WO2010080505A2 - Procédé de conduite d'une réaction organique dans des liquides ioniques - Google Patents

Procédé de conduite d'une réaction organique dans des liquides ioniques Download PDF

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WO2010080505A2
WO2010080505A2 PCT/US2009/068498 US2009068498W WO2010080505A2 WO 2010080505 A2 WO2010080505 A2 WO 2010080505A2 US 2009068498 W US2009068498 W US 2009068498W WO 2010080505 A2 WO2010080505 A2 WO 2010080505A2
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mim
ionic liquid
methyl
ethanone
trimethylcyclohex
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PCT/US2009/068498
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WO2010080505A3 (fr
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Daniel Martin Bourgeois
Gregory Scot Miracle
Philip John Porter
Eva Boros
Kenneth Richard Seddon
Harambage Quintus Nimal Gunaratne
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The Procter & Gamble Company
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Priority to EP09796207A priority Critical patent/EP2370387A2/fr
Publication of WO2010080505A2 publication Critical patent/WO2010080505A2/fr
Publication of WO2010080505A3 publication Critical patent/WO2010080505A3/fr

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    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06Q—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
    • G06Q30/00—Commerce
    • G06Q30/02—Marketing; Price estimation or determination; Fundraising

Definitions

  • the present invention is related to processes for producing cyclic organic compounds using Lewis acidic ionic liquids.
  • substituted cyclohexenes may be synthesized in Diels-Alder type cycloadditions using Lewis acidic ionic liquids in the reaction medium.
  • the cyclohexene products have use as components in commercial compositions.
  • Perfume and aroma enhancing compounds are widely used as additives in the detergent and food industries. These compounds are used, for example, to augment or enhance the aromas of certain detergent compositions and perfumes, or to enhance the aroma and flavor characteristics of certain food or tobacco products among other products. Compounds with floral, fruity, woody, or other pleasing aroma are particularly desirable.
  • fragrance components may include a substituted cyclohexene structure. These structures include, for example, various isomers of ionone, isomers of damascone, isomers of cyclogeranate, and isomers of irone. Other cyclic fragrance compounds are also known.
  • the damascones including ⁇ -damascone, ⁇ -damascone, and ⁇ -damascone are examples of compounds having pleasing floral, fruity aromas used in the perfumery art.
  • the damascone isomers differ in the position of the ring double bond as shown in Scheme 1.
  • transjrans-b-d&m&scom is one of the most widely used fragrance additives in the detergent and food industries. Therefore, the industrial scale production of ⁇ -damascone and other related compounds is of great interest.
  • Ayyer et al., Journal of the Chemical Society Perkin Trans., 1975, 1, 1727-1736 discloses a 3-step synthesis of damascone starting from 1,3-pentadiene (piperylene) and mesityl oxide.
  • the synthesis of the isomers of damascene involved three separate reaction processes, a Diels- Alder cycloaddition, epimerization of the resulting cyclohexenyl methyl ketone, and condensation/elimination with acetaldehyde in an aldol condensation process.
  • the cycloadduct is a mixture of the cis and trans ring isomers, with the cis-isomer of the cycloadduct predominating.
  • the present disclosure provides for the synthesis of substituted cyclohexene reaction products from acyclic materials in high yield and in a process suitable for scale -up to industrial scale.
  • the present disclosure provides for a process for producing substituted cyclohexenes.
  • the process comprising the steps of providing to a reactor an ⁇ , ⁇ -unsaturated carbonyl dienophile of Formula I:
  • R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of H and
  • R ⁇ 5 , r R>6 , r R>7 , memo R8 , memo R9 and R , 10 are each independently selected from the group consisting of H and Ci-C 4 alkyl or any of R 6 and R 7 , R 7 and R 8 , R 8 and R 10 , or R 5 and R 9 may optionally be joined together to form a 5-, 6-, or 7-membered ring; providing a Lewis acidic ionic liquid to the reactor; and reacting the ⁇ , ⁇ -unsaturated carbonyl dienophile with the 1,3-diene to form a substituted cyclohexene product.
  • the present disclosure provides a process for producing a substituted cyclohexene product.
  • the process comprises reacting mesityl oxide with piperylene in a Lewis acidic ionic liquid to form predominantly cis-l-(2,6,6- trimethylcyclohex-3-en-l-yl)ethanone.
  • the l-(2,6,6- trimethylcyclohex-3-en-l-yl)ethanone may be further converted to trans, trans- ⁇ -damascone.
  • Still another embodiment of the present disclosure provides a process for producing ( ⁇ )- ⁇ -damascone.
  • the process comprises reacting mesityl oxide with piperylene in a Lewis acidic ionic liquid to form predominantly cis-l-(2,6,6-trimethylcyclohex-3-en-l-yl)ethanone; epimerizing the cis-l-(2,6,6-trimethylcyclohex-3-en-l-yl)ethanone to trans-l-(2,6,6- trimethylcyclohex-3-en-l-yl)ethanone; and condensing the trans-l-(2,6,6-trimethylcyclohex- 3-en-l-yl)ethanone with acetaldehyde to form ( ⁇ )- ⁇ -damascone.
  • the Lewis acidic ionic liquid is selected from the group consisting of AlCl 3 :[C 2 mim]Cl, AlCl 3 :[C 8 mim]Cl, and mixtures thereof.
  • Fig. 1 illustrates one approach for a Diels-Alder cycloaddition in a Lewis acidic ionic liquid according to the present disclosure.
  • Fig. 2 illustrates the effect of the amount of piperylene on a Diels-Alder cycloaddition according to one embodiment of the present disclosure.
  • the term “comprising” means various components conjointly employed in the preparation of the compositions of the present disclosure. Accordingly, the terms “consisting essentially of and “consisting of are embodied in the term “comprising”.
  • Diels-Alder cycloaddition describes a [4+2] cycloaddition between a diene component having a conjugated 1,3-diene functionality and a dienophile component having a reactive double or triple bond. Reactions via step-wise or concerted mechanisms are included within this term.
