- METHOD FOR PRODUCING 3-METHYLCYCLOALKENONE COMPOUND
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The present invention relates to a method for producing a 3-methylcycloalkenone compound and a method for producing muscone. In the presence of a zirconium oxide catalyst, a diketone represented by the following general formula (1): wherein in formula (1), n represents 8, 9, 10, 11 or 12, is subjected to a vapor-phase intramolecular condensation reaction, whereby a 3-methylcycloalkenone compound can be produced with high reaction efficiency. When a 3-methylcyclopentadecenone compound produced by this method is hydrogenated in a known manner, muscone can be produced efficiently.
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- Preparation method of musk ketone
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The invention relates to a preparation method of muscone, which includes the steps of: 1) adding 1,2-diol supported on polystyrene resin, 3-methyl dienone, methylbenzene and pyridinium p-toluenesulfonate, stirring and heating the materials, cooling the materials to room temperature, and filtering the materials to produce a first ketal compound; 2) adding a first solvent and a catalyst, performingheating reflux until the reaction is finished, cooling a reaction product to room temperature and filtering the reaction product to produce a second ketal compound; 3) adding a first solvent and an acid solution, stirring the mixture until the reaction is finished, cooling a reaction product to room temperature, washing the reaction product to separate a first organic layer, and performing normalpressure recovery to the solvent in the first organic layer to collect a first ketene compound; 4) adding an alcohol solution and a metal catalyst into a reaction bottle, repeatedly replacing gas in the reaction bottle with N2 and H2, and performing a reaction at normal temperature and under normal pressure, and when the reaction is finished, performing filtration and pressure reduced rectification to obtain the muscone. The preparation method is simple in technical process and low in cost, and allows industrial large-scale production.
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Paragraph 0046; 0056-0058
(2020/12/30)
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- Preparation method for L-muscone
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The invention provides a preparation method for L-muscone. Dehydrogenated muscone is taken as a starting material, chiral amine is taken as an inducer, homogeneous phase iridium is taken as a catalyst, hydrogen is taken as a reducing agent, and the L-muscone product is synthesized through imine synthesis, asymmetric hydrogenation and hydrolysis reaction. The homogeneous phase iridium catalyst usedin the method has low dose and low cost; the synthetic route has high total yield and few three wastes and is suitable for industrial production of L-muscone.
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Paragraph 0050; 0053
(2019/05/08)
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- Transfer Hydrogenation of Alkenes Using Ethanol Catalyzed by a NCP Pincer Iridium Complex: Scope and Mechanism
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The first general catalytic approach to effecting transfer hydrogenation (TH) of unactivated alkenes using ethanol as the hydrogen source is described. A new NCP-type pincer iridium complex (BQ-NCOP)IrHCl containing a rigid benzoquinoline backbone has been developed for efficient, mild TH of unactivated C-C multiple bonds with ethanol, forming ethyl acetate as the sole byproduct. A wide variety of alkenes, including multisubstituted alkyl alkenes, aryl alkenes, and heteroatom-substituted alkenes, as well as O- or N-containing heteroarenes and internal alkynes, are suitable substrates. Importantly, the (BQ-NCOP)Ir/EtOH system exhibits high chemoselectivity for alkene hydrogenation in the presence of reactive functional groups, such as ketones and carboxylic acids. Furthermore, the reaction with C2D5OD provides a convenient route to deuterium-labeled compounds. Detailed kinetic and mechanistic studies have revealed that monosubstituted alkenes (e.g., 1-octene, styrene) and multisubstituted alkenes (e.g., cyclooctene (COE)) exhibit fundamental mechanistic difference. The OH group of ethanol displays a normal kinetic isotope effect (KIE) in the reaction of styrene, but a substantial inverse KIE in the case of COE. The catalysis of styrene or 1-octene with relatively strong binding affinity to the Ir(I) center has (BQ-NCOP)IrI(alkene) adduct as an off-cycle catalyst resting state, and the rate law shows a positive order in EtOH, inverse first-order in styrene, and first-order in the catalyst. In contrast, the catalysis of COE has an off-cycle catalyst resting state of (BQ-NCOP)IrIII(H)[O(Et)···HO(Et)···HOEt] that features a six-membered iridacycle consisting of two hydrogen-bonds between one EtO ligand and two EtOH molecules, one of which is coordinated to the Ir(III) center. The rate law shows a negative order in EtOH, zeroth-order in COE, and first-order in the catalyst. The observed inverse KIE corresponds to an inverse equilibrium isotope effect for the pre-equilibrium formation of (BQ-NCOP)IrIII(H)(OEt) from the catalyst resting state via ethanol dissociation. Regardless of the substrate, ethanol dehydrogenation is the slow segment of the catalytic cycle, while alkene hydrogenation occurs readily following the rate-determining step, that is, β-hydride elimination of (BQ-NCOP)Ir(H)(OEt) to form (BQ-NCOP)Ir(H)2 and acetaldehyde. The latter is effectively converted to innocent ethyl acetate under the catalytic conditions, thus avoiding the catalyst poisoning via iridium-mediated decarbonylation of acetaldehyde.
