WO2008057915A1 - PROCESSES FOR THE HYDROGENATION OF α,β-UNSATURATED KETONES - Google Patents

PROCESSES FOR THE HYDROGENATION OF α,β-UNSATURATED KETONES Download PDF

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WO2008057915A1
WO2008057915A1 PCT/US2007/083295 US2007083295W WO2008057915A1 WO 2008057915 A1 WO2008057915 A1 WO 2008057915A1 US 2007083295 W US2007083295 W US 2007083295W WO 2008057915 A1 WO2008057915 A1 WO 2008057915A1
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alkyl
branched
chain
straight
ketones
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Stephen E. Belmont
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Albemarle Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/227—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
    • C07C49/233—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings

Definitions

  • the reaction medium employed can be alcohols, such as methanol, ethanol, isopropanol, b ⁇ tanol, aliphatic or aromatic hydrocarbons, such as toluene, xylene, cyclohexane, isooctane and the like, ethers, such as tetrahydrofuran, dioxane or methyl tert-butyl ether, esters, such as ethyl acetate and lastly the reaction product itself if it is liquid at the reaction temperature; and, further that a proportion of water (for example up to 20% by weight of the total reaction medium) does not interfere, particularly if the reaction medium is water-soluble.
  • alcohols such as methanol, ethanol, isopropanol, b ⁇ tanol
  • aliphatic or aromatic hydrocarbons such as toluene, xylene, cyclohexane, isooctane and the like
  • ethers such as t
  • the weight percent of the ⁇ , ⁇ -unsaturated ketones to be hydrogenated as to the total weight of the ketones and the reaction medium ranges from about 17 wt% (63 g of ketones; 300 g of tetrahydrof ⁇ ran) to about 40 wt% (120 g of ketones; 180 g of methanol).
  • a need remains for such processes that accommodate a higher percentage weight throughput of ketones per total weight of the ketones and the reaction medium and provide additional commercial advantages
  • the hydrogenation has several advantages.
  • the water layer can be separated after filtration of the Ni-contaning catalyst, which removes most of the inorganic salts, This eliminates the need for a separate wash after the reaction medium/solvent strip or an extreme strip to near absolute dryness followed by 1-micron filtration. This can provide a considerable improvement ' m cycle time over other similar processes.
  • Any C 4 -C 10 alcohol is suitable for use in this invention.
  • Suitable alcohols include without limitation; butanol, hexanol, heptanol, octanol, decanol, etc.
  • Use of C 10+ alcohols would aiso be suitable.
  • the reaction medium can comprise an alcohol and water in a mass ratio of about 1 :2 to about 2: t , for example, in a mass ratio of about 1:1
  • the alcohol can comprise at least one C 4 -C 10 alcohol, which encompasses mixtures of two or more C 4 - C 10 alcohol.
  • the reaction medium can comprise an alcohol and water in a mass ratio of about 1 :2 to about 2:1 , wherein the alcohol comprises at least one C 4 -C 10 alcohol
  • the reaction medium can comprise an alcohol and water in a mass ratio of about 1:2 to about 2:1, wherein the alcohol comprises a mixture of two or more C 4 -C 10 alcohols.
  • the alcohol can consist essentially of at least one C 4 -C 10 alcohol.
  • the water can comprise of potable water from any suitable source.
  • C 1 -C 12 -alkyl can be, for example, methyl, ethyt, propyl, isopropyl : butyl, isobulyl, tert-butyl, armyl, hexyl, octyl, decyl or dodecyl; C 1 -C 8 -alkyl and C 1 -C 4 ⁇ alkyl are included.
  • Hydroxyalkyl carries a hydroxyl group in any position, for example in the ⁇ -position, and may furthermore be interrupted in the carbon chain by ether oxygen.
  • Carboxy-alkyl carries a carboxyl group in any position, e.g., in the ⁇ - or ⁇ -position.
  • Carboxy-alkyl can be C 1 -C 12 -alky; C 1 -C 8 -alkyl and C 1 -C 4 -alkyl are induded.
  • C 2 -C 12 -alkenyl can be, for example, vinyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl, octenyl, decenyl or dodecenyl; C 2 -C 6 -alkeny! and C 2 ⁇ C 4 ⁇ aikenyl are included.
  • C 3 -C 8 -cycfoafkyl can be, for example, cyclopropyl, cyclobutyl, cydopentyl, cyclohexyl, cydohepty! or cyclooetyl, any of which can be substituted by one or two methyl or ethyl groups; substituted or unsubstituted cyclopropyi, cycfopentyl or cydohexyl are included.