  • dienophile includes compounds having a reactive double or triple carbon-carbon bond that is reactive with a diene, for example, in a Diels-Alder cycloaddition.
  • Lewis acid includes an electrophilic compound capable of accepting an electron pair.
  • ionic liquid includes ionic compounds that are liquid under the reaction conditions.
  • Lewis acidic ionic liquid includes complexes formed between a Lewis acid component and an ionic liquid component.
  • the Lewis acid component may be dissolved in the ionic liquid.
  • Lewis acidic ionic liquids may be represented by the generic formula M(A) n : [Cation] + A " , where the Lewis acid is represented by M(A) n and the ionic liquid is represented by [Cation] + A ⁇ .
  • piperylene means a 1,3-diene having the IUPAC name 1,3- pentadiene.
  • the term "mesityl oxide” means a compound having the IUPAC name 4-methyl-3-penten-2-one,
  • the phrase "performed in a single reactor” means that the two or more reaction processes are performed in one (or more) reactor without an intermediate isolation step. In certain examples, the two or more reaction processes may also be performed without an intermediate workup or quenching step.
  • component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
  • the present invention is related to processes for producing cyclic organic compounds using Lewis acidic ionic liquids.
  • substituted cyclohexene reaction products may be synthesized in Diels-Alder type cycloadditions using a diene and a dienophile under Lewis acidic ionic liquid conditions in the reaction medium.
  • the processes disclosed herein have certain advantages over the prior art approaches, including, but not limited to, more concentrated reaction protocols, reduced side reactions, simplified workup conditions, recycling of reaction components, and fewer waste products.
  • the processes disclosed herein may more readily be utilized on an industrial scale since equipment needs and solvents are reduced and process steps are eliminated.
  • the processes disclosed herein provide distinct advantages over the prior art methods for synthesizing substituted cyclohexene reaction products.
  • the Diels-Alder cycloaddition involves a [4+2] reaction between a 1,3-diene and a dienophile to produce a cyclohexene product.
  • Certain Diels-Alder cycloadditions may occur under thermal conditions.
  • other Diels-Alder cycloadditions require a catalyst, such as a Lewis acid, for the diene to react with the dienophile to produce a cyclohexene product.
  • Lewis acid catalysis may increase the regioselectivity of the reaction, extent of endo addition (i.e., diastereoselectivity), and in the case of enantioselective reactions, the extent of enantioselectivity.
  • Lewis acid catalysis may have certain drawbacks, including, but not limited to, polymerization of reactants, more complicated work-up protocols, lack of recycling of the catalyst, and disposal of metal containing waste products. Many of these drawbacks are highly undesired when performing reactions on an industrial scale. Thus, new protocols for using Lewis acid catalysis in Diels-Alder cycloadditions are needed,
  • Ionic liquids typically have melting temperatures of about 100 0 C or less, or even 60 0 C or less. Some ionic liquids exhibit no discernible melting point (based on DSC analysis) but are '"flowable" at temperatures ranging from about 2O 0 C to about 100 0 C.
  • An ionic liquid comprises an anionic component and a cationic component and neutral in overall charge. In liquid form, the cationic and anionic components of an ionic liquid may freely associate with one another (i.e., in a scramble). For example, when two or more ionic liquids are combined, the binary, ternary or more complex mixtures of ionic liquid components may be prepared. Such combinations are discussed in further detail in U.S. Application Publication Nos.
  • the mixtures of ionic liquids may have melting points of 100 0 C or less.
  • the various embodiments of the reactions herein may use ionic liquids, including mixtures of ionic liquids.
  • Ionic liquids may be used in combination with a Lewis acid to form a Lewis acidic ionic liquid. Such combinations may display improved catalytic activity and reaction characteristics compared to the Lewis acid or the ionic liquid alone.
  • the present disclosure provides improved methods for the synthesis of substituted cyclohexenes utilizing a Diels-Alder reaction in a Lewis acidic ionic liquid.
  • the present methods provide cyclohexenes that may be transformed in to compounds suitable for use as aroma or perfume ingredients.
  • the process may comprise providing to a reactor an ⁇ , ⁇ -unsaturated carbonyl dienophile of Formula I:
  • R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are as described herein; providing a Lewis acidic ionic liquid to the reactor; and reacting the ⁇ , ⁇ -unsaturated carbonyl dienophile with 1,3-diene to form a substituted cyclohexene product.
  • the dienophiles and/or dienes may be saturated or unsaturated, branched, unbranched or cyclic, which can be unsubstituted or mono- or polysubstituted.
  • the dienophile may be an ⁇ , ⁇ -unsaturated ketone, aldehyde, ester, amide, acid, or anhydride; and may be acyclic or cyclic.
  • each of R 1 , R 2 , R 3 and R 4 may be independently selected from hydrogen, alkyl (such as C 1 -C 8 alkyl or even Ci-C 4 alkyl), aromatic (e.g., phenyl) or halogen.
  • each of R 1 , R 2 , R 3 and R 4 may be independently selected from hydrogen or C 1 - C 4 alkyl.
  • two of the R groups for example, R 1 and R 2 , R 1 and R 4 , R 3 and R 4 , or R 2 and R 3 , may optionally be joined together to form a cyclic structure, such as a 5-, 6-, or 7-membered ring.
  • R 1 and R 2 , R 1 and R 4 , R 3 and R 4 , or R 2 and R 3 may be joined together by a 1, 2, 3, 4, or 5 atom chain comprising carbon atoms and, optionally heteroatoms to form a cyclic structure.
  • the atoms in the chain may be substituted (for example, with one or more alkyl chains) or unsubstituted and may include various functionality, such as a carbonyl, lactone, lactam, anhydride, ether, amino or other functionality.