- Wang, Yulei,Huang, Zhidao,Leng, Xuebing,Zhu, Huping,Liu, Guixia,Huang, Zheng
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supporting information
p. 4417 - 4429
(2018/04/05)
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- Continuous preparation method of DL-muscone
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The invention discloses a continuous preparation method of DL-muscone. The preparation method comprises the following steps: 1) dissolving 2,15-hexadecanedione diketone in an aprotic solvent, then carrying out a continuous reaction in a fixed-bed cyclization reactor for generating a 3-methylcyclopentanone analogue under the action of a cyclization catalyst; 2) carrying out desolvation on the 3-methylcyclopentanone analogue, dissolving the obtained product in a protic solvent, then carrying out a continuous reaction with hydrogen in a fixed-bed hydrogenation reactor under the action of a hydrogenation catalyst to obtain muscone; and 3) carrying out desolvation on the product obtained in the step 2), carrying out continuous chromatographic separation, and carrying out desolvation on the product liquid containing the DL-muscone to obtain the DL-muscone product. The method for preparing the DL-muscone provided by the invention has high process stability and high product yield, continuous production of the DL-muscone can be realized, the production cost is greatly reduced, and the effective capacity of a device is improved.
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Paragraph 0046; 0048; 0050; 0051; 0053; 0054; 0055; 0056
(2018/07/15)
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- Method for synthesizing muscone by utilizing beta-monomethyl methylglutarate
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The invention discloses a method for synthesizing muscone by utilizing beta-monomethyl methylglutarate. According to the method, beta-monomethyl methylglutarate and alpha,omega-dodecanedioic acid monomethyl ester respectively prepared through a heteropoly acid catalytic transesterification method are used as raw materials, and Kolbe electrolysis, acyloin condensation and reduction reaction are performed to prepare the muscone. The method of the present invention has advantages of high raw material utilization rate, mold condition, easy control and environmental protection, and is suitable for industrial production .
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- Preparation method of E-2-cyclopentadecenone
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The invention provides a novel method for synthesizing E-2-cyclopentadecenone by utilizing 2-hydroxy-cyclopentadecanone. The 2-hydroxycyclopentadecanone, metal oxide, concentrated sulfuric acid or concentrated phosphoric acid are added into a non-polar organic solvent and are subjected to elimination reaction to obtain the E-2-cyclopentadecenone. In the reaction, a catalytic amount of the metal oxide is added so that a condition that the elimination reaction cannot be realized through the concentrated sulfuric acid before becomes possible; the raw materials in the novel method are relatively cheap; reaction conditions are moderate, the operation is simple and the production cost is reduced so that the novel method is very suitable for industrialized production.
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Paragraph 0005; 0039; 0040; 0041
(2017/08/31)
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- Synthesis of Macrocyclic Ketones through Catalyst-Free Electrophilic Halogen-Mediated Semipinacol Rearrangement: Application to the Total Synthesis of (±)-Muscone
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A series of macrocycles were successfully prepared using electrophilic halogen-mediated semipinacol rearrangement under mild conditions. Although the expansion from small ring to medium ring is an energetically unfavorable process, the electrophilic halog
- Liu, Yi,Yeung, Ying-Yeung
-
supporting information
p. 1422 - 1425
(2017/03/23)
-
- The chemistry of thiophene-based bis-(p-quinodimethanes): An approach to macrocycles
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Bis-2,5-dimethylene-2,5-dihydrothiophenes have been generated in the gas-phase by flash vacuum pyrolysis (FVP) of diester precursors. These thiophene-based bis-(p-quinodimethanes) are shown to undergo reactions leading to macrocycles. The conversions are consistent with a mechanism involving cyclic diradical intermediates followed by disproportionation of the radical centers.