  • C 3 -C 8 -cycloalkeny! can be, for example, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexehyl, cycloheptenyl orcyclooctenyl
  • C 7 -C 14 -aralkyl can be, for example, benzyi, phenylethyl, naphthylmethyl, naphthylethyl, biphenyl-methyl of biphenyi-ethyl,
  • C 6 -C 12 -aryi can be, for example, phenyl, e.g., 4-chlorophenyf, or naphthyl or biphenyl.
  • At least one of R 1 and R 2 in the ⁇ , ⁇ -unsaturated ketone is monosubstituted to trisubstltuted by halogen, such as fluorine, chlorine or bromine.
  • halogen such as fluorine, chlorine or bromine.
  • one substitution can be by fluorine and a second substitution by bromine.
  • Each R 1 or R 2 that is aromatic can furthermore carry one or two methyl or ethyl groups, or rnethoxy or eth ⁇ xy groups, and aiso the hydroxy! group.
  • R 1 and R 2 independently of one another denote straight-chain or branched C 1 -C 8 -alkyi, C 2 -C 8 -alkenyi, cyciopropyi, cydopenty!, cyclchexyl, benzyl, phenytethyf or phenyl, where at least one of R 1 and R 2 represents phenyl and where furthermore at least one of R 1 and R 2 is monosubstituted to trisubstituted by halogen.
  • ketones are 5-halophenyl-2,2-dimethylpent-4-en-3-ones. particularly 5-(4-ch(orophenyl)-2,2-dimethyl-pent-4-en-3-one, and
  • All ⁇ -unsaturateci ketones are In each case distinguished by at least one substituent which is substituted by halogen.
  • the ⁇ , ⁇ unsaturated ketones to be used can be prepared via aldol condensation, as will be familiar to those skilled in the art.
  • Basic substances useful in this invention can comprise organic amine.
  • suitable organic amines include aliphatic amines, e.g., thriethylamine or tripropylamine, and heterocyclic amines.
  • the basic substances may, if they are water- soluble, be used as aqueous solution or as solid.
  • tripropylamine is used and the reaction medium consists essentially of hexanol and water in about a 1 :1 mass ratio, because the hexanol (bp 156) and tripropyfamme (bp 155-158) have almost identical boiling points, they will co-dtsii and can be almost completely recycled. Any water that co-distills with the alcohol and amine has no effect as the reaction medium mix is about 1:1 water: hexanol.
  • Catalysts used according to this invention can be Ni-containing, such as Ni on supports, Ni in the form of elemental nickel sponge, Ni oxide, Raney nickel and others.
  • Supports can be, for example, SiO 2 , AI 2 O 3 , pumice, carbon and other supports known to those skilled in the art.
  • Raney catalysts such as Raney nickel, Raney nickeHron, Raney nickel-cobalt or Raney nickel-iron-cobalt in anhydrous or even water-moist or reaction medium/solvent-moist form can be used.
  • Examples of such compounds are bis-(2-hydroxyethyl) sulphide, bis-(2-hydroxypropyl ⁇ sulphide, thiodiacetic acid and its alkali metal salts, thioanisole, thiodipropionic acid, its salts and its dimethyl ester, diphenyl sulphide, dithiane, thioxane, thiophene, benzothiazole, dimethyl sulphoxide, methyl ethyl sulphoxide and diethyl sulphoxide.
  • the addition of the organic sulphur compound can be carried out together with the catalyst, before the addition or after the addition of the catalyst.
  • the organic sulphur compound in general only needs to be added to the catalyst or to the reaction mixture on the first use. A subsequent addition of the organic sulphur compound is possible, but generally only necessary If fresh catalyst is added in place of somewhat consumed or exhausted catalyst.
  • the process can be carried out either batchwise or continuously.
  • the process may furthermore be applied using either pure ⁇ , ⁇ -unsaturated ketones or crude ⁇ , ⁇ unsaturated ketones, for example from the aldoi condensation, in which such ⁇ , ⁇ -unsaturated ketones can be obtained from an aldehyde and a methyl ketone.
  • the basic substance can be added in an amount from about 0.001 to about
  • the Ni ⁇ containing catalyst can be added in an amount from about 0.001 to about 0,1 parts by weight, e.g., about 0.003 to about 0.04 parts by weight, per part by total weight of the ⁇ , ⁇ -unsaturated ketones and the Ni-containing catalyst.