  • the dienophile may be an ⁇ , ⁇ -unsaturated carbonyl dienophile selected from the group consisting of 3-methyl-2-butenal, 3-methyl-2-butenoic acid, methyl 3-methyl-2-butenoate, ethyl 3-methyl-2-butenoate, sec -butyl 3-methyl-2- butenoate, tert-butyl 3-methyl-2-butenoate, (E)-2-butenoic acid, methyl (E)-2-butenoic acid, ethyl (E)-2-butenoic acid, sec-butyl (E)-2-butenoic acid, tert-butyl (E)-2-butenoic acid, (E)-2- butenal, 3-pentene-2-one (both E and Z isomers), 3-butene-2-one, 3-methyl-3-pentene-2-one (both E and Z isomers), and mesityl oxide. Dienophiles, such as the ones listed here
  • each of R 5 , R 6 , R 7 , R 8 , R 9 and R 10 may be independently selected from hydrogen, alkyl (such as C 1 -C 4 alkyl), alkoxy (such as Ci-C 4 alkoxy), siloxy (-OSi(alkyl) 3 ), aromatic (e.g., phenyl) or halogen.
  • alkyl such as C 1 -C 4 alkyl
  • alkoxy such as Ci-C 4 alkoxy
  • siloxy -OSi(alkyl) 3
  • aromatic e.g., phenyl
  • each of R 5 , R 6 , R 7 , R 8 , R 9 and R 10 may be independently selected from hydrogen or Ci-C 4 alkyl.
  • two of the R groups in Formula II may optionally be joined together to form a cyclic structure, such as a 5-, 6-, or 7-membered ring.
  • R 6 and R 7 , R 7 and R 8 , R 8 and R 10 , or R 5 and R 9 may be joined together by a 1, 2, 3, 4, or 5 atom chain comprising carbon atoms and, optionally heteroatoms to form a cyclic structure.
  • the atoms in the chain may be substituted (for example, with one or more alkyl chains) or unsubstituted and may include various functionality, such as a carbonyl, lactone, lactam, anhydride, ether, amino or other functionality.
  • Other cyclic structures corresponding to the general structures of Formula I and/or Formula II are within the subject matter of the present application.
  • the 1,3-diene may be selected from the group consisting of piperylene, 2,4-hexadiene, 2-methyl-2,4-hexadiene, 4-methyl-l,3-pentadiene, cyclopentadiene, isoprene, and butadiene.
  • the process of the present disclosure comprises providing a Lewis acidic ionic liquid.
  • the Lewis acidic ionic liquid may serve as both a solvent and a catalyst for the Diels-Alder [4+2] cycloaddition.
  • the Lewis acidic ionic liquid may be added in smaller quantities in the presence of an organic or inorganic solvent such that the Lewis acidic ionic liquid acts primarily as a catalyst for the Diels-Alder [4+2] cycloaddition.
  • Specific ratios of the Lewis acid to the ionic liquid may display improved catalysis of the Diels-Alder cycloaddition.
  • the Lewis acid ionic liquid complex may have a ratio of Lewis acid to ionic liquid ranging from 1:1 up to 4:1.
  • the Lewis acid to ionic liquid ration may range from about 1.1:1 to about 3:1, and even from about 1.5:1 to about 2:1.
  • the ratio of Lewis acid to ionic liquid that produces the highest yield of cycloadduct may vary depending on the Lewis acid and the ionic liquid.
  • the Lewis acid to ionic liquid ratio for AlCi 3 :[emim]Cl may range from about 1.1:1 to about 3:1, and even from about 1.5:1 to about 2: 1.
  • the Lewis acid to ionic liquid ratio for AlCl 3 : [omim]Cl may range from about 1:1 to about 3:1, and even from about 1.1:1 to about 2:1.
  • the Lewis acidic ionic liquid comprises two Lewis acids, for example, AlCl 3 : [C 2 InHn]Cl and GaCl 3 : [C 2 mim]Cl
  • the Lewis acid to ionic liquid ratio of each Lewis acidic ionic liquid may be independent of the other.
  • the greatest yields in this embodiment are observed when the molar fraction of Lewis acid to the ionic liquid ranges from 0.6 to 0.7.
  • the Lewis acidic ionic liquid has a structure:
  • the Lewis acid component is represented by M(A) n , where M is may be a metal such as a transition metal, an alkali earth metal, an alkali metal, a lanthanide metal, or another metal, such as aluminum, gallium, germanium, indium, thallium, strontium, bismuth and the like; A is a non-metal component, such as a alkyl, halogen, alkoxy or anionic component; and n is an integer corresponding to the valence of M, for example, in certain embodiments, n is an integer ranging from 2 to 4.
  • the metal may be a metal such as Ti, Ni, Ru, Nd, Sc, Y, Al, Ga, In, Zn, Sm, and Zr.
  • the metal M may be selected from the group consisting of Al, Ga, In, Zn, and Zr or in particular embodiments, Al, Ga, and In.
  • the non-metal part of the Lewis acid, A may be selected from a variety of non-metal counterparts of Lewis acids, such as alkoxy, alkyl, methane sulfonate ("mesylate", CH 3 SO 3 " ), trifluoromethane sulfonate ("triflate” or "OTf, CF 3 SO 3 " ), p-toluene sulfonate ("tosylate", CH 3 C 4 H 4 SO 3 " ), Cl, Br, or I.
  • the non-metal counterpart of the Lewis acid is selected from the group consisting of Cl, Br, I, and CF 3 SO 3 " or in particular embodiments, Cl and CF 3 SO 3 " .
  • the ionic liquid component is represented by [CaUOn] + A " , where [Cation] "1" is the cationic component of the ionic liquid and A " is the anionic component of the ionic liquid.
  • the anionic component of the ionic liquid is typically the same as the non-metal component of the Lewis acid, however, it should be noted that Lewis acidic ionic liquids where the anionic component of the ionic liquid is different that the non- metal component of the Lewis acid are also contemplated for the Lewis acidic ionic liquids used herein.