- Trahanovsky, Walter S.,Klumpp, Douglas A.
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supporting information
p. 2386 - 2389
(2016/05/19)
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- Efficient macrocyclization by a novel oxy-oxonia-cope reaction: Synthesis and olfactory properties of new macrocyclic musks
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Musk made to odor: A new oxy-oxonia-Cope macrocyclization to (3Z)-configured cycloalk-3-en-1-yl formates is reported, which is useful in the synthesis of unsaturated and saturated macrocyclic ketones (see scheme). The synthesized structures provide new insight into the structure-odor correlation of musks, making it likely for macrocyclic and linear alicyclic musks to address the same olfactory receptors.
- Zou, Yue,Mouhib, Halima,Stahl, Wolfgang,Goeke, Andreas,Wang, Quanrui,Kraft, Philip
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supporting information; experimental part
p. 7010 - 7015
(2012/07/03)
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- PROCESS FOR PREPARING KETONES, IN PARTICULAR MACROCYCLIC KETONES
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Ketones of the formula II where A is optionally alkyl-substituted C2-C12-alkanediyl, R1 and R2 are each, independently of one another, C1-C6-alkyl, or R1 and R2 together form optionally alkyl-substituted C3-C10-alkanediyl, and R3 is hydrogen or C1-C6-alkyl, are prepared by reacting a cyclic olefin of the formula I with dinitrogen monoxide to form the ketone of the formula II. The ketone of the formula II can be further hydrogenated to form the saturated ketone of the formula III. Macrocyclic ketones of the formula III, e.g. muscone, are sought after as fragrances.
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- PROCESS FOR PRODUCTION OF 3-METHYL-CYCLOPENTADECENONE, PROCESS FOR PRODUCTION OF R/S-MUSCONE, AND PROCESS FOR PRODUCTION OF OPTICALLY ACTIVE MUSCONE
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By intramolecular condensation reaction of 2,15-hexadecanedione in a gaseous phase with a compound of a Group II element of the Periodic Table as a catalyst, 3-methyl-cyclopentadecenones is generated. Magnesium oxide, calcium oxide, or zinc oxide is desirable as the catalyst for the intramolecular condensation reaction. (R)- and (S)-muscone is generated by subjecting 3-methyl-cyclopentadecenones obtained as above to hydrogenation by using a catalyst. Palladium catalyst is desirable as the hydrogenation catalyst. Optically active muscone is generated by separating 3-methyl-cyclopentadecenones into respective components thereof by means of precision distillation and subsequently subjecting the separated 3-methyl-cyclopentadecenones to asymmetric hydrogenation by using an optically active ruthenium complex catalyst. The production methods described above enable easy and economical production of 3-methyl-cyclopentadecenones, (R)-and (S)-muscone, and optically active muscone.
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- A practical synthesis of (rac)-muscone and (R)-(-)-muscone
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A practical synthesis of (rac)-muscone in three steps is described, using commercially available 1,10-dibromodecane as the starting material. In the first step, an aldol reaction of 1,10-dibromodecane with ethyl acetoacetate affords the important intermediate 2,15-hexadecanedione in 70% yield. A cyclisation reaction in the second step aided by propyl zinc iodide gives dehydro-muscone in 84% yield. Hydrogenation of dehydro-muscone with Pd-C completes the synthesis of (rac)-muscone. Furthermore, (R)-(-)-muscone is enantioselectively prepared via the formation of a ketal intermediate from dehydro-muscone and 1,4-di-O-benzyl-D-threitol.
- Cheng, Chuanjie,Ding, Wei,Ding, Shaomin
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p. 195 - 197
(2011/07/30)
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- PERFUME COMPOSITIONS
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Perfume ingredients have been investigated and classified for their effectiveness in detaching biofilms from surfaces. Based on this classification, perfume compositions that are effective in assisting biofilm detachment can be formulated, whilst also allowing a degree of freedom in formulation that permits consideration of the hedonic properties of the composition. The compositions can be used in a wide range of perfumed consumer products, such as personal, domestic and industrial products, e.g. hard surface cleaning products, dental care products, and deodorant products.
