WO2008057919A1 - Procédés d'hydrogénation de cétones α,β-insaturées - Google Patents

Procédés d'hydrogénation de cétones α,β-insaturées Download PDF

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Publication number
WO2008057919A1
WO2008057919A1 PCT/US2007/083302 US2007083302W WO2008057919A1 WO 2008057919 A1 WO2008057919 A1 WO 2008057919A1 US 2007083302 W US2007083302 W US 2007083302W WO 2008057919 A1 WO2008057919 A1 WO 2008057919A1
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WIPO (PCT)
Prior art keywords
alkyl
alcohol
product
ketones
basic substance
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Application number
PCT/US2007/083302
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English (en)
Inventor
Hao V. Phan
Stephen E. Belmont
John K. Roberg
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Albemarle Corporation
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Publication date
Application filed by Albemarle Corporation filed Critical Albemarle Corporation
Publication of WO2008057919A1 publication Critical patent/WO2008057919A1/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, butanol, 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. It is also disclosed that in a preferred variant, the process is carried out by the addition of a basic substance at a pH of 8 - 14. Numerous basic substances are disclosed, including basic substances that comprise organic amine and those that do not comprise organic amine.
  • 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 tetrahydrofuran) to about 40 wt% (120 g of ketones; 180 g of methanol).
  • the weight percent of the Ni-containing catalyst as to the total weight of the catalyst and the ⁇ , ⁇ -unsaturated ketones to be hydrogenated ranges from about 4 wt% (5.6 g of Ni-containing catalyst; 139 g of ⁇ , ⁇ -unsaturated ketone) to about 14 wt% (10 g of Ni-containing catalyst; 63 g of ⁇ , ⁇ -unsaturated ketone).
  • the weight percent of the organic sulphur compound as to the total weight of the organic sulphur compound and the ⁇ , ⁇ -unsaturated ketones to be hydrogenated ranges from about 0.01 wt% (0.015 g of organic sulphur compound; 120 g of ⁇ , ⁇ -unsaturated ketone) to about 0.71 wt% (0.45 g of organic sulphur compound; 63 g of ⁇ , ⁇ -unsaturated ketone).
  • At least about 90 volume percent, at least about 99 volume percent, or substantially all of the Ni-containing catalyst can be filtered from the product.
  • At least about 90 volume percent, at least about 99 volume percent, or substantially all of the alcohol can be distilled from the end product.
  • At least about 90 volume percent, at least about 99 volume percent, or substantially all of the water can be distilled from the end product.
  • At least about 90 volume percent, at least about 95 volume percent or substantially all of the inorganic chloride can be filtered from the end product.
  • the combining can be done in amounts such that the wt% of the organic sulphur compound based on the total weight of the organic sulphur compound and the ⁇ , ⁇ -unsaturated ketones is less than about 0.50 wt% and/or in amounts such that the wt% of the Ni-containing catalyst based on the total weight of the Ni-containing catalyst and the ⁇ , ⁇ -unsaturated ketones is less than about 4 wt%.
  • the first basic substance can comprise organic amine and the ⁇ , ⁇ -unsaturated ketones and alcohol can be combined in amounts such that the wt% of the ⁇ , ⁇ -unsaturated ketones based on the total weight of the ⁇ , ⁇ -unsaturated ketones and the alcohol is at least about 60 wt%.
  • compositions and methods wherein the composition is an activator composition.
  • C 1 -C 12 -alkyl can be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, hexyl, octyl, decyl or dodecyl; C 1 -C 6 -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 6 -alkyl and C 1 -C 4 -alkyl are included.
  • Straight-chain or branched C 2 -C 12 -alkenyl can be, for example, vinyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl, octenyl, decenyl or dodecenyl;
  • C 3 -Ca-cycloalkyl can be, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl which can be substituted by one or two methyl or ethyl groups; substituted or unsubstituted cyclopropyl, cyclopentyl or cyclohexyl are included.
  • C 3 -C 8 -cycloalkenyl can be, for example, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl or cyclooctenyl.
  • C 7 -C 14 -aralkyl can be, for example, benzyl, phenylethyl, naphthylmethyl, naphthylethyl, biphenyl-methyl or biphenyl-ethyl.
  • C 6 -C 12 -aryl can be, for example, phenyl, e.g., 4-chlorophenyl, or naphthyl or biphenyl.
  • At least one of R 1 and R 2 in the ⁇ , ⁇ -unsaturated ketone is monosubstituted to trisubstituted 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 methoxy or ethoxy groups, and also the hydroxyl group.
  • R 1 and R 2 independently of one another denote straight-chain or branched C 1 -C 6 -alkyl
  • ketones are 5-halophenyl-2,2-dimethylpent-4-en-3-ones, particularly 5-(4-chlorophenyl)-2,2-dimethyl-pent-4-en-3-one, and
  • All ⁇ , ⁇ -unsaturated ketones are in each case distinguished by at least one substituent which is substituted by halogen.
  • ⁇ , ⁇ -unsaturated ketones to be used can be prepared via aldol condensation, as will be familiar to those skilled in the art.
  • Alcohol used in processes of this invention can be any suitable alcohol or mixture of alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, sec butanol and/or mixtures comprising methanol, ethanol, propanol, isopropanol, butanol, or sec butanol.
  • Basic substances useful in this invention can comprise sodium hydroxide, potassium hydroxide, calcium hydroxide (for example in the form of slaked lime), calcium oxide, potassium carbonate, sodium carbonate, sodium acetate, and/or organic amines.
  • Suitable organic amines include aliphatic amines, such as triethylamine or tripropylamine, and heterocyclic amines.
  • the basic substances may, if they are water-soluble, be used as aqueous solution or as solid.
  • 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 O3, pumice, carbon and other supports known to those skilled in the art.
  • Raney catalysts such as Raney nickel, Raney nickel-iron, 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. [0033] The process can furthermore be applied using either pure ⁇ , ⁇ -unsaturated ketones or crude ⁇ , ⁇ -unsaturated ketones, for example from the aldol condensation, in which such ⁇ , ⁇ -unsaturated ketones can be obtained from an aldehyde and a methyl ketone.
  • the ⁇ , ⁇ -unsaturated ketones and alcohol can be added in amounts such that the wt% of the ⁇ , ⁇ -unsaturated ketones based on the total weight of the ⁇ , ⁇ -unsaturated ketones and the alcohol is at least about 60 wt%.
  • 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 weight of the ⁇ , ⁇ -unsaturated ketones and the basic substance.
  • 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, e.g., such that the weight percent of the Ni-containing catalyst based on the total weight of the Ni- containing catalyst and the ⁇ , ⁇ -unsaturated ketones to be hydrogenated is less than about 4 wt%.
  • the organic sulphur compound can be used in an amount from 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 weight of the total weight of the ⁇ , ⁇ -unsaturated ketones and the organic sulphur compound.
  • the organic sulphur compound can be used in amounts such that the wt% of the organic sulphur compound based on the total weight of the organic sulphur compound and the ⁇ , ⁇ -unsaturated ketones to be hydrogenated is less than about 0.50 wt%, or such that the wt% of the organic sulphur compound based on the total weight of the organic sulphur compound and the ⁇ , ⁇ -unsaturated ketones is from about 0.04 wt% to about 0.50 wt%.
  • the process can be carried out such that the unsaturated alkyl ketone, the alcohol, the basic substance, 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 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 100°C to greater than 99% conversion of the unsaturated alkyl ketone to saturated alkyl ketone in produced crude product, which also comprises trace amounts of amine hydrochloride.
  • the crude product comprising saturated alkyl 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 lime), calcium oxide, 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., triethylamine.
  • alcohol and/or any water present 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 an aqueous wash to remove salts.
  • the saturated alkyl ketone can then be distilled, using one or more distillation columns, e.g., two distillation columns. Continuous distillation can be used.
  • Example 1 1-(4-chlorophenyl)-4,4-dimethylpent-1-en-3-one (500 g), methanol (81 g), 2,2'-thiodiethanol (0.21 g), Raney nickel 2800 (3.0 g), and triethylamine (1.85 g) were added to a 1-L autoclave in a purgebox. After purging with nitrogen and hydrogen, the autoclave was pressured to 300 psig H2 and heated to 100 C, with 1800 RPM agitation. After reaching 100°C, the pressure was increased to 500 psig and periodically repressured to maintain 500 psig H2.
  • Example 2 (comparative example):
  • the reaction was cooled to 25°C, depressured, and purged with nitrogen, after which the Raney nickel was filtered off.
  • the methanol was stripped off on a rotovap, and the neat product was extracted with 2 g 85% H 3 PO 4 diluted in 200 ml. of water. The residual water was stripped out under vacuum, and the reaction mixture refiltered to remove traces of inorganic solids. Purification was by distillation.
  • the weight percent of the Ni-containing catalyst based on the total weight percent of the Ni-containing catalyst and the ketones to be hydrogenated is about 3.3 wt%.
  • Example 1 after filtering of the Raney nickel, addition of basic substance and distillation of reaction medium/solvent and water eliminated the need for the aqueous wash, such as the aqueous H 3 PO 4 extraction of Example 2.
  • the benefits can be savings in throughput as there is no need to fill a reactor with the aqueous wash solution, savings in waste disposal costs, and savings in cycle time, and can be significantly advantageous from an economic standpoint.
  • 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