  • Lewis acids have been used as catalysts in conventional Diels- Alder cycloadditions, including, but not limited to, InCl 3 , Al(OTf) 3 , SnCl 4 , ZnCl 2 , Zn(OTf) 2 , TiCl 4 , Ti(OAlkyl) 4 , Y(OTf) 3 , ZrCl 4 , NdCl 3 , SmCl 3 , RuCl 3 XH 2 O and NiCl 2 -OH 2 O; the chloroaluminate compounds, such as, for example, AlCl 3 , (alkyl)AlCl 2 , and (alkyl) 2 AlCl, have proven to be effective catalysts for a Diels-Alder reaction under certain reaction conditions.
  • Lewis acidic ionic liquid may comprise a mixture of Lewis acids, for example, AlCl 3 and GaCl 3 .
  • the ionic liquid component of the Lewis acidic ionic liquid may be represented by [Cation] + A " .
  • “Cation” represented the cationic component of the ionic liquid and may be any cationic component suitable for ionic liquids.
  • the cationic component may comprise a cationic sulfur, such as a trialkylsulfonium cation (i.e., R 3 S + ) or a cationic phosphorus, such as a tetraalkylphosphonium cation (i.e., R 4 P + ).
  • a cationic sulfur such as a trialkylsulfonium cation (i.e., R 3 S + ) or a cationic phosphorus, such as a tetraalkylphosphonium cation (i.e., R 4 P + ).
  • the cationic component of the ionic liquid may comprise a cationic nitrogen or a cationic phosphorus.
  • the cationic component i.e., the "Cation”
  • the cationic component may be a quaternary ammonium cation, choline, a tetraalkylphosphonium cation, or a nitrogen containing heterocyclic or heteroaromatic cation, such as, but not limited to, an N,N-dialkylimidazolium cation, a N,N-dialkylpyrazolium cation, a l,2-dialkyl-l,2,3-triazolium cation, a l,3-dialkyl-l,2,3-triazolium cation, a 1,4- dialkyl-l,2,4-triazolium cation, an N-alkyl-l,3-oxazolium cation, an N-alkyl-l,3-thi
  • the cationic component of the ionic liquid may be an N,N-dialkylimidazolium cation, such as an l-(C 2 -C 8 )alkyl-3- methylimidazolium cation.
  • the cationic component ("Cation") of the ionic liquid may be a cationic compound having a structure selected from the group shown in Scheme 2.
  • the substituents R 11 through R 22 may be any suitable substituent, such as but not limited to, linear or branched, substituted or unsubstituted, cyclic or acyclic, and/or saturated or unsaturated alkyl, hydroxyalkyl, haloalkyl, alkoxyalkyl, phenyl, aryl or heteroaryl.
  • R 11 through R may each independently be a substituent selected from the group consisting of -H, -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -C 6 H 13 , -C 7 H 15 , -C 8 H 17 , -C 9 H 19 , (C 2 -C 6 )alkenyl. hydroxyalkyl, haloalkyl, alkoxyalkyl, (C 6 -Cio)aryl, and (C 8 -Ci 6 )alkenylaryl, 13
  • the length of the substituent chains (e.g., any of R > 1 1 1 1 1 through R , 2 z 2 z )s in the cationic structures may range from C 2 -C 14 and in other embodiments from C 2 -Cs.
  • the Lewis acidic ionic liquid may be selected from the group consisting of AlCl 3 : [C n mim] Cl; GaCl 3 : [C n mim]Cl; ZrCl 4 : [C n mim]Cl; Al(OTf) 3 :[C n mim] [OTf]; and mixtures of any thereof, wherein n is an integer from 2 to 8.
  • the cationic component of the ionic liquid + may be 1-ethyl- 3-methylimidazolium ion, l-propyl-3-methylimidazolium ion, l-butyl-3-methylimidazolium ion, l-pentyl-3-methylimidazolium ion, l-hexyl-3-methylimidazolium ion, l-heptyl-3- methylimidazolium ion, or l-octyl-3-methylimidazolium ion.
  • the length of the side chain in the cationic component of the ionic liquid may affect a variety of characteristics the Diels- Alder cycloaddition, such as, for example, reagent solubility, separation ease, stereoselectivity, diastereoselectivity. cycloadduct yield, and the like.
  • a Lewis acidic ionic liquid comprising AlCl 3 : [C 8 inim]Cl displayed a higher yield of the desired cycloadduct than a similar Diels-Alder cycloaddition of mesityl oxide and piperylene utilizing the Lewis acidic ionic liquid comprising AlCl 3 : [C 2 mim]Cl.
  • the longer side chain in the imidazolium ionic liquid is believed to increase the solubility of the starting materials in the ionic liquid.
  • the anionic component may be any suitable counter anion for the cationic component of the ionic liquid.
  • suitable anionic components include, but are not limited to, halide anions (i.e., F “ , Cl “ , Br “ , or I “ ), methane sulfonate ("mesylate”, CH 3 SO 3 " ), trifluoromethane sulfonate ("triflate” or "OTf, CF 3 SO 3 " ), p-toluene sulfonate ("tosylate", CH 3 C 4 H 4 SO 3 “ ), hydrogen sulfate (HOSO 3 " ), alkyl sulfate (alkylOSO 3 ), hexafluorophosphate (PF 6 “ ), tetrafluoroborate (BF 4 “ ), bistriflimide ((CF 3 SO 2 ) 2 N “ ), hexafluoroantimonate
  • the anionic component of the ionic liquid may be halide, such as chloride (Cl " ), bromide (Br “ ) or iodide (I ); or trifluoromethane sulfonate ("triflate” or “OTf, CF 3 SO 3 " ) and in particular embodiments, chloride or trifluoromethane sulfonate.
  • halide such as chloride (Cl " ), bromide (Br " ) or iodide (I ); or trifluoromethane sulfonate ("triflate” or "OTf, CF 3 SO 3 " ) and in particular embodiments, chloride or trifluoromethane sulfonate.
