- Synthesis of Unsaturated Spiroacetals, Cyclopentanone Derivatives, in the Presence of Natural Aluminosilicate Modified with Zirconium Cations
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Abstract: Conditions for the condensation of cyclopentanone and n-valeric aldehyde to 2-pentylidenecyclopentanone in the presence of an alcoholic solution of piperidine have been developed. The isomerization of the latter in a continuous-flow system over γ-Al2O3 yields 2-pentylcyclopent-2-en-1-one. The condensation of the obtained unsaturated ketones with ethane-1,2-diol in the presence of a heterogeneous catalyst, a natural aluminosilicate (perlite) modified with zirconyl sulfate, has been studied. The optimum conditions for the preparation of the corresponding unsaturated spiroacetals have been found. The synthesized compounds can be used as synthetic fragrances for different purposes.
- Abbasov,Alimardanov, Kh. M.,Abbaszade,Guseinova,Azimli
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p. 603 - 607
(2019/06/24)
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- Chemo-Enzymatic Oxidative Rearrangement of Tertiary Allylic Alcohols: Synthetic Application and Integration into a Cascade Process
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A chemo-enzymatic catalytic system, comprised of Bobbitt's salt and laccase from Trametes versicolor, allowed the [1,3]-oxidative rearrangement of endocyclic allylic tertiary alcohols into the corresponding enones under an Oxygen atmosphere in aqueous media. The yields were in most cases quantitative, especially for the cyclopent-2-en-1-ol or the cyclohex-2-en-1-ol substrates without an electron withdrawing group (EWG) on the side chain. Transpositions of macrocyclic alkenols or tertiary alcohols bearing an EWG on the side chain were instead carried out in acetonitrile by using an immobilized laccase preparation. Dehydro-Jasmone, dehydro-Hedione, dehydro-Muscone and other fragrance precursors were directly prepared with this procedure, while a synthetic route was developed to easily transform a cyclopentenone derivative into trans-Magnolione and dehydro-Magnolione. The rearrangement of exocyclic allylic alcohols was tested as well, and a dynamic kinetic resolution was observed: α,β-unsaturated ketones with (E)-configuration and a high diastereomeric excess were synthesized. Finally, the 2,2,6,6-tetramethyl-1-piperidinium tetrafluoroborate (TEMPO+BF4?)/laccase catalysed oxidative rearrangement was combined with the ene-reductase/alcohol dehydrogenase cascade process in a one-pot three-step synthesis of cis or trans 3-methylcyclohexan-1-ol, in both cases with a high optical purity. (Figure presented.).
- Brenna, Elisabetta,Crotti, Michele,De Pieri, Matteo,Gatti, Francesco G.,Manenti, Gabriele,Monti, Daniela
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supporting information
p. 3677 - 3686
(2018/06/04)
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- Method of manufacturing methylcyclopentanone deriv. (by machine translation)
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PROBLEM TO BE SOLVED: To provide an efficient method for producing a cyclopentanone derivative usable as an intermediate for a methyl (3-oxocyclopentyl)acetate derivative useful as a perfumery material.SOLUTION: The method for producing the cyclopentanone derivative expressed by general formula (III) comprises Michael addition reaction of a 2-cyclopenten-1-one derivative and an ester compound in the presence of a solid base catalyst containing a phosphazene base or a guanidine base. In the formula, Ris a 1-10C hydrocarbon group; Ris 1-4C alkyl; and Ris 1-4C alkyl or alkoxyl.
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Paragraph 0037
(2018/11/22)
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- PROCESS FOR PRODUCING 2-ALKYLCYCLOALKANONE
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The present invention relates to a process for producing 2-alkylcycloalkanones with a high yield and a high purity. In addition, the present invention also relates to a process for producing lactones as a useful perfume material for cosmetics, flavors, etc. More specifically, the present invention relates to a process for producing a 2-alkylcycloalkanone represented by the following general formula (2) which includes the step of subjecting a 2-(1-hydroxyalkyl)-cycloalkanone to dehydration and hydrogenation reaction in a flow of a hydrogen gas under a pressure of from 20 to 200 kPa (absolute pressure) in the presence of an acid and a platinum group metal catalyst; and a process for producing a lactone which includes the step of subjecting the 2-alkylcycloalkanone to oxidation reaction using a percarboxylic acid: wherein n is an integer of 1 or 2; and R1 and R2 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms with the proviso that R1 and R2 may form a ring through a carbon atom adjacent thereto.
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Page/Page column 10
(2012/08/28)
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- PROCESS FOR PRODUCING A 2-ALKYL-2-CYCLOALKENE-1-ONE
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The present invention relates to a process for producing a 2-alkyl-2-cycloalken-1-one represented by the following general formula (2), including the step of reacting a 2-alkylidene cycloalkanone in the presence of a palladium and/or platinum catalyst which is treated in the following steps (a) and (b); and a method for activating the palladium and/or platinum catalyst including the following steps (a) and (b): Step (a): activating the palladium and/or platinum catalyst in an atmosphere containing a hydrogen gas; and Step (b): replacing the hydrogen gas being present as the atmosphere for the catalyst in the step (a), with an inert gas to remove the hydrogen gas out of the reaction system, wherein m is 0 to 3; n is 1 or 2; R1 and R2 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and R3 is an alkyl group having 1 to 5 carbon atoms. In accordance with the present invention, the 2-alkyl-2-cycloalken-1-one can be produced with a high purity and a high productivity.