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- Palladium-supported ionic liquid catalyst (Pd-SH-SILC) immobilized on mercaptopropyl silica gel as a chemoselective, reusable and heterogeneous catalyst for catalytic hydrogenation
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Palladium acetate was immobilized as Pd-SH-SILC (Pd-supported ionic liquid catalyst) in the pores of amorphous mercaptopropyl silica gel with the aid of an ionic liquid [bmim]BF4. The heterogeneous Pd-SH-SILC was effective for catalytic hydrogenation of a variety of olefins at atmospheric pressure and room temperature. It withstood recycling up to 10 times by decantation.
- Hagiwara, Hisahiro,Nakamura, Tomomi,Hoshi, Takashi,Suzuki, Toshio
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scheme or table
p. 1133 - 1137
(2011/06/26)
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- A three-carbon (n+1+2) ring expansion method for the synthesis of macrocyclic enones. Application to muscone synthesis
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The three-carbon ring expansion methodology commences with the preparation of a cyclic allene (C9, C11, C13), readily available from the corresponding cycloalkene via dibromocarbene addition and subsequent treatment with methyllithium. Dichloroketene addition to the cyclic allene regioselectively provides the [2+2] cycloadduct, which is reductively dechlorinated with zinc in methanol. The resulting cyclobutanone is then catalytically hydrogenated; cyclobutanone ring opening is affected with trimethylsilyl iodide; immediate dehydroiodination of the resulting β-iodocycloalkanone with diazabicycloundecane (DBU) provides the corresponding macrocyclic enone. The 15-membered enone was converted to d,l-muscone with (CH3)2CuLi.
- Erden, Ihsan,Cao, Weiguo,Price, Mary,Colton, Michael
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p. 5497 - 5501
(2008/09/21)
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- Efficient formation of ring structures utilizing multisite activation by indium catalysis
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Lewis acidic indium(III) salts, in particular In(NTf2) 3, effect the conversion of α-(ω′-alkynyl)-β- ketoesters and ω-alkynyl-β-ketoesters to the corresponding cyclic products in a manner known as the Coniaene reaction. This reaction
- Itoh, Yoshimitsu,Tsuji, Hayato,Yamagata, Ken-Ichi,Endo, Kohei,Tanaka, Iku,Nakamura, Masaharu,Nakamura, Eiichi
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scheme or table
p. 17161 - 17167
(2009/04/13)
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- A practical synthesis of (E)-2-cyclopentadecen-1-one: an important precursor of macrocyclic muscone
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A practical synthesis of (E)-2-cyclopentadecen-1-one (E)-2 which is an important precursor of macrocyclic muscone (1) was investigated. Olefination of 2-mesyloxycyclopentadecanone (7c) with strong acid such as sulfuric acid or trifluoromethanesulfonic acid afforded the desired (E)-2 in high yield with extremely high stereoselectivity, which was treated with methylmagnesium cuprate to furnish the dl-muscone in good yield.
- Hisanaga, Yusuke,Asumi, Yuya,Takahashi, Masaki,Shimizu, Yasuhiro,Mase, Nobuyuki,Yoda, Hidemi,Takabe, Kunihiko
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p. 548 - 551
(2008/04/13)
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- Indium-catalyzed cycloisomerization of ω-alkynyl-β-ketoesters into six- to fifteen-membered rings
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(Chemical Equation Presented) Many different sizes of rings available: Heating ω-alkynyl-β-ketoesters in the presence of In(NTf 2)3 (Tf=trifluoromethanesulfonyl) produces six- to fifteen-membered ring products in good yields. The reaction features low catalyst loading and moderately dilute conditions, and the formation of medium-sized rings is sometimes faster than that for the corresponding six-membered rings. A synthesis of (±)-muscone is also reported.
