WO2008057915A1 - PROCÉDÉS POUR L'HYDROGÉNATION DE CÉTONES α,β-INSATURÉS - Google Patents

PROCÉDÉS POUR L'HYDROGÉNATION DE CÉTONES α,β-INSATURÉS Download PDF

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Publication number
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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WIPO (PCT)
Prior art keywords
alkyl
branched
chain
straight
ketones
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Application number
PCT/US2007/083295
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English (en)
Inventor
Stephen E. Belmont
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Albemarle Corporation
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Publication date
Application filed by Albemarle Corporation filed Critical Albemarle Corporation
Publication of WO2008057915A1 publication Critical patent/WO2008057915A1/fr

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

Abstract

La présente invention concerne l'hydrogénation catalytique de cétones α,β-insaturés R1-CH=CH-CO-R2 dans lesquels R1 et R2 sont indépendamment l'un de l'autre C1-C12-alkyle ou C2-C12-hydroxyalkyle droit ou ramifié, C2-C12-alcényle droit ou ramifié, C3-C8-cycloalkyle, C3-C8-cycloalcényle, C7-C14-aralkyle ou C6-C12-aryle, l'un au moins de R1 et R2 étant monosubstitué à trisubstitué par halogène, pour donner les cétones saturés correspondants R11-CH2-CH2-CO-R12 dans lesquels R11 et R12 reprennent le rôle de R1 et R2 à cette différence près que l'alcényle et le cycloalcényle sont hydrogénés en alkyle ou cycloalkyle. En l'occurrence, le procédé d'hydrogénation consiste à combiner les cétones α,β-insaturés et un milieu de réaction comprenant un alcool en C4-C10 et de l'eau dans un rapport massique d'environ 1:2 à environ 2:1. L'hydrogénation se fait en présence (i) d'une substance basique comprenant une amine organique, (ii) d'un catalyseur au nickel, et (iii) d'un composé organo-soufré.
PCT/US2007/083295 2006-11-02 2007-11-01 PROCÉDÉS POUR L'HYDROGÉNATION DE CÉTONES α,β-INSATURÉS WO2008057915A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US85611306P 2006-11-02 2006-11-02
US60/856,113 2006-11-02
US98032107P 2007-10-16 2007-10-16
US60/980,321 2007-10-16

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112062662A (zh) * 2020-09-11 2020-12-11 安达市多森新材料科技有限公司 一种1-(4-氯苯基)-4,4-二甲基-3-戊酮的制备方法

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 (zh) * 2020-09-11 2020-12-11 安达市多森新材料科技有限公司 一种1-(4-氯苯基)-4,4-二甲基-3-戊酮的制备方法

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