes et composés associés Download PDF

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Publication number
WO2012005694A1
WO2012005694A1 PCT/SG2011/000240 SG2011000240W WO2012005694A1 WO 2012005694 A1 WO2012005694 A1 WO 2012005694A1 SG 2011000240 W SG2011000240 W SG 2011000240W WO 2012005694 A1 WO2012005694 A1 WO 2012005694A1
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copper
starting material
acid
compound
reaction
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Yugen Zhang
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Agency for Science Technology and Research Singapore
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Agency for Science Technology and Research Singapore
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/867—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an aldehyde or a ketone
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/18—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving halogen atoms of halogenated compounds
    • 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
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane

Definitions

  • the present invention relates to synthesis of dihydroindenes and related compounds.
  • the Friedel-Crafts cyclization reaction is a very important methodology for generating various useful carbocyclic compounds through carbon-carbon bond formation with aromatic substrates.
  • Bimolecular Friedel-Crafts cycloadditions in which bifunctional electrophiles react intramolecularly with the same aromatic ring, are more of a challenge to perform as competitive intermolecular reactions lead to non-ring products. It is well known that a bifunctional substrate capable of both acylation and alkylation of aromatic compounds is appealing for the formation of important cyclic aromatic ketones. Excess amount of A1C1 3 /BF 3 and/or strong protic acids were typically used to promote these cycloaddition reactions, as shown in Fig. 1. The cyclic aromatic ketones could be further reduced to form dihydroindenes.
  • Ar is an optionally substituted aromatic or heteroaromatic ring system (i.e. Ar may have non-hydrogen substituents or may have no non-hydrogen substituents) having at least one hydrogen attached to an aromatic carbon atom
  • R 1 , R 2 , R 3 , R 4 and R 3 are independently selected from the group consisting of H, alkyl and aryl.
  • the step of reacting the precursor with the allyl compound may be conducted in situ.
  • the step of producing the starting material may generate the acid and the starting material, so that the process is a one pot process for making the compound having a five membered ring fused to an aromatic ring from the precursor and the allyl compound.
  • the process may be conducted in the presence of an acid.
  • the copper (II) salt may be copper (II) trifiate. It may be catalytic. It may be catalytic for the coupling reaction of the precursor to the allyl compound or for the cyclisation reaction to convert the starting material to the product or for both the coupling reaction and the cyclisation reaction.
  • the process may be conducted in a halogenated solvent.
  • the first aspect being conducted as a two step reaction (the first step being making the starting material and second step being reacting the starting material in the presence of acid), either may be conducted in a halogenated solvent or both may be conducted in a halogenated solvent.
  • Ar may be a carbocyclic aromatic ring system.
  • Ar may be a monocyclic aromatic ring system.
  • Ar may be both monocyclic and carbocyclic.
  • the process (or any one of the steps in the process) may be accompanied by migration of a substituent on the aromatic ring. In this case, the substituent which migrates may be an alkyl substituent or an aryl substituent.
  • X may be a halide, an alcohol or an ester.
  • the process may be conducted with no added base. It may be conducted under acidic conditions. It may be conducted under anhydrous conditions.
  • R 1 , R 2 and R 3 are all H.
  • R 4 and R 5 are either both alkyl or one is hydrogen and the other is an aryl group.
  • Ar is an optionally substituted aromatic or heteroaromatic ring system having at least one hydrogen attached to an aromatic carbon atom
  • R 4 and R 5 are either both alkyl groups or one is hydrogen and the other is an aryl group.
  • a product having a five membered ring fused to an aromatic ring, said compound being made by the process of the first or second aspect.
  • Figure 1 is a scheme illustrating Friedel-Crafts cycloaddition reaction on aromatic ring
  • Figure 2 is a scheme illustrating Proposed reaction mechanism
  • Figure 3 is a scheme illustrating Transformation conditions between 1, 2 and 7;
  • Figure 4 is a scheme illustrating Blank reaction of cinnamyl chloride in Cu(OTf) 2 catalyst system.
  • Figure 5 is an X-ray crystal structure showing the molecular structure of compound 7. Hydrogen atoms have been omitted for clarity.
  • the present invention relates to a process for making a product having a five membered ring fused to an aromatic ring.
  • the product may be an dihydroindene (i.e. an indane) or it may be an indane-like compound.
  • a substituted propene starting material cyclises in the presence of acid and a copper II salt of a superacid to produce the product.
  • the starting material has structure
  • Ar is an optionally substituted aromatic or heteroaromatic ring system having at least one hydrogen attached to an aromatic carbon atom
  • R J , R 2 , R 3 , R 4 and R 5 are independently selected from the group consisting of H, alkyl and aryl.
  • the product will have structure:
  • the Ar ring system in the may be substituted, e.g. with one or more alkyl groups, aryl groups, alkoxy groups, aryloxy groups or hydroxy groups. It should be noted that the Ar ring system will not change through this reaction, however the substitution pattern may change, since substituent groups, particularly substituent alkyl groups may migrate. This is particularly the case when there are no hydrogen atoms on the Ar ring system ortho to the group in the starting material, e.g. if both ortho substituents are alkyl groups.