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Page/Page column 7
(2011/01/12)
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- METHOD FOR PRODUCING OF 2-ALKYL-2-CYCLOALKEN-1-ONE
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The present invention relates to [1] a process for producing a 2-alkyl-2-cycloalken-1-one represented by the following general formula (2), which includes the step of subjecting a 2-(1-hydroxyalkyl)cycloalkan-1-one to dehydration and isomerization in the co-existence of an acid and a platinum group metal catalyst, and [2] a process for producing an alkyl(3-oxo-alkylcycloalkyl)acetate which is useful as a perfume material, using the 2-alkyl-2-cycloalken-1-one: wherein n is an integer of 1 or 2; and R1 and R2 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms with the proviso that R1 and R2 may form a ring through a carbon atom adjacent thereto.
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Page/Page column 7
(2011/02/26)
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- PROCESS FOR PRODUCING 2-(1-HYDROXYALKYL)CYCLOALKANONE
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The present invention relates to a process for producing a 2-(1-hydroxyalkyl)cycloalkanone which includes the steps of (i) continuously mixing a cycloalkanone and an alkyl aldehyde in the water and a base catalyst to form a reaction system and allow both the compounds to react with each other; (ii) continuously withdrawing a reaction mixture produced in the step (i) out of the reaction system while allowing the step (i) to proceed; and (iii) adding an additional amount of water containing the base catalyst to the reaction system to maintain a constant concentration of the base catalyst and/or a constant amount of water in the reaction system while allowing the step (ii) to proceed.
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Page/Page column 8
(2010/09/17)
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- METHOD FOR PRODUCING OF 2-ALKYL-2-CYCLOALKEN-1-ONE
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The present invention relates to [1] a process for producing a 2-alkyl-2-cycloalken-1-one represented by the following general formula (2), which includes the step of subjecting a 2-(1-hydroxyalkyl)cycloalkan-1-one to dehydration and isomerization in the co-existence of an acid and a platinum group metal catalyst, and [2] a process for producing an alkyl(3-oxo-alkylcycloalkyl)acetate which is useful as a perfume material, using the 2-alkyl-2-cycloalken-1-one: wherein n is an integer of 1 or 2; and R1 and R2 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms with the proviso that R1 and R2 may form a ring through a carbon atom adjacent thereto.
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Page/Page column 11
(2011/01/12)
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- Cycloalkanone composition
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The present invention relates to a cycloalkanone composition which contains cycloalkanone (1) in an amount of 70 wt% or more based on the composition, wherein the content of a dimer of a cycloalkanone represented by formula (2) is 0.055 or less in terms of weight ratio to the cycloalkanone (1), a process for producing the same, a process for producing a composition containing alkyl acetate (5) by using the cycloalkanone composition, and an alkyl acetate composition obtained by the process wherein n is an integer of 1 or 2, R1 and R2 each represent H, a C1 to C8 alkyl group etc., and R3 represents a C1 to C3 alkyl group.
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Page/Page column 6-9
(2008/06/13)
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- Method of producing acetate derivative
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The present invention relates to a method of producing an acetate derivative represented by the formula (II) by demonocarboxylating dimalonate represented by the formula (I), wherein water is supplied while the concentration of water in a demonocarboxylating reaction solution is controlled to 0.4% by weight or less to run demonocarboxylation: wherein n denotes an integer of 1 or 2, R1 and R2 represent H, a C1-8 alkyl group or the like and R3 represents a C1-3 alkyl group.
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- Process for producing cycloalkanone derivatives
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The present invention provides a process for producing 2-(1-hydroxyalkyl)cycloalkanone and/or 2-(1-hydroxyaryl)cycloalkanone in high yield and selectivity, as well as a process using the same to produce a cycloalkanone derivative useful as a perfume material and a physiologically active substance. Disclosed is a process for producing compound (3), which includes subjecting a cycloalkanone, and aldehyde (2) containing carboxylic acid (1), to aldol condensation in the presence of water and a basic catalyst, wherein the molar amount (referred to hereinafter as A) of the basic catalyst added is not less than the molar amount (referred to hereinafter as B) of the carboxylic acid (1) contained in the aldehyde (2) and the difference between A and B, that is, (A - B) is 0.06 mol or less per mol of the aldehyde (2) , as well as a process for producing compounds (7) and (8) by using the compound (3) obtained by the above process.
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- Method for producing 2-(alkyl)cycloalkenone
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A method for producing 2-(alkyl)cycloalkenone and a method for producing alkyl(3-oxo-2-alkylcycloalkyl) acetate and 5-alkyl-5-alkanolide which are useful as flavoring materials and physiologically active substances using the same are provided. A method for producing Compound (2) including the steps of: dehydrating Compound (1) using an acid catalyst until the conversion ratio of dehydration reaction reaches 20 to 90% based on Compound (1), thereby obtaining a mixture containing Compound (1) and Compound (3); and isomerizing Compound (3) while dehydrating the remaining Compound (1), and a method for producing Compound (5) or (6) using obtained Compound (2).
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- Process for producing 2-alkyl-2cyclopentenones
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Industrially advantageous processes for producing a 2-alkyl-2-cyclopentenone in high yields starting from a 2-(1-hydroxyalkyl)cyclopentanone or a 2-alkylidenecyclopentanone, which are obtainable from a cyclopentanone and a carbonyl compound. A 2-(1-hydroxyalkyl)cyclopentanone represented by the following general formula (1): (wherein R1, R2, R3, R4, R5, R6 and R7 each independently represents hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have one or more substituents or an aromatic group which may have one or more substituents, and each of (1) R6 or R7 with R3 and (2) R6 or R7 with R4 or R5 may be together combined to form a ring which may have a double bond) is subjected to dehydrative isomerization in the presence of a bromine compound and/or an iodine compound.
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