  • the organic sulphur compound can be used in an amount from about 0.0002 to about 0.1 parts by weight, for example about 0.0004 to about 0,075, or about 0.01 to about 0.05 parts by weight, per part by total weight of the ⁇ . ⁇ -unsaturated ketones and the organic suiphur compound.
  • the process can be carried out such that the unsaturated alkyl ketones, the reaction medium comprising an alcohol and water in a mass ratio of about
  • the hydrogenation can be carried out at about 30°C to about 250°C, for example at about 50°C to about 140°C, and at an H 2 pressure of about 150 psi to about 1000 psi, for example about 400 psi to about 800 psi.
  • the exothermic hydrogenation reaction can proceed for about 3 hours at about 10Q°C to greater than 99% conversion of the unsaturated alkyl ketone to saturated alkyi ketone in produced crude product, which also comprises trace amounts of amine hydrochloride.
  • the crude product comprising saturated alky! ketone can be filtered to remove Ni-containing catalyst; filtering methods and aids known to those skilled in the art can be used, e.g., filter/body aids can be used.
  • a basic substance at a pH of about 8 to about 14, such as sodium hydroxide, potassium hydroxide, calcium hydroxide (for example in the form of slaked time), catdum o ⁇ ide, potassium carbonate, sodium carbonate, sodium acetate, or mixtures thereof, can be added to the crude product to convert the amine hydrochloride to a chloride, e.g., inorganic chloride, metal chloride (such as sodium chloride), or the like, and an amine, e,g>, tripropylamine. Phases can be separated and the water layer, which contains the inorganic salts, can be discarded. Then alcohol and any remaining water can be distilled out using means known to those skilled in the art.
  • Substantially all of the alcohol can be distilled due to the volatility difference between the alcohol and the saturated alkyl ketone product.
  • a benefit is that the saturated alkyl ketone product can be distilled without the need for a separate aqueous wash to remove salts.
  • the saturated alkyl ketone can men be distilled, using one or more distillation columns, e.g., two distillation columns. Continuous distillation can be used.
  • reactants and components are identified as ingredients to be brought together in connection with performing a desired chemical reaction or In forming a mixture to be used in conducting a desired reaction. Accordingly, even though the claims hereinafter may refer to substances, components and/or ingredients in the present tense ("comprises”, “is”, etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, combined, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure. Whatever transformations, if any. which occur in situ as a reaction is conducted is what the claim is intended to cover.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The catalytic hydrogenation of α,β-unsaturated ketones R1-CH=CH-CO-R2 in which R1 and R2 independently of one another represent straight-chain or branched C1-C12-alkyl or C2-C12-hydroxyalkyl, straight-chain or branched C2-C12-alkenyl, C3-C8-cycloalkyl, C3-C8-cycloalkenyl, C7-C14-aralkyl or C6-C12-aryl, where at least one of R1 and R2 is monosubstituted to trisubstituted by halogen, to give the respective saturated ketones R11-CH2-CH2-CO-R12 in which R11 and R12 assume the meaning of R1 and R2 with the exception that alkenyl and cycloalkenyl are hydrogenated to the respective alkyl or cycloalkyl, wherein the hydrogenation process comprises combining the α,β-υnsaturated ketones and a reaction medium comprising a C4-C10 alcohol and water in about a 1:2 to about a 2:1 mass ratio, and the hydrogenation is earned out in the presence of (i) basic substance comprising organic amine, (ii) Ni-containing catalyst, and (iii) organic sulphur compound.