  • the starting material described above may be prepared by reacting an aryl compound precursor with a suitable allyl compound having a leaving group in the allyl position, in the presence of a suitable copper II compound.
  • acid is generated in reacting the allyl compound with the precursor to produce the starting material. Unless the acid is scavenged (by addition of a base, e.g. carbonate or amine) this acid can convert the starting material in situ into the product in the presence of the copper II compound.
  • the starting material is cyclised in the presence of acid and the copper II salt to provide the product.
  • the allyl compound and the aryl precursor are reacted in the presence of a suitable copper II compound to form the product.
  • the starting material is formed as an intermediate, and reacts in situ.
  • the allyl compound and the aryl precursor are reacted in the presence of a suitable copper II compound to form the starting material. This may in some cases be conducted in the presence of base in order to suppress further reaction.
  • the starting material may then be cyclised to the product by addition of acid, either with or without separation of the starting material from the reaction mixture. In the event that the starting material is separated, further copper II compound may be added.
  • this compound contains an aromatic ring system.
  • the ring system of the precursor may be a monocyclic aromatic ring, e.g. a benzene ring or a heterocyclic ring (e.g. pyridine, pyrazine, pyridazine, thiophene, furan etc.). It may be a 6 membered ring, or may be a 5 membered ring or may be some other ring size.
  • the precursor may contain a bicyclic or polycyclic ring system. This may be a carbocyclic aromatic ring fused with either a second carbocyclic aromatic ring or with a heterocyclic aromatic ring. It may comprise two fused heterocyclic rings, which may be the same or may be different.
  • n may be 2, 3, 4, 5 or more than 5.
  • Non-hydrogen substituents in the precursor follows directly from the structure of the ring system and the number of hydrogen atoms n.
  • Ar has no non-hydrogen substituents.
  • Ar has at least one (e.g. 1, 2, 3 or 4 or more than 4) non-hydrogen substituent, e.g. an alkyl substituent.
  • Suitable starting materials include 1,2,4,5- tetraalkylbenzene, 1,2,4- and 1,2,3-trialkylbenzene, ortho- and meta-xylene, alkoxyxylenes (e.g. 2,5- and 2,6-dialkylanisole, 2,3,4-, 2,3,5- and 2,3,6-trialkylphenols etc.
  • alkyl includes cycloalkyl groups.
  • the alkyl groups may be straight chain or may be branched. They may be CI to C 12 or longer, or may be CI to C6, CI to C3, C2 to C12, C6 to C12 or C2 to C6 (provided that if the alkyl group is cyclic or branched it is greater than C2).
  • the alkyl groups may in some cases be substituted.
  • Suitable alkyl groups include optionally substituted methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, pentyl, neopentyl, hexyl, octyl, isooctyl, cyclopentyl or cyclohexylmethyl.
  • the precursor is not 1,3,5-trimethylbenzene or o- xylene.
  • each of R 1 to R 5 may, independently be alkyl or aryl or hydrogen.
  • the carbon-carbon double bond may be in the cis- form or the anti- form or there may be a mixture of cis and trans forms.
  • Suitable allyl compounds include cinnamates (in which R 5 is phenyl and R 1 to R 4 are all H and the double bond is trans). In other suitable allyl compounds the R 4 and R 5 are both alkyl (e.g. methyl) and R 1 to R 3 are all H. Common leaving groups in the allyl compound include chloride, bromide, toxylate, hydroxyl, acetate, benzoate etc.
  • the allyl compound When reacting the allyl compound with the precursor, the allyl compound may be used in approximately equimolar amount to the precursor, or in slight molar excess. It may for example be used in a molar ratio to the substrate of about 1.1 (i.e.
  • Alkyl groups which may be used for R 1 to R 5 may be linear, branched, cyclic or a combination of any or all of these. They may be as described earlier (under “precursor")- They may optionally be substituted, for example by alkyl groups, aryl groups, halides, esters, hydroxyl groups, ether groups etc.
  • Aryl groups may be carbocyclic or heterocyclic. They may be 5 membered, 6 membered or some other ring size. They may be monocyclic or may be bicyclic or polycyclic, and may be fused or linked.
  • the double bond may be cis or it may be trans or there may be a mixture of cis and trans forms.
  • the starting material may have the same structure as described for the allyl compound except that X is replaced by Ar. In the one pot process from precursor and allyl compound to product, the starting material may be regarded as an intermediate.
  • copper salt this is a copper (II) salt of a superacid. It may be for example a triflate (trifluoromethanesulfonate). It may be a salt of an acid having pKa of less than about -12, or less than about -13, -14 or -15, or of about -12, -12.5, -13, -13.5, -14, -14.5 or -15. Triflic acid has been estimated to have pKa of about -15.
  • Other suitable superacids include fluoroantimonic acid fluorosulfonic acid. Superacids are considered to be those acids with an acidity greater than that of 100% pure sulfuric acid (which has a Hammett acidity function (H 0 ) of -12).
  • the Hammett acidity function of the superacid may therefore be less than about -12, or less than about -13, -14 or -15, or may be about -12, -12.5, -13, -13.5, -14, -14.5 or -15.
  • the copper salt may be soluble in the solvent used in the reaction.
  • the copper salt may be a copper catalyst. It may be used in a catalytic amount. It may be used in a molar ratio to the precursor or to the starting material of about 1 to about 10mol%, or about 1 to 5, 5 to 10 or 3 to 7mol%, e.g. about 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10mole%.