  • the anionic component of the ionic liquid may be the same as the non-metal component of the Lewis acid.
  • the anionic component of the ionic liquid and the non- metal component of the Lewis acid may both be chloride, bromide, or triflate.
  • Suitable Lewis acidic ionic liquids that may be used to catalyze the Diels-Alder cycloadditions described herein include, but are not limited to, AlCl 3 : [C 2 mim]Cl; AlCl 3 :[C 8 mim]Cl; InCl 3 :[C 2 mim]Cl; InCl 3 : [C 8 mim]Cl; ZnCl 2 :[C 2 mim]Cl; ZnCl 2 : [C 8 mim] Cl; ZrCl 4 : [C 2 mim]Cl; ZrCl 4 : [C 8 mim] Cl; NdCl 3 : [C 2 mim] Cl; NdCl 3 : [C 8 mim]Cl; SmCl 3 : [C 2 mim]Cl; SmCl 3 :[C 8 mim]Cl; RuCl 3 -xH 2 O:[C 2 mim]Cl; RuCl 3
  • C 2 mim means l-ethyl-3-methylimidazolium
  • C ⁇ inim means l-hexyl-3- methylimidazolium
  • Csinim means l-methyl-3-octylimidazolium
  • the Lewis acidic ionic liquid is selected from the group consisting of AlCl 3 :[C 2 mim]Cl; AlCl 3 :[C 8 mim]Cl; GaCl 3 : [C 2 HUm]Cl; ZrCl 4 : [C 2 mim] Cl; ZrCl 4 : [C 8 mim]Cl; Al(OTf) 3 :[C 2 mim][OTf]; Al(OTf) 3 : [C 8 mim] [OTf]; and mixtures of any thereof.
  • the Diels- Alder cycloaddition involves a reaction between a 1,3- diene and a dienophile to produce a substituted cyclohexene
  • the dienophile may be an ⁇ , ⁇ -unsaturated carbonyl dienophile (that is the dienophile includes a carbon-carbon double bond in conjugation with a carbon-oxygen double bond).
  • the ⁇ , ⁇ -unsaturated carbonyl dienophile is mesityl oxide and the 1,3-diene is piperylene
  • the mesityl oxide reacts with the piperylene in a Diels-Alder cycloaddition to give a substituted cyclohexene.
  • this Diels-Alder cycloaddition may be catalyzed by a Lewis acid.
  • prior art examples of Lewis acid catalyzed Diels-Alder cycloadditions of mesityl oxide and piperylene suffer from low yields and significant polymer formation.
  • the mesityl oxide and piperylene undergo a facile Diels-Alder cycloaddition in the presence of a Lewis acidic ionic liquid, such as those described herein.
  • the Lewis acidic ionic liquid may be AlCl 3 :[C 2 inim]Cl; AlCl 3 :[C 8 inim]Cl; or mixtures thereof.
  • the substituted cyclohexene product may comprise a mixture of cis- and trans-l-(2,6,6- trimethylcyclohex-3-en-l-yl)ethanone where the methyl substituent at the C2 ring carbon and the ethyl ketone substituent at the Cl ring carbon are on the same face (i.e., cis) or the opposite face (i.e., trans) of the cyclohexene ring.
  • the substituted cyclohexene product may comprise predominantly cis-l-(2,6,6-trimethylcyclohex-3-en-l- yl)ethanone, with the minor cycloaddition component comprising the trans-l-(2,6,6- trimethylcyclohex-3-en-l-yl)ethanone.
  • the cis to trans ratio of the l-(2,6,6-trimethylcyclohex-3-en-l- yl)ethanone may be greater than 10:1.
  • the structure of l-(2,6,6-trimethylcyclohex-3-en-l- yl)ethanone is shown in Formula III.
  • the process for producing substituted cyclohexenes of the present disclosure may further comprise the step of purifying the substituted cyclohexene product.
  • any conventional method of purification may be used.
  • the substituted cyclohexene product may be purified, for example, by crystallization or recrystallization, Crystallization or recrystallization using a single solvent or mixed solvent system are contemplated.
  • the substituted cyclohexene product may be purified using a distillation method, such as, but not limited to simple distillation, steam distillation, fractional distillation, azeotropic distillation, spinning band distillation, vacuum or reduced pressure distillation, and combination of these methods (for example, vacuum fractional distillation).
  • a distillation method such as, but not limited to simple distillation, steam distillation, fractional distillation, azeotropic distillation, spinning band distillation, vacuum or reduced pressure distillation, and combination of these methods (for example, vacuum fractional distillation).
  • the substituted cyclohexene product may be purified by chromatographic methods, such as, but not limited to column chromatography, liquid chromatography, flash chromatography, medium pressure liquid chromatography, high performance liquid chromatography (HPLC), thin layer chromatography, reverse-phase chromatography, and combinations of these methods.
  • the substituted cyclohexene may be purified by using a combination of any of the above referenced purification methods.
  • Still further embodiments of the processes for producing substituted cyclohexenes may further comprise converting to substituted cyclohexene to a desired product by one or more further chemical transformations.
  • the process may further comprise converting the substituted cyclohexene product to a product useful as a perfume, fragrance or aroma enhancing compound or product.