- Tsuji, Hayato,Yamagata, Ken-Ichi,Itoh, Yoshimitsu,Endo, Kohei,Nakamura, Masaharu,Nakamura, Eiichi
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p. 8060 - 8062
(2008/09/18)
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- Method for the production of 1,7-octadiene and use thereof
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The invention relates to a method for the production of 1,7 octadiene by reacting metathesis of cyclohexene with ethylene. The invention also relates to the production of 1,10-decandiol by hydroformulating 1,7 octadiene produced according to said method. The invention further relates to a method for the production of muscone or olefinically unsaturated analogs thereof using 1,10 decandiol which is obtainable in said manner.
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- Novel synthetic method for muscone
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Muscone is a precious fragrant compound scarce in nature. Many attempts to synthesize this unique natural product have been carried out. In this work, a novel synthetic method for the preparation of muscone from 3-methyl-15- hydroxypentadecanoate is provided. Benzimidazolium salt was used as tetrahydrofolate coenzyme model at formic acid oxidation level and Grignard reagent as nucleophile to which a one-carbon unit was transferred. The biomimetic synthesis of muscone was successfully accomplished using the addition-hydrolysis reaction of benzimidazolium salt with the Grignard reagent. Copyright Taylor & Francis, Inc.
- Guo, Yuan,Wu, Xin-Liang,Li, Jian-Li,Xu, Ruo-Qian,Shi, Zhen
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p. 2489 - 2494
(2007/10/03)
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- Diradical-promoted (n + 2 - 1) ring expansion: An efficient reaction for the synthesis of macrocyclic ketones
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(Chemical Equation Presented) A diradical-promoted (n + 2 - 1) ring expansion reaction based on vinyl side chain insertion (+2C) and decarbonylation (-1C) has been developed. Flash vacuum pyrolysis (FVP) of medium- and large-ring 2-trimethylsilyloxy-2-vinyl-cycloalkanones at 500-600°C affords the one-carbon ring-expanded cycloalkanones in good yields. Methyl groups on the vinyl moiety are transformed regiospecifically as corresponding α- and β-substituents, respectively. 2-Ethynyl precursor analogues react in a manner similar to give α,β-unsaturated cyclic ketones.
- Rueedi, Georg,Oberli, Matthias A.,Nagel, Matthias,Hansen, Hans-Jurgen
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p. 3179 - 3181
(2007/10/03)
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- Cyclopropylcarbinyl radicals as three-carbon insertion units: Easy synthesis of C-15 macrocyclic ketones by three-carbon ring expansion
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Thermal isomerization of cyclic 3-cyclopropyl ketones under FVP conditions at 620°C provides a new and convenient route to δ,ε-unsaturated cycloalkanones. The synthetic potential of this novel three-carbon ring expansion has been demonstrated by the synthesis of (±)-muscone from inexpensive C-12 starting material.
- Rüedi, Georg,Hansen, Hans-Jürgen
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p. 5143 - 5145
(2007/10/03)
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- Serine carbonates
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Serine carbonates of formula I are precursors for organoleptic compounds, masking agents and antimicrobial agents. Further they are alternative substrates for malodor producing enzymes. The symbols in formula I are defined in claim 1.
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- Short and versatile two-carbon ring expansion reactions by thermo-isomerization: Novel straightforward synthesis of (±)-muscone, nor- and homomuscones, and further macrocyclic ketones
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Thermo-isomerization of 1-vinyl substituted medium-and large-ring cycloalkanol derivatives in a flow reactor system at temperatures of 600°C to about 650°C leads directly to the ring-expanded macrocyclic ketones. Alkyl substituents at the vinylic moiety are transferred locospecifically to the ring-expanded ketone as corresponding α-, and β-substituents, respectively. This novel thermal 1,3-C shift reaction therefore provides a new access to short syntheses of many alkyl-substituted macrocyclic ketone derivatives [e.g. (±)-muscone and analogues] in a systematic manner.
- Nagel, Matthias,Hansen, Hans-Jürgen,Fráter, Georg
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p. 280 - 284
(2007/10/03)
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- Compounds having protected hydroxy groups
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The present invention relates to compounds with protected hydroxy groups of formula (I) These compounds are precursors for organoleptic agents, such as fragrances, and masking agents and for antimicrobial agents. When activated, the compounds of formula (I) are cleaved and form one or more organoleptic and/or antimicrobial compounds.
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- Compounds having protected hydroxy groups
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The present invention relates to compounds with protected hydroxy groups of formula (I) These compounds are precursors for organoleptic agents, such as fragrances, and masking agents and for antimicrobial agents. When activated, the compounds of formula (I) are cleaved and form one or more organoleptic and/or antimicrobial compounds.