  • the conversion of the starting material to the product requires the presence of an acid. This may be generated in situ, or may be added discretely. It may have a pKa of less than about 5, or less than about 4.5, 4, 3.5, 3, 2.5, 2, 1.5 or 1. It may be a strong acid It may be an organic acid or may be a mineral acid. It may be derived from, or may be the conjugate acid of, the leaving group on the allyl compound. Thus for example if X in the allyl compound is CI, the acid may be hydrochloric acid and if X is acetate, the acid may be acetic acid.
  • the starting material may be added in at least 1 mole equivalent relative to the starting material, or at least about 1.5 or 2 mole equivalents, e.g. about 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2 mole equivalents or more. It may be hydrochloric acid, sulfuric acid, trifluoroacetic acid or some other acid.
  • the solvent may be a solvent for the substrate and for the allyl compound in the amounts in which these are used. It may be a solvent for the copper salt. It may be an anhydrous solvent. It may be an aprotic solvent. It may be a polar solvent. It may be a halogenated solvent, e.g. chlorinated or brominated or both. It may be a haloalkane. It may be a dihaloalkane, e.g. a dichloroalkane, or a polyhaloalkane. It may be for example methylene chloride or dichloroethane (1,1- or 1,2-).
  • reaction may be a mixture of halogenated solvents, or may be a mixture of a halogenated solvent with a non-halogenated solvent, preferably an aprotic non-halogenated solvent.
  • the reaction involves a homogeneous reaction mixture and in other embodiments it involves a heterogeneous reaction mixture.
  • the conversion from starting material to product may be conducted with no added base. It may be conducted under acidic conditions. It may be conducted in the presence of an acid. It may be conducted under anhydrous conditions.
  • the conversion from precursor to starting material may be conducted under basic conditions or neutral conditions or acidic conditions. It may be conducted under anhydrous conditions. In the event that it is conducted under basic conditions, it may not proceed all the way to the product and may stop at the starting material. This may be subsequently converted to the product under acidic conditions as described above.
  • the combined process may be conducted as a one pot process by addition of acid to the reaction mixture containing the starting material. Sufficient acid should then be added to neutralise any base present in the reaction mixture and to acidify the reaction mixture.
  • the starting material may be isolated and then converted under acidic conditions to the product, making the overall process a two pot process.
  • the reaction may be conducted in a sealed container. It may be conducted at reflux. It may be conducted at a temperature of about 40 to about 80°C, or about 40 to 60, 60 to 80 or 50 to 70°C, e.g. about 40, 50, 60, 70 or 80°C. It may be conducted in solution, in suspension or both in solution and suspension (i.e. some components may be in solution and others in suspension).
  • the reaction time will depend on the actual reagents, concentrations and reaction temperature used. It may be for example about 12 to about 24 hours, or about 12 to 18, 18 to 24 or 14 to 18 hours, e.g. about 12, 14, 16, 18, 20, 22 or 24 hours. It may be conducted under air or under some other atmosphere, e.g. nitrogen, argon, helium, carbon dioxide or a mixture of these.
  • a one pot process for making a compound having an indane nucleus comprises combining a precursor comprising an alkyl and/or alkoxy substituted benzene ring having at least two hydrogen atoms attached to the benzene ring, and an allyl compound having an allylic substituent which is a halide or an ester, in a halogenated solvent and in the presence of copper (II) triflate.
  • an acid e.g. a hydrogen halide, may be added.
  • the present invention relates to a direct, one-step catalytic synthesis of dihydroindene skeleton from substituted benzenes and haloalkenes.
  • the reaction is thought to involve a [3+2] cycloaddition onto an aromatic ring with Cu(OTf) 2 catalyst under relatively mild conditions.
  • This simple method can be applied to a variety of indane skeletons or benzo-fused carbbcycles synthesis.
  • This new method can be applied to a variety of indane skeletons or benzo-fused carbocycles synthesis.
  • Allylic halides possess two reactive centers susceptible to Friedel-Crafts alkylation. It is known that haloalkenes generally favor reaction at the double bond with protic acid catalysts. ?-Toluenesulfonic acid can promote cinnamyl halide alkylation on the allylic position, but is not applicable to other simple haloalkenes. Metal catalysts also favor the reaction at the allylic position. When Cu(OTf) 2 was tested in catalyzing allylation of substituted benzene with allylic halide, an unexpected [3+2] cycloaddition dihydroindene product was produced in high yield.
  • intermediate 2 underwent double methyl migration under acidic conditions to form intermediate 3, Fig. 2 B.
  • Lewis acid promoted methyl migration is well known as a reversible process and generally the efficiency of this migration is low.
  • intermediate 3 underwent fast intramolecular alkylation, the methyl migration was very efficient and all intermediate 2 was converted to 7 via intermediate 3.
  • intermediate 3 underwent acid induced intramolecular alkylation to form cycloaddition product 7, shown in step C in Fig. 2.
  • Cu(OTf 2 catalyzed the first step allylation reaction. After that, acid generated in the first step played an important role in the following methyl migration and intramolecular alkylation steps.
  • Diffraction-quality crystals were obtained by slowly vaporizing of hexane solution. Crystals were mounted in Infineum® oil on a fiber on a goniometer head which was placed in the dinitrogen cold stream on a Siemens (Bruker®) SMART CCD-based diffractometer at 223 K. Cell parameters were retrieved using SMART software and refined using SAINT on all observed reflections.

