WO2004009523A1 - Procede pour produire des cetals et des ethers d'enol - Google Patents

Procede pour produire des cetals et des ethers d'enol Download PDF

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Publication number
WO2004009523A1
WO2004009523A1 PCT/EP2003/007938 EP0307938W WO2004009523A1 WO 2004009523 A1 WO2004009523 A1 WO 2004009523A1 EP 0307938 W EP0307938 W EP 0307938W WO 2004009523 A1 WO2004009523 A1 WO 2004009523A1
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WO
WIPO (PCT)
Prior art keywords
formula
alcohol
catalyst
compound
reaction mixture
Prior art date
Application number
PCT/EP2003/007938
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German (de)
English (en)
Inventor
Christian Miller
Peter Rudolf
Joaquim Henrique Teles
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO2004009523A1 publication Critical patent/WO2004009523A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C07C41/08—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only to carbon-to-carbon triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/54—Preparation of compounds having groups by reactions producing groups by addition of compounds to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/58—Separation; Purification; Stabilisation; Use of additives

Definitions

  • the invention relates to a process for the preparation of a ketal of the formula I, if desired while simultaneously obtaining an enol ether of the formula II
  • R 1 is alkyl
  • R independently of one another are hydrogen or alkyl
  • m is 0 or 1.
  • EP-B 887 332 and EP-A 887 330 disclose processes for the preparation of ketals of the formula I and / or enol ethers of the formula II by adding an alcohol to a suitable alkyne and / or all in the gas phase on a zinc or cadmium silicate catalyst.
  • the reaction proceeds with high selectivity to the desired compounds.
  • the reaction mixtures always contain small amounts of unreacted alcohol, even if the alcohol is used in a substoichiometric amount to form the ketal.
  • the separation of the alcohol is complex, in particular since the alcohol generally forms an azeotrope with the enol ether, the separation of which requires extractive processes or a two-pressure distillation.
  • GB 1 386 094 describes the preparation of ketals by reacting enols with alcohols in the presence of strongly acidic cation exchangers.
  • the invention is based on the object of specifying a process mentioned at the outset which provides essentially pure ketal of the formula I or easily separable, essentially alcohol-free mixtures of the ketal of the formula I and the enol ether of the formula II.
  • This object is achieved according to the invention by a method in which
  • Step b) optionally with the addition of further alcohol, is subjected to a wet reaction in the liquid phase in the presence of an acidic catalyst.
  • step c) the alcohol contained in the reaction mixture from step a) or in the distillation fraction from step b) reacts essentially quantitatively with the enol ether of formula II present.
  • the alcohol content in the product obtained in step ⁇ ) is generally less than 1% by weight, usually less than 0.5% by weight. So that a sufficient amount of the enol ether of the formula II is available in the mixture for this wet reaction, it is expedient to use in step a) an amount of alcohol which is insufficient for the complete conversion of the alkyne or alien into the ketal of the formula I. Is suitable for.
  • B. a molar ratio of alkyne / allen to alcohol from 0.5 to 2, preferably 0.7 to 1.4.
  • step ⁇ ) further alcohol can be added in step ⁇ ) in order to increase the proportion of the ketal of the formula I in the mixture ultimately obtained or to obtain the ketal of the formula I quantitatively.
  • the relative Vary the proportion of the enol ether of the formula II or the ketal of the formula I in the product mixture obtained, in order, for. B. respond flexibly to fluctuations in demand. If you are only interested in the ketal of the formula I, then in step ⁇ ) an amount of alcohol is added which is necessary for converting the compound of the formula II contained in the reaction mixture or the fraction into the compound of the formula I, otherwise a smaller amount Amount or no alcohol.
  • step a) alkynes of the formula are the starting compounds
  • R 1 is alkyl and the radicals R independently of one another are hydrogen or alkyl.
  • alkyl preferably stands for Cx-C ö alkyl, such as methyl, ethyl, n-propyl, 2-propyl, n-butyl or t-butyl.
  • the process according to the invention is particularly suitable for the preparation of 2,2-dimethoxypropane and optionally 2-methoxypropene, using propyne and / or allen as the alkyne of the formula III or all of the formula IV and methanol as the alcohol.
  • Step a) can be carried out in a manner known per se as described in EP-B 887 332 or EP-A 887 330.
  • a catalyst is used whose active composition contains an oxide and / or silicate of zinc and / or cadmium. They are particularly suitable
  • e takes a value from 0 to the sum of 2a + 2c and the ratio a: ⁇ 1 to 3.5, preferably 1.5 to 2.8, in particular 2 to 2.1, and the ratio