  • Suitable fragrance enhancing products that may be produced by the substituted cyclohexene products of the present disclosure include, but are not limited to, fragrance products selected from the group consisting of ( ⁇ )-(E)- ⁇ -damascone, ( ⁇ )-(E)- ⁇ -damascone, ( ⁇ )-(E)- ⁇ -damascone, (+)-(E)- ⁇ - damascone, l-(2,2,6-trimethylcyclohexyl)-2-buten-l-one, l-(2,2,6-trimethylcyclohexyl)-l- butanone, trans-4-(2,2,6-trimethylcyclohexyl)-3-buten-2-one, ( ⁇ )-(E)- ⁇ -ionone, ( ⁇ )-(E)- ⁇ - ionone, ( ⁇ )-dihydro- ⁇ -ionone, ( ⁇ )-dihydro- ⁇ -ionone, ( ⁇ )-tetrahydroionone,
  • the process for producing a substituted cyclohexene may further comprise converting the l-(2,6,6-trimethylcyclohex-3-en-l-yl)ethanone to (+)- ⁇ - damascone which has a structure represented by Formula IV:
  • Methods of converting the l-(2,6,6-trimethylcyclohex-3-en-l-yl)ethanone may include the following chemical transformations: epimerizing the cis-l-(2,6,6-trimethylcyclohex-3-en-l- yl)ethanone to trans-l-(2,6,6-trimethylcyclohex-3-en-l-yl)ethanone: condensing the trans-1- (2,6,6-trimethylcyclohex-3-en-l-yl)ethanone with acetaldehyde to form ( ⁇ )- ⁇ -damascone.
  • epimerizing the cis-l-(2,6,6-trimethylcyclohex-3-en-l- yl)ethanone to the trans isomer may be affected by reacting the cis-l-(2,6,6- trimethylcyclohex-3-en-l-yl)ethanone with a base, for example, potassium hydride or a metal alkoxide base, such as potassium tert-butoxide.
  • a base for example, potassium hydride or a metal alkoxide base, such as potassium tert-butoxide.
  • bases known in the art may also be suitable for epimerizing the cis isomer to the trans-l-(2,6,6-trimethylcyclohex-3-en-l- yl)ethanone.
  • the trans-l-(2,6,6-trimethylcyclohex-3-en-l- yl)ethanone may be condensed with acetaldehyde to form ( ⁇ )- ⁇ -damascone.
  • the trans-l-(2,6,6-trimethylcyclohex-3-en-l-yl)ethanone may condense with the acetaldehyde via an aldol condensation (i.e., reaction of the enolate of the ketone with acetaldehyde to form the aldol addition product followed by a dehydration) to form the ( ⁇ )- ⁇ - damascone.
  • the condensing step for the trans-l-(2,6,6-trimethylcyclohex-3-en-l-yl)ethanone may also be performed with another aldehyde or ketone reagent to form a condensation product.
  • the condensation products i.e., aldol reaction and, optionally the elimination reaction
  • the processes may further comprise purifying the condensation product, for example, but a purification method selected from crystallization, distillation or chromatography. Suitable examples of these purification methods are described herein in reference to purifying the Diels-Alder cycloaddition product.
  • the epimerization step and the condensation step may be performed in a single reactor.
  • the phrase '"single reactor means that two or more chemical transformations are performed without an intermediate isolation or workup step.
  • the mixture or cis- and trans- 1-(2, 6,6- trimethylcyclohex-3-en-l-yl)ethanone may be submitted to epimerization conditions and once the epimerization is substantially complete, the reaction solution comprising substantially all trans- l-(2,6,6-trimethylcyclohex-3-en-l-yl)ethanone is subjected directly to the condensation conditions by adding the aldehyde to the epimerization product.
  • Non- limiting examples of performing the epimerization step and the condensing step in a single reactor are described in detail in co-pending U.S. Provisional Application identified by Attorney Docket No. 11213P, entitled “Processes for Epimerizing Cyclohexenyl Ketones with Subsequent Aldol Condensation to Produce Fragrance Compounds", filed on a date even with the present application and assigned to The Procter & Gamble Company, Cincinnati, Ohio.
  • Specific embodiments of the present disclosure provide a process for producing a substituted cyclohexene product comprising reacting mesityl oxide with piperylene in an Lewis acidic ionic liquid to form predominantly cis-l-(2,6,6-trimethylcyclohex-3-en-l- yl)ethanone.
  • the Lewis acidic ionic liquid may be any of the Lewis acidic ionic liquids discussed herein.
  • the Lewis acidic ionic liquid may be AlCl 3 :[C 2 mim]Cl; AlCl 3 :[C 8 mim]Cl; GaCl 3 : [C 2 HUm]Cl; ZrCl 4 : [C 2 mim] Cl; ZrCl 4 : [C 8 mim]Cl; Al(OTf) 3 :[C 2 mim] [OTf]; Al(OTf) 3 : [C 8 mim] [OTf]; or mixtures of any thereof.
  • the ratio of Lewis acid to ionic liquid may be any ratio described herein as suitable, for example, a Lewis acid to ionic liquid ratio ranging from 1:1 to 4:1,
  • inventions of the process comprising reacting mesityl oxide with piperylene in an Lewis acidic ionic liquid to form predominantly cis-l-(2,6,6-trimethylcyclohex-3-en-l- yl)ethanone may further comprise converting the cis-l-(2,6,6-trimethylcyclohex-3-en-l- yl)ethanone to ( ⁇ )- ⁇ -damascone.
  • the process comprising reacting mesityl oxide with piperylene in an Lewis acidic ionic liquid to form predominantly cis-1- (2,6,6-trimethylcyclohex-3-en-l-yl)ethanone may further comprise epimerizing the cis-1- (2,6,6-trimethylcyclohex-3-en- 1 -yl)ethanone to trans- 1 -(2,6,6-trimethylcyclohex-3-en- 1 - yl)ethanone and condensing the trans-l-(2,6,6-trimethylcyclohex-3-en-l-yl)ethanone with an aldehyde to form a condensation product,
  • the process may further comprise purifying the condensation product, as described herein.
  • the aldehyde may be acetaldehyde when the condensation product is ( ⁇ )- ⁇ -damascone, which may then optionally be purified, for example, by a distillation process.
  • the epimerizing step and the condensing step may be performed in a single reactor.
  • the present disclosure provides a process for producing ( ⁇ )- ⁇ -damascone.