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- Precursors for fragrant ketones and fragrant aldehydes
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The present invention refers to fragrance precursors of formula I for a fragrant ketone of formula II and one or more fragrant aldehydes or ketones of formula III and IV, These fragrance precursors are useful in perfumery, especially in the fine and functional perfumery.
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- Beta-ketoester compounds
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The beta-ketoesters of formula I are useful as precursors for organoleptic compounds, especially for flavors, fragrances and masking agents and antimicrobial compounds.
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- Ketone precursors for organoleptic compounds
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The invention discloses ketones of formula I: wherein, Y is an optionally substituted alkyl, cycloalkyl, or cycloalkylalkyl, wherein each alkyl group is straight or branched and each alkyl and cycloalkyl group is saturated or unsaturated; R1is hydrogen or a C1-6alkyl group that is substituted, saturated or unsaturated, straight or branched; A is a chromophoric substituted aromatic ring or ring system; n is an integer; and with the proviso that formula I is not 2-ethoxy-1-phenyl-ethanone. These compositions are useful for the delivery of organoleptic compounds, especially of flavors, fragrances, masking agents and antimicrobial compounds.
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- Electroorganic synthesis 65. Anodic homocoupling of carboxylic acids derived from fatty acids
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Fatty acid derived carboxylic acids with double bonds, hydroxy-, amino-, keto-, ester- and epoxy groups are anodically coupled to dimers (Kolbe electrolysis) in 29 to 81% yield and up to a 2.5 mol scale. Problems due to the low conductivity of fatty acid salts were overcome by the use of a flow cell with a narrow electrode gap. Fatty acids with branched alkyl chains gave dimers with interesting emulsifying properties. Dimethyl hexadecanedioate, accessible from methyl azelate, could be cyclized and further converted into homomuscone and muscone in a few steps. A commercial mixture of dimeric fatty acids (C36-dicarboxylic acids) has been coupled to give C70-diesters. Acta Chemica Scandinavica 1998. Part 64: Nielsen, M. F., Batanero, B.,.
- Weiper-Idelmann, Andreas,Aus Dem Kahmen, Martin,Schaefer, Hans J.,Gockeln, Marianne
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p. 672 - 682
(2007/10/03)
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- Hydroformylation of ω-functionalized 1,1-disubstituted alkenes and its use toward the synthesis of (±)muscone
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The rhodium-catalyzed hydroformylation of ω-functionalized 1,1-disubstituted alkenes and the synthesis of (±)-muscone using this hydroformylation and cyanohydrin alkylation are described. Kuraray.
- Takahashi, Takashi,Machida, Kazuhiro,Kido, Yoichi,Nagashima, Kensuke,Ebata, Satoshi,Doi, Takayuki
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p. 1291 - 1292
(2007/10/03)
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- SmI2-Promoted conjugate reduction of α,β-unsaturated esters and ketones studied in comparison with Mukaiyama-Michael reaction of ketene silyl acetal
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SmI2-promoted conjugate reduction of α,β-unsaturated esters and ketones proceeds in a manner quite similar to Mukaiyama-Michael reaction of ketene silyl acetal. The more substituted eaters are reduced more preferentially than the less substituted ones. The substrates with a 12 or 16 membered-ring structure undergo reduction smoothly. On the other hand, the 6-membered substrates completely fail to react under the same conditions. These results indicate generation of intermediate enolate radicals to be a key step for the conjugate reduction.