Description

PROCESSES FOR THE HYDROGENATION OF α,β-UNSATURATED KETONES
BACKGROUND
[9001] US Patent 4,540,819 describes a process for the catalytic hydrogenation of α,β-unsaturated ketones R1 -CH=CH-CO-R2 in which R1 and R2 independently of one another represent straight-chain or branched C1-C12-alkyl or C2-C12 -hydroxyalkyl, straight-chain or branched C2-C12-alkenyl, C3-C8-cyclocycloalkyl, C3-C8-cycloalkenyl, C7-C14-aralkyl or C6-C12 -ary!, where at least one of R1 and R2 is monosubstituted to trisubstituted by halogen, to give the respective saturated ketones R11-CH2-CH2-CO-R12 in which R11 and R12 assume the meaning of R1 and R2 with the exception that alkenyl and cycloalkenyt are hydrogenated to the respective alkyl or cycloalkyl, which is characterized in that a Ni-containing catalyst is employed and that the reaction is carried out in the presence of an organic sulphur compound R3-S(=O)n-R4 In which R3 and R4 independently of one another denote straight-chain or branched C1-C12~alkyl, hydroxy- C2-C12-alkyl, carboxy- C1-C12-alkyl or phenyl, and furthermore R3 and R4 may together represent -CH=CH-CH=CH-; -(CH2)4-, -CH2)5-, -(CH2)2-S-(CH2)2- or -(CH2)2-O-(CH2)2-, R4 may additionally denote hydrogen or CO- C1-C12-alkyl and n assumes me value 0 or 1. it is disclosed that the reaction medium employed can be alcohols, such as methanol, ethanol, isopropanol, bυtanol, aliphatic or aromatic hydrocarbons, such as toluene, xylene, cyclohexane, isooctane and the like, ethers, such as tetrahydrofuran, dioxane or methyl tert-butyl ether, esters, such as ethyl acetate and lastly the reaction product itself if it is liquid at the reaction temperature; and, further that a proportion of water (for example up to 20% by weight of the total reaction medium) does not interfere, particularly if the reaction medium is water-soluble.
[0002] In the examples provided in US Patent 4,940,819, the weight percent of the α,β-unsaturated ketones to be hydrogenated as to the total weight of the ketones and the reaction medium ranges from about 17 wt% (63 g of ketones; 300 g of tetrahydrofυran) to about 40 wt% (120 g of ketones; 180 g of methanol). [0003] In spite of the disclosure of US 4,940.819, and other known processes for the catalytic hydrogenatioπ of α,β-unsaturated ketones, a need remains for such processes that accommodate a higher percentage weight throughput of ketones per total weight of the ketones and the reaction medium and provide additional commercial advantages,
THE INVENTION
[0004] This invention meets the above-described need by providing processes for the catalytic hydrogenation of α,β-unsaturated ketones R1-CH=CH-CO-R2 in which R1 and R2 independently of one another represent straight-chain or branched C1-C12-alkyl or C2-C12-hydroxya!kyl, straight-chain or branched C2-C12-alkenyf, C3-C8-cycioalkyl, C3-C8-cycloalkenyi, C7-C14-aralkyl or C6-C12-aryl where at least one of R1 and R2 is monosubsiituted to irisubstituted by halogen, to give the respective saturated ketones R11-CH2-CH2-CO-R12 in which R11 and R12 assume the meaning of R1 and R2 with the exception that alkenyl and cydoalkenyl are hydrogenated to the respective aikyi or cycloalkyl, which is characterized in that the process comprises combining at least a reaction medium comprising an aicohoi and water in a mass ratio of about 1:2 to about 2:1 and the αβ-unsaturated ketones, wherein the alcohol comprises at least one C4 - C10 alcohol and the hydrogeπatioπ is carried out in the presence of (i) basic substance comprising organic amine, (ii) Ni-containing catalyst, and (iii) organic sulphur compound R8-S(=O)n-R4 in which R3 and R4 independently of one another denote straight-chaϊn or branched C1-C12-alkyl. hydroxy- C2-C12-alkyl, carboxy- C1-C12-alky! or phenyl, add furthermore R3 and R4 may together represent -CH=CH-CH=CH-, -(CH2)4,- -CH2)5-, -(CH2)2-S-(CH2)2~ or -(CH2)2-O-(CH2)2-, R4 may additionally denote hydrogen or CO- C1-C12 alky! and n assumes the value 0 or 1. [0005] We have discovered that by using a reaction medium comprising an afcobol and water in & mass ratio of about 1 :2 to about 2:1 , wherein the alcohol comprises 3t least one C4 - C19 alcohol : the hydrogenation has several advantages. For example, the water layer can be separated after filtration of the Ni-contaning catalyst, which removes most of the inorganic salts, This eliminates the need for a separate wash after the reaction medium/solvent strip or an extreme strip to near absolute dryness followed by 1-micron filtration. This can provide a considerable improvement 'm cycle time over other similar processes.
[0006] As will be familiar to those skilled in the art, the terms "combined" and "combining" as used herein mean that the components that are "combined" or that one is "combining" are put into a container with each other. Likewise a "combination" of components means the components having been put together in a container. This invention also provides such compositions and methods wherein the composition is an activator composition.
[0007] This invention is described in connection with specific embodiments. It is understood that this invention is not limited to any one of these specific embodiments.