  • the process may comprise reacting mesityl oxide with piperylene in a Diels-Alder cycloaddition in a Lewis acidic ionic liquid to form predominantly cis-l-(2,6,6- trimethylcyclohex-3-en-l-yl)ethanone; epimerizing the cis-l-(2,6,6-trimethylcyclohex-3-en- l-yl)ethanone to trans-l-(2,6,6-tnmethylcyclohex-3-en-l-yl)ethanone; and condensing the trans-l-(2,6,6-trimethylcyclohex-3-en-l-yl)ethanone with acetaldehyde to form ( ⁇ )- ⁇ - damascone.
  • the Lewis acidic ionic liquid may be any of those described herein and in specific embodiments may be AlCl 3 :[C 2 inim]Cl; AlCl 3 :[C 8 mim]Cl; or mixtures thereof.
  • the epimerizing step and the condensing step may be performed in a single reactor vessel.
  • the novel process for producing substituted cyclohexenes described herein may improve the yield of the desired cyclohexene compounds without the use of volatile solvents and without significant formation of by-products.
  • the Diels-Alder cycloaddition of mesityl oxide and piperylene in AlCl 3 : [C 2 inim] Cl; AlCl 3 :[Cgmim] Cl; or mixtures thereof may be particularly suitable for the industrial production of substituted cyclohexene reaction products considering the increased efficiency of producing the cis-isomer of the cycloadduct.
  • the reagents and reaction conditions have been designed such that the recycling of the catalyst may be achieved.
  • a proper amount of solvent may be used in conducting the Diels-Alder cycloaddition.
  • Many standard organic or inorganic solvents may be suitable for use in the processes described herein, however, the solvents used in the reaction may affect the yield of the reaction and stereoselectivity of the reaction products.
  • solvents can comprise from about 50% to about 95% by weight of the reaction mixture.
  • Suitable solvents include ionic, polar or non-polar; organic or inorganic solvents, for example, but not limited to, aromatic solvents, such as, but not limited to, toluene; halogenated solvents, such as, but not limited to, dichloromethane, ionic liquids [C 2 inim] [NTf 2 ], and water.
  • the Diels-Alder reaction may be performed neat or with the Lewis acidic ionic liquid acting as the solvent.
  • the effectiveness of the Lewis acidic ionic liquids to generate the desired cyclic organic compounds may depend, at least in part, on the reaction conditions and the specific Lewis acid and ionic liquid used in the reaction.
  • the properties of the Lewis acidic ionic liquids utilized in the processes described herein, e.g., the Lewis acidity, may be adjusted by changing the ratio of the metal salt in the ionic liquid.
  • the ratio of the Lewis acid to the ionic liquid may affect the stereochemistry of the reaction products, for example, the exo and endo ratio of the Diels -Alder cycloaddition products.
  • the ratio of the ⁇ , ⁇ - unsaturated carbonyl dienophile to 1,3-diene may have an effect on the yield of the cycloadduct.
  • the 1,3-diene was used in excess due to competing polymerization of the diene.
  • isolation of the cycloaddition product may be complicated by formation of significant polymer co-product.
  • the ratio of the ⁇ , ⁇ -unsaturated carbonyl dienophile to 1,3-diene may range from about 1:2 to about 1:10.
  • the 1,3-diene may be used in excess, for example, where the ratio of the ⁇ , ⁇ -unsaturated carbonyl dienophile to 1,3- diene ranges from 1:2 to 1:6, or in other embodiments, from 1:3 to 1:5.
  • the ratio of the ⁇ , ⁇ - unsaturated carbonyl dienophile to 1,3-diene may range from about 1:2 to about 1:10 and in certain embodiments, from 1:3 to 1:6 or even around 1:5.
  • Figure 2 the effect of changes in the dienophile to diene ratio on yield for the Diels-Alder cycloaddition of mesityl oxide and piperylene is presented. As shown in Fig.
  • the Lewis acidic ionic liquids that catalyze the Diels-Alder cycloadditions may also catalyze the undesirable polymerization of the starting materials.
  • polymerization of the dienophile and/or the 1,3-diene may reduce the overall yield of the Diels-Alder cycloadduct. Therefore, the reaction conditions may have a critical effect on the yield and efficiency of the Diels-Alder reaction and may also influence the kinetics and thermodynamics of the undesirable polymerization of the starting materials.
  • the reaction conditions of the present disclosure have been carefully selected to increase the yield and efficiency of the Diels-Alder reaction and reduce the undesirable polymerization of the starting materials.
  • the reaction conditions that may have a critical effect on the yield and efficiency of the Diels-Alder reaction include, for example, but not limited to, the reaction temperature, pressure, pH, atmosphere, and time; the addition speed of reagents to the reaction mixture, the ratio of reagents, and the effect of any solvents, such as the effect of water.
  • the reaction rate of the Diels-Alder reaction and competing side reactions, such as the polymerization of starting materials, may increase with the addition speed of the reagents to the reaction mixture, reaction temperature, and reaction time.
  • the 1,3-diene reagent may be added slowly to the reaction mixture at a rate ranging from about 0.1 mL/min to about 1 mL/min, and in other embodiments from about 0.25 mL/min to about 0.75 mL/min and in still other embodiments from about 0.5 mL/min to about 0.625 mL/min.
  • the proper addition speed of thel,3-diene reagent may be important for increasing yield and efficiency of the Diels-Alder cycloaddition.
  • the reagents may be added slowly to the reaction mixture at a slow rate to reduce the temperature rise associated with the exothermic reaction and, thus, minimize the undesirable polymerization of the starting materials.
  • Temperature of the Diels-Alder cycloaddition process may also have an effect on the efficiency of the reaction.
  • the reaction temperature ranges from about -25 0 C to about HO 0 C.
  • Increased reaction temperature including, for example, the exothermic reaction resulting from the addition of the reagents to the reaction mixture, may promote the undesirable polymerization of the starting materials.
  • the temperature of the reaction mixture when the dienophile is added to the solution comprising the Lewis acidic ionic liquid may range from about 16 0 C to about HO 0 C, and in other embodiments from about 16°C to about 8O 0 C, and in even further embodiments from about 16 0 C to about 6O 0 C.