- Fujita, Yukihiro,Fukuzumi, Shunichi,Otera, Junzo
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p. 2121 - 2124
(2007/10/03)
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- A New Synthesis of (+/-)-Phoracantholide, (+/-)-Dihydrorecifeiolide, and (+/-)-Muscone via α-Nitro Ketones
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Cα' alkylation of α-nitro cycloalkanones 1a-c with methyl iodide at -35 to -70 deg C in THF/heptane/DMPU/TMDA in the presence of LDA as a base furnished the methylated α-nitro ketones 2a-c.Denitration of 2a, b with Bu3SnH/AIBN in dry benzene afforded the α'-methylated ketones 3a, b, which were converted to (+/-)-phoracantholide (4a) and (+/-)-dihydrorecifeiolide (4b), respectively, by the Bayer-Villiger oxidation.Reduction of 2c with NaBH4 and dehydration of the obtained nitro alkanol 5 with Al2O3/DMAP furnished the corresponding nitro alkene 6.Nef conversion of 6 with sodium hypophosphite and Raney nickel afforded (+/-)-muscone (7) in good yields. - Keywords: (+/-)-Phoracantholide / (+/-)-Recifeiolide / (+/-)-Muscone / α-Nitro ketones
- Ballini, Roberto,Marcantoni, Enrico,Petrini, Marino
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p. 1381 - 1384
(2007/10/02)
-
- Copper-Catalyzed Conjugate Addition of Trimethylaluminium to α,β-Unsaturated Ketones
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The conjugate methylation of α,β-unsaturated ketones with trimethylaluminium occurs smoothly in a very simple procedure under the catalytic CuI salts.Scope and limitations of this process as well as the influence of solvent and catalyst on the kinetics were studied.In addition, the effect of chlorotrimethylsilane as an additive was investigated.Attack on the carbonyl group in 1,2-fashion could not be observed under the reaction conditions.- Key Words: Conjugate alkylation / Trimethylaluminium / Copper catalysis
- Kabbara, Jazid,Flemming, Steffen,Nickisch, Klaus,Neh, Harribert,Westermann, Juergen
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p. 1489 - 1494
(2007/10/02)
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- Dianion Methodology for the Construction of Large-Membered Ring Systems: Application to the Synthesis of Muscone.
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A dianion method for the construction of the macrocycles has been developed and applied to the synthesis of natural fragrance muscone.Conformational analysis of the macrocycle using MM2-Monte Carlo method was carried out to evaluate whether the rationally designed intermediate will readily cyclize.
- Takahashi, Takashi,Yamada, Haruo,Haino, Takeharu,Kido, Yoichi,Fukazawa, Yoshimasa
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p. 7561 - 7564
(2007/10/02)
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- Homologation of large rings
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Free radical-promoted, one-carbon, ring expansion of twelve, fourteen-, and fifteen-membered cyclic β-keto esters is described. The method is then extended to include a three-carbon ring expansion of cyclododecanone, the targets being (±)-muscone and natu
- Dowd,Choi
-
p. 4773 - 4792
(2007/10/02)
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- 3-amino-2-hydroxybornane derivatives, asymmetric Michael reaction using the same, and process for preparing optically active muscone utilizing Michael reaction
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A 3-amino-2-hydroxybornane derivative represented by formula (I): STR1 wherein R represents a furfuryl group, a 1-methylpyrrolylmethyl group, or a benzyl group, is disclosed. The compound is useful as a ligand in an asymmetric Michael reaction, particularly for the production of an optically active muscone.
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- Free radical ring expansion and rearrangement of large carbocyclic rings
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Free radical initiated ring expansion of twelve-, thirtheen-, and fourteen-membered carbocyclic rings is described together with a new synthesis of (R)-(-)-muscone.
- Dowd, Paul,Choi, Soo-Chang
-
p. 565 - 568
(2007/10/02)
-
- 92. A Short Synthesis of (+/-)-Muscone
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(+/-)-Muscone ((+/-)-1) has been synthesized in three steps from 2-(2'-methylprop-2'-enyl)cyclododecan-1-one (2).The synthesis involves two key transformations: a Lewis-acid-mediated intramolecular ene reaction (2 -> 3) and the β-cleavage of the bicyclic potassium alkoxide 3a' to the macrocyclic enone (Z)-11.
- Rautenstrauch, Valentin,Snowden, Roger L.,Linder, Simon M.
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p. 896 - 901
(2007/10/02)
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- A NEW TWO-CARBON OLEFIN HOMOLOGATION PROCEDURE THAT LEADS TO α-CHLOROENONES. AN EFFICIENT SYNTHESIS OF d,l-MUSCONE
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Dichloroketene-olefin cycloadducts, α,α-dichlorocyclobutanones, are easily converted to α-chloroenones through a 3-step (2-pot) sequence of reactions.The overall result is the insertion of a functionalized 2-carbon unit between the original olefinic carbons.The efficiency of the method is demonstrated by a high-yield synthesis of d,l-muscone.