C4-C10 Alcohols
[0008] Any C4-C10 alcohol is suitable for use in this invention. Suitable alcohols include without limitation; butanol, hexanol, heptanol, octanol, decanol, etc. Use of C10+ alcohols would aiso be suitable.
Reaction Medium
[0009] The reaction medium can comprise an alcohol and water in a mass ratio of about 1 :2 to about 2: t , for example, in a mass ratio of about 1:1 The alcohol can comprise at least one C4-C10 alcohol, which encompasses mixtures of two or more C4 - C10 alcohol. The reaction medium can comprise an alcohol and water in a mass ratio of about 1 :2 to about 2:1 , wherein the alcohol comprises at least one C4-C10 alcohol The reaction medium can comprise an alcohol and water in a mass ratio of about 1:2 to about 2:1, wherein the alcohol comprises a mixture of two or more C4-C10 alcohols. The alcohol can consist essentially of at least one C4-C10 alcohol. The water can comprise of potable water from any suitable source.
α.β-Unsaturated Ketones
[0010] α,β-unsaturated ketones suitable for hydrogenating according to this invention include α,β~unsaturated ketones R1-CH =CH-CO-R2 in which R1 and R2 independently of one another represent straight-chain or branched C1-C12-alky or C2-C12-hydroxyalkyl, straight-chain or branched C2-C12-alkenyl, C3-C8-cycloalkyl, C3-C8-cycloalkenyl, C7-C14-aralkyl or C8-C12-aryl, where at least one of R1 and R2 is monosubstituted to trisubstituted by halogen.
[0011] Straight-chain or branched C1-C12-alkyl can be, for example, methyl, ethyt, propyl, isopropyl: butyl, isobulyl, tert-butyl, armyl, hexyl, octyl, decyl or dodecyl; C1-C8-alkyl and C1-C4~alkyl are included. Hydroxyalkyl carries a hydroxyl group in any position, for example in the ω-position, and may furthermore be interrupted in the carbon chain by ether oxygen. Carboxy-alkyl carries a carboxyl group in any position, e.g., in the σ- or ω-position. Carboxy-alkyl can be C1-C12-alky; C1-C8-alkyl and C1-C4 -alkyl are induded.
[0012] Straight-chain or branched C2-C12-alkenyl can be, for example, vinyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl, octenyl, decenyl or dodecenyl; C2-C6-alkeny! and C2~C4~aikenyl are included.
[0013] C3-C8-cycfoafkyl can be, for example, cyclopropyl, cyclobutyl, cydopentyl, cyclohexyl, cydohepty! or cyclooetyl, any of which can be substituted by one or two methyl or ethyl groups; substituted or unsubstituted cyclopropyi, cycfopentyl or cydohexyl are included.
[0014] C3-C8-cycloalkeny! can be, for example, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexehyl, cycloheptenyl orcyclooctenyl
[0015] C7-C14-aralkyl can be, for example, benzyi, phenylethyl, naphthylmethyl, naphthylethyl, biphenyl-methyl of biphenyi-ethyl,
[0016] C6-C12-aryi can be, for example, phenyl, e.g., 4-chlorophenyf, or naphthyl or biphenyl.
[0017] At least one of R1 and R2 in the α,β-unsaturated ketone is monosubstituted to trisubstltuted by halogen, such as fluorine, chlorine or bromine. In the case of multiple substitution, it is not required that each substitution be by the same type of halogen atom. For example, one substitution can be by fluorine and a second substitution by bromine.
[0018] Each R1 or R2 that is aromatic can furthermore carry one or two methyl or ethyl groups, or rnethoxy or ethαxy groups, and aiso the hydroxy! group.
[0019] α.β-unsaturated ketones R1CH=CH-CO-R2 can be used in which
R1 and R2 independently of one another denote straight-chain or branched C1-C8-alkyi, C2-C8-alkenyi, cyciopropyi, cydopenty!, cyclchexyl, benzyl, phenytethyf or phenyl, where at least one of R1 and R2 represents phenyl and where furthermore at least one of R1 and R2 is monosubstituted to trisubstituted by halogen.
[0020] Further suitable α.β-unsaturated ketones are R1-CH=CH-CO-R2 in which R1 denotes phenyl and R2 denotes straight-chain or branched C1-C8-aiky(, C2-C8-aikenyl, cyclopropyi, benzyl or phenyl, where at least one of R1 and R2 is monosuostituted to trisubstituted by halogen.