  • the temperature of the reaction mixture when the dienophile is added to the Lewis acidic ionic liquid may range from about 16 0 C to about 2O 0 C.
  • the complex formed between the dienophile and the Lewis acidic ionic liquid may then be cooled prior to addition of the 1,3-diene.
  • the reaction temperature when the 1,3-diene is added to the reaction mixture comprising the complex of the dienophile and the Lewis acidic ionic liquid may range from about -2O 0 C to about 2O 0 C, and in some embodiments from about -2O 0 C to about O 0 C.
  • the reaction temperature when the 1,3-diene is added to the reaction mixture ranges from about -20 0 C to about -18°C.
  • any sudden increase in the reaction temperature may significantly increase the undesirable polymerization of the starting materials.
  • the yield and efficiency of the Diels-Alder reaction may be decreased if the reaction mixture is overcooled such that complexation of the reagents is diminished. Therefore, the proper reaction temperature at each step of the process may be important to increase the yield of the reaction and decrease the undesirable polymerization of the starting materials.
  • the reaction time may range from about 0.5 hour to about 240 hours, and in other embodiments from about 5 hours to about 180 hours, and in still other embodiments from about 24 hours to about 80 hours.
  • the reaction time may be important to increasing yield and efficiency of the Diels-Alder reaction.
  • the Diels-Alder cycloadduct and/or reactants may further undergo undesirable reactions that generate undesirable products and reduces its yield.
  • the yield and efficiency of the Diels-Alder reaction may also be affected by the quality of the Lewis acidic and ionic liquids.
  • certain chloroaluminate Lewis acid catalysts and ionic liquids may be sensitive to moisture and should be prepared, stored, and used under nitrogen.
  • an amount of a proton scavenger for example, a base, such as an amine base, for example, but not limited to, triethylamine, Hunig's base (diisopropyl ethyl amine), and the like, may be added to the Diels-Alder reaction mixture to improve the effectiveness of the cycloaddition, for example, by neutralizing protic acids, such as hydrochloric acid produced by partially hydrolyzed Lewis acid catalysts.
  • protic acids may catalyze polymerization of ⁇ , ⁇ -unsaturated carbonyl compounds and/or 1,3-dienes, so adding a proton scavenger may increase the yield of the reaction by decreasing the undesirable polymerization of the starting materials.
  • the amount of proton scavenger, such as Hunig's base, added to the reaction mixture may range from about 2 molar percent to about 10 molar percent.
  • the Lewis acid and/or ionic liquid used in the Diels-Alder reaction may be recycled. Recycling one or more of the Lewis acid and the ionic liquid may significantly reduce the cost and reduce and/or eliminate the formation of waste products, such as hydrolysis products, for example, the Al(OH) 3 solid waste that is generated when AlCl 3 is used. This may increase the industrial utility of the processes described herein.
  • the cycloadduct products may be isolated from the ionic liquid without the use of water. This may allow for the recovery and reuse of the Lewis acid, ionic liquid or both.
  • the isolation process may comprise treating the reaction products with an excess of a compound that generates an ionic liquid phase comprising the Lewis acid and ionic liquid, extracting the Lewis acid and ionic liquid into an immiscible organic solvent, and evaporating the organic solvent. The Lewis acid and/or ionic liquid may then be recycled.
  • the compounds of the present invention are prepared according to methods which are well-known to those skilled in the art.
  • the starting materials used in preparing the compounds of the invention are well-known to those skilled in the art, made by known methods, or are commercially available.
  • EXAMPLES Example 1 Lewis acid catalyzed Diels-Alder cycloaddition
  • a substituted cyclohexene product comprising predominately cis-1- (2,6,6-trimethylcyclohex-3-en-l-yl)ethanone is formed.
  • the ⁇ , ⁇ -unsaturated carbonyl dienophile is mesityl oxide
  • the 1,3-diene is piperylene
  • the Lewis acidic ionic liquid is AlCl 3 :[C 2 mim]Cl.
  • a substituted cyclohexene product comprising predominately cis-1- (2,6,6-trimethylcyclohex-3-en-l-yl)ethanone is formed.
  • the ⁇ , ⁇ -unsaturated carbonyl dienophile is mesityl oxide
  • the 1,3-diene is piperylene
  • the Lewis acidic ionic liquid is GaCl 3 : [C 2 HUm]Cl.

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Abstract

La présente invention porte sur des procédés de production de cyclohexènes à l'aide de liquides ioniques acides de Lewis, comprenant les étapes consistant à adresser à un réacteur un diénophile carbonylé à insaturation α,β, à adresser au réacteur un 1,3-diène, à adresser au réacteur un liquide ionique acide de Lewis; et à faire réagir le diénophile carbonylé à insaturation α,β avec le 1,3-diène pour former un produit cyclohexène substitué. Le diénophile carbonylé à insaturation α,β peut être l'oxyde de mésityle, le 1,3-diène peut être le pipérylène; et le liquide ionique acide de Lewis peut être AlCl3 : [C2mim]C1; A1C13 : [C8mim]C1; ou leurs mélanges.
PCT/US2009/068498 2008-12-19 2009-12-17 Procédé de conduite d'une réaction organique dans des liquides ioniques WO2010080505A2 (fr)

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JP2020503383A (ja) * 2016-12-23 2020-01-30 エスセエ フランス ホウ素族からの元素をベースにした化合物、および電解質組成物中でのその使用
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JP7055817B2 (ja) 2016-12-23 2022-04-18 エスセエ フランス ホウ素族からの元素をベースにした化合物、および電解質組成物中でのその使用
CN110746283A (zh) * 2018-07-24 2020-02-04 新乡市博源生物科技有限公司 一种β-突厥酮的合成工艺
CN111303324A (zh) * 2020-03-27 2020-06-19 中国科学院青岛生物能源与过程研究所 一种低分子量、高trans-1,4-聚异戊二烯及其制备方法

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