- Depres, Jean-Pierre,Navarro, Brigitte,Greene, Andrew E.
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p. 2989 - 2998
(2007/10/02)
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- A New Synthesis of Muscone and Exaltone. The Enamine Approach of Ring-Enlargement Reaction
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Key reaction in the synthesis of the title compounds in the treatment of the aldehydes 6 and 7 (obtained from 1) with a primary amine, e.g. pentylamine, in EtOH at room temperature.After stirring overnight, the products 8 and 9, respectively, are obtained in good yields.Both are enlarged by three ring members and can be transformed to Exalton (12) and (+/-)-muscone, (13), respectively.
- Bienz, Stefan,Hesse, Manfred
-
p. 1704 - 1707
(2007/10/02)
-
- Substituent Control of Sigmatropic Periselectivity: Application to the Synthesis of (+/-)-Muscone
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The thermal and anionic rearrangements of trans-1-vinylcyclotridec-3-en-1-ol compounds substituted in the α and β vinyl positions have been examined to determine whether the substituents can be used to control the periselectivity.For the anionic rearrangements, trimethylsilyl groups were found to be unsuitable, and terminal vinyl methyl or isopropyl groups did not provide a useful selectivity.Under thermal conditions, either a terminal trimethylsilyl or methyl gave high periselective control favoring the 1,3-shift siloxy Cope ring expansion relative to the 3,3-shift.This was used in a new synthesis of muscone.
- Thies, Richard W.,Daruwala, Khushroo P.
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p. 3798 - 3806
(2007/10/02)
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- A SIMPLE NEW GENERAL SYNTHESIS OF MACROCYCLIC KETONES: A NEW ENTRY TO THE SYNTHESIS OF EXALTONE AND (+/-)-MUSCONE
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We describe an efficient new synthesis of 15-membered cyclic ketones, exaltone and (+/-)-muscone, based on a three-carbon annelation of cyclic ketones followed by the regioselective radical cleavage of the fused bond of the resulting bicyclic systems.
- Suginome, Hiroshi,Yamada, Shinji
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p. 3963 - 3966
(2007/10/02)
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- A SIMPLE AND FACILE SYNTHESYS OF d,1-MUSCONE
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An efficient method for the synthesis of d,1-muscone has been developed.
- Taechachoonhakit, Siriwan,Ratananukul, Piniti
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p. 911 - 912
(2007/10/02)
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- Substituent Control of Periselectivity: Application to the Synthesis of (+/-)-Muscone
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The thermal, -shift siloxy-Cope, ring expansion is shown to be highly favoured relative to the -shift for the large-ring system required for the synthesis of muscone.
- Thies, Richard W.,Daruwala, Khushroo P.
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p. 1188 - 1189
(2007/10/02)
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- CHEMISTRY OF ORGANOSILICON COMPOUNDS CLXXXVIII. REACTION OF ORGANODISILANES WITH DIENES CATALYZED BY TRANSITION METAL COMPLEXES. PREPARATION OF 1,8-BIS(TRIMETHYLSILYL)OCTA-2,6-DIENE AND ITS USE IN THE SYNTHESIS OF dl-MUSCONE
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Organodisilanes, Me3-nXnSiSiXnMe3-n (X = Cl and MeO, n = 0, 1, 2) undergo efficient 1:2 addition reactions with butadiene and isoprene in the presence of a catalytic amount of a suitable palladium complex.One of the products, the title compound, was used as a starting material for a short synthesis of dl-muscone.
- Sakurai, Hideki,Eriyama, Yuichi,Kamiyama, Yoshiyasu,Nakadaira, Yasuhiro
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p. 229 - 238
(2007/10/02)
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- STRATEGY FOR CYCLOPENTENONE ANNULATION OF OLEFINS: A GENERAL PROTOCOL FOR BICYCLOENONE SYNTHESIS
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Several bicyclic α-chloro enones obtained through Greene annulation of cyclic olefins are shown to undergo efficient, two step, enone transposition via Luche reduction and aq. formic acid treatment.Application of this methodology to the formal synthesis of exaltone and (+/-)-muscone is described.
- Mehta, Goverdhan,Rao, K. Srinivas
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p. 1839 - 1842
(2007/10/02)
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