[0021] Further ketones are 5-halophenyl-2,2-dimethylpent-4-en-3-ones. particularly 5-(4-ch(orophenyl)-2,2-dimethyl-pent-4-en-3-one, and
6ahalophenyl-3,3-dimethylrrex~5-en~4~ones.
[0022] All αβ-unsaturateci ketones are In each case distinguished by at least one substituent which is substituted by halogen.
[0023] The α,β~unsaturated ketones to be used can be prepared via aldol condensation, as will be familiar to those skilled in the art.
Basic Substances
[0024] Basic substances useful in this invention can comprise organic amine. Examples of suitable organic amines include aliphatic amines, e.g., thriethylamine or tripropylamine, and heterocyclic amines. The basic substances may, if they are water- soluble, be used as aqueous solution or as solid. When tripropylamine is used and the reaction medium consists essentially of hexanol and water in about a 1 :1 mass ratio, because the hexanol (bp 156) and tripropyfamme (bp 155-158) have almost identical boiling points, they will co-dtsii and can be almost completely recycled. Any water that co-distills with the alcohol and amine has no effect as the reaction medium mix is about 1:1 water: hexanol.
Ni-Containing Catalysts
[0025] Catalysts used according to this invention can be Ni-containing, such as Ni on supports, Ni in the form of elemental nickel sponge, Ni oxide, Raney nickel and others. Supports can be, for example, SiO2, AI2O3, pumice, carbon and other supports known to those skilled in the art. However, Raney catalysts, such as Raney nickel, Raney nickeHron, Raney nickel-cobalt or Raney nickel-iron-cobalt in anhydrous or even water-moist or reaction medium/solvent-moist form can be used.
Organic Sulphur Compounds
[0028] Processes according to this invention can be carried out in the presence of one or more organic sulphur compounds R13-S(=O)n-R14 , where R13 and R14 independently of one another denote alkyl, hydroxy- C2-C12-alkyl or carboxy~ C1-C12-alkyl, and where R14 additionally may denote CO- C1-C8-aikyl and n assumes the value 0 or 1.
[0027] Examples of such compounds are bis-(2-hydroxyethyl) sulphide, bis-(2-hydroxypropyl} sulphide, thiodiacetic acid and its alkali metal salts, thioanisole, thiodipropionic acid, its salts and its dimethyl ester, diphenyl sulphide, dithiane, thioxane, thiophene, benzothiazole, dimethyl sulphoxide, methyl ethyl sulphoxide and diethyl sulphoxide. |0028] The addition of the organic sulphur compound can be carried out together with the catalyst, before the addition or after the addition of the catalyst. If the catalyst is reused repeatedly, the organic sulphur compound in general only needs to be added to the catalyst or to the reaction mixture on the first use. A subsequent addition of the organic sulphur compound is possible, but generally only necessary If fresh catalyst is added in place of somewhat consumed or exhausted catalyst.
Process Details
[0029] The process can be carried out either batchwise or continuously.
[0030] The process may furthermore be applied using either pure α,β-unsaturated ketones or crude α,β~unsaturated ketones, for example from the aldoi condensation, in which such α,β-unsaturated ketones can be obtained from an aldehyde and a methyl ketone.
[0031] The basic substance can be added in an amount from about 0.001 to about
0.025 parts by weight, e.g. , about 0.002 to about 0.01 parts by weight, per part by total weigh, of the α.β-unsaturated ketones and the basic substance.
[0032] The Ni~containing catalyst can be added in an amount from about 0.001 to about 0,1 parts by weight, e.g., about 0.003 to about 0.04 parts by weight, per part by total weight of the α,β-unsaturated ketones and the Ni-containing catalyst.
[0033] The organic sulphur compound can be used in an amount from about 0.0002 to about 0.1 parts by weight, for example about 0.0004 to about 0,075, or about 0.01 to about 0.05 parts by weight, per part by total weight of the α.β-unsaturated ketones and the organic suiphur compound.
[0034] In general, the process can be carried out such that the unsaturated alkyl ketones, the reaction medium comprising an alcohol and water in a mass ratio of about
1 :2 to about 2:1 as described herein, wherein the alcohol comprises at least one C4 -
C10 alcohol as described herein, the basic substance comprising organic amine, the Ni- containing catalyst, and the organic sulphur compound are added to the hydrogenator.
The hydrogenation can be carried out at about 30°C to about 250°C, for example at about 50°C to about 140°C, and at an H2 pressure of about 150 psi to about 1000 psi, for example about 400 psi to about 800 psi. The exothermic hydrogenation reaction can proceed for about 3 hours at about 10Q°C to greater than 99% conversion of the unsaturated alkyl ketone to saturated alkyi ketone in produced crude product, which also comprises trace amounts of amine hydrochloride. The crude product comprising saturated alky! ketone can be filtered to remove Ni-containing catalyst; filtering methods and aids known to those skilled in the art can be used, e.g., filter/body aids can be used. After the Ni~containing catalyst is filtered, a basic substance at a pH of about 8 to about 14, such as sodium hydroxide, potassium hydroxide, calcium hydroxide (for example in the form of slaked time), catdum oκide, potassium carbonate, sodium carbonate, sodium acetate, or mixtures thereof, can be added to the crude product to convert the amine hydrochloride to a chloride, e.g., inorganic chloride, metal chloride (such as sodium chloride), or the like, and an amine, e,g>, tripropylamine. Phases can be separated and the water layer, which contains the inorganic salts, can be discarded. Then alcohol and any remaining water can be distilled out using means known to those skilled in the art. Substantially all of the alcohol can be distilled due to the volatility difference between the alcohol and the saturated alkyl ketone product. A benefit is that the saturated alkyl ketone product can be distilled without the need for a separate aqueous wash to remove salts. The saturated alkyl ketone can men be distilled, using one or more distillation columns, e.g., two distillation columns. Continuous distillation can be used.
[0035] A process according to this invention can comprise preparing a composition consisting essentially of (i) the α,β-unsaturated ketones, (ii) a reaction medium comprising alcohol and water in about a 1:2 to about a 2:1 mass ratio, (iii) organic amine, (iv) Ni-containing catalyst and (v) organic sulphur compound R5-S(=O)n-R4 in which:
R3 and R4 Independently of one another denote straight-chain or branched C1-C12~aikyl, hydroxy- C2-C12-alkyi, carboxy- C1-C12-alkyl or phenyl, and furthermore; R3 and R4 may together represent -CH=CH-CH =CH~, -(CH2)4- -CH2)5- -(CH2)2-S-(CH2)2- or -(CH2)2-O-(CH2)2- R4 may additionally denote hydrogen or CO- C1-C12-alkyl and n assumes tth ealue 0 or 1.
EXAMPLE
[0036] 1 -(4-chlorophenyl)-4,4-dimethylpent- 1 -en-3-one (500 g), 1:1 water-hexanol (90 g), 2,2'thiodiethanol (0.23 g), Raney nickel 2800 (about 2.5 g), and tripropylamine (2.70 g) were added to a 1-L autoclave in a purgebox. After purging three times with nitrogen (50 psig) and three times with hydrogen (200 psig), the autoclave was pressured to 250 psig H2 and heated to 100°G, with 1200 RPM agitation. After reaching 100°C, the pressure was increased to 500 psig and periodically repressured to maintain 500 psig H2. After 1 hour, there was a 99,8% conversion, and after 1.5 hours, there was a 99.9% conversion. The reaction was cooled to 25°C and depresβured. After purging three times with nitrogen (200 psig), the Raney nickel was filtered away using a Celite pre-coat, followed by a water wash (15 mL). 25% NaGH (1.0 g) was added, the mixture was stirred tor 1 hour, and the layers were separated. [0037] It Is to be understood that the reactante and components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to being combined with or coming into contact wfth another substance referred to by chemical name or chemical type {e.g., another reactant, a reaction medium/solvent, or etc.). ft matters not what chemical changes, transformations anqVor reactions, If any, take place fn the resulting mixture or solution or reaction medium as such changes, transformations and/or reactions are the natural result of bringing the specified reactaπts and/or components together under the conditions called for pursuant to this disclosure. Thus the reactants and components are identified as ingredients to be brought together in connection with performing a desired chemical reaction or In forming a mixture to be used in conducting a desired reaction. Accordingly, even though the claims hereinafter may refer to substances, components and/or ingredients in the present tense ("comprises", "is", etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, combined, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure. Whatever transformations, if any. which occur in situ as a reaction is conducted is what the claim is intended to cover. Thus the fact that a substance, component or ingredient may have lost its original identity through a chemical reaction or transformation during the course of contacting, combining, blending or mixing operations, if conducted in accordance with this disclosure and with the application of common sense and the ordinary skill of a chemist is thus wholly immaterial for an accurate understanding and appreciation of the true meaning and substance of this disclosure and the claims thereof.