L'invention concerne l'hydrogénation catalytique de cétones α,β-insaturées R1 -CH=CH-CO-R2, R1 et R2 représentant indépendamment l'un de l'autre un alkyle en C1-C12 ou un hydroxyalkyle en C2-C12 linéaire ou ramifié ; un alcényle en C2-C12 linéaire ou ramifié, un cycloalkyle en C3-C8, un cycloalcényle en C3-C8, un aralkyle en C7-C14 ou un aryle en C6-C12, au moins un radical parmi R1 et R2 étant monosubstitué à trisubstitué par un halogène, pour obtenir les cétones saturés respectives R11-CH2-CH2-COR12, R11 et R12 ayant les significations de R1 et R2 à l'exception que l'alcényle et le cycloalcényle sont hydrogénés en alkyle ou cycloalkyle respectivement, ledit procédé d'hydrogénation comprenant le mélange de cétones α,β-insaturées et d'alcools ; l'hydrogénation étant réalisée en présence de (i) une substance basique, (ii) un catalyseur contenant du Ni et (iii) un composé de soufre organique pour obtenir un produit comprenant les cétones saturées, le catalyseur contenant du Ni et l'alcool et/ou de l'eau, et le procédé comprenant également la filtration d'au moins une partie du catalyseur contenant du Ni du produit pour obtenir un produit filtré ; l'ajout d'une substance basique au produit filtré pour obtenir un produit final comprenant les cétones saturées, l'alcool et/ou de l'eau, un chlorure inorganique et une amine ; la distillation d'au moins une partie de l'alcool et d'au moins une partie de l'eau du produit final ; et la filtration d'au moins une partie du chlorure inorganique du produit final.
PCT/US2007/083302 2006-11-02 2007-11-01 Procédés d'hydrogénation de cétones α,β-insaturées WO2008057919A1 (fr)

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US60/856,085 2006-11-02

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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

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