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

Abstract

L'invention concerne un procédé de fabrication d'un composé comprenant un cycle à cinq éléments fusionné à un cycle aromatique. Dans le procédé, une matière première comprenant le cycle aromatique et un composé allylique dans lequel au moins un substituant allylique est un groupe partant sont combinés dans un solvant et en présence d'un sel de cuivre (II) d'un super-acide. La matière première peut être fabriquée in situ par mise en réaction d'un précurseur aromatique avec un composé allylique en présence du sel de cuivre II.
PCT/SG2011/000240 2010-07-07 2011-07-07 Dihydroindènes et composés associés Ceased WO2012005694A1 (fr)

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SG201004889-0 2010-07-07
SG201004889 2010-07-07

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WO2012005694A1 true WO2012005694A1 (fr) 2012-01-12

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989012612A1 (fr) * 1988-06-24 1989-12-28 Amoco Corporation Preparation d'une dimethyltetraline

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989012612A1 (fr) * 1988-06-24 1989-12-28 Amoco Corporation Preparation d'une dimethyltetraline

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
OLAH, G. A. ET AL., SUPERACID CHEMISTRY, 2009, pages 63 - 65 *
PRAKASH, G. K. S. ET AL.: "Superacidic trifluoromethanesulfonic acid-induced cycli- acyalkylation of aromatics", CATALYSIS LETTERS., vol. 87, 2003, pages 109 - 112 *
ZHANG, Y. ET AL.: "A Copper(II) Triflate-Catalyzed Tandem Friedel-Crafts Alkylation/Cyclization Process towards Dihydroindenes", ADVANCED SYNTHESIS & CATALYSIS., vol. 353, 2011, pages 1055 - 1060 *

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