[0038] While the present invention has been described in terms of one or more preferred embodiments, it is to be understood that other modifications may be made without departing from the scope of the invention, which is set forth in the claims below.

Claims

CLAIMS We Claim:
1. A process for the catalytic hydrogenation of α,β-unsaturated ketones R1CH=CH-CO-R2 in which:
R1 and R2 independently of one another represent straight-chain or branched C1-C12-alkyl or C2-C12-hydrσxyaikyi, straight-chain or branched C2-C12-alkenyl, C3-C8-cycloalkyl C3-C8-cycloalKenyl, C7-C14-aralkyl or C6-C12 aryl, where at least one of R1 and R2 is monosubstituted to trisubstituted by halogen, to give saturated ketones R11-CH2-CH2-CO-R12 in which:
R11 and R12 assume the meaning of R1 and R2, respectively, with the exception that alkenyl and cycloalkenyl are hydrogenated to the respective alkyl or cycloalkyl, wherein the process comprises combining at least (I) a reaction medium comprising an alcohol and water in a mass ratio of about 1:2 to about 2:1 and (ii) the α,β-unsaturated ketones, wherein the alcohol comprises at least one C4-C10 alcohol and the hydrogenation is carried out in the presence of (i) basic substance comprising organic amine, (ii) Ni-containing catalyst and (Hi) organic sulphur compound R3-S(=O)n-R4 in which:
R3 and R4 independently of one another denote straight-chain or branched C1-C12-alkyl, hydroxy- C2-C12-alkyl, carboκy- C1-C12-alkyl or phenyl, and furthermore; R3 and R4 may together represent -CH =CH-CH=CH-, -(CH2)4-. -CH2)5-, -(CH2)2-S-(CH2)S- or -CCH2)2-O-(CH2)2-,R4 may additionally denote hydrogen or CO- C1-C12-alkyl and n assumes the value O or 1.
2. The process of Claim 1 wherein the organic amine comprises tripropylamine,
3. the process of Claim 1 wherein the alcohol comprises hexanol
4. A process for the catalytic hydrogenation of α, β-unsaturated ketones R1-CH=CH~CO-R2 in which: R 1 and R4 independently of one another represent straight-chain or branched C1-C12-alkyl or C2-C12-hydroxyalkyl, straight-chain or branched C2-C12-alkenyl, -3-C8~cycloalkyl, C3-C8-cycloalkenyl, C7-C14-aralkyl or C6-C12-ary!, where at least one of R1 and R2 is monosubstltuted to trisubstituted by halogen, to give saturated ketones R11 -CH2-CH2-CO-R12 in which:
R11 and R12 assume the meaning of R1 and R2, respectively, with the exception that alkenyl and cycloalkenyl are hydrogenated to the respective alky! or cycloalkyl, wherein the process comprises preparing a composition consisting essentially of (i)the α,β-unsaturated ketones, (ii) a reaction medium comprising hexanol and water in about a 1:2 to about a 2:1 mass ratio, (iii) tripropylamine, (iv) Ni-containing catatyst and (v) organic sulphur compound R3-S(=O)n-R4 in which:
R5 and R4 independently of one another denote straight-chain or branched C1-C12-alkyl hydroxy- C2-C12-alkyl, carboxy- C1-C12-alkyl or phenyl, and furthermore; R3 and R4 may together represent ~CH=CH~CH=CH- -(CH2)4-, -CH2)5-, -(CN2)2~S~{CH2)2~ or ~(CH2)2~O~(CH2)2-, R4 may additionally denote hydrogen or CO- C1-C12-alkyl and n assumes the value O or 1
PCT/US2007/083295 2006-11-02 2007-11-01 PROCESSES FOR THE HYDROGENATION OF α,β-UNSATURATED KETONES Ceased WO2008057915A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112062662A (en) * 2020-09-11 2020-12-11 安达市多森新材料科技有限公司 Preparation method of 1- (4-chlorphenyl) -4, 4-dimethyl-3-pentanone

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4940819A (en) * 1988-07-20 1990-07-10 Bayer Aktiengesellschaft Process for the hydrogenation of α,β-unsaturated ketones

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4940819A (en) * 1988-07-20 1990-07-10 Bayer Aktiengesellschaft Process for the hydrogenation of α,β-unsaturated ketones

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112062662A (en) * 2020-09-11 2020-12-11 安达市多森新材料科技有限公司 Preparation method of 1- (4-chlorphenyl) -4, 4-dimethyl-3-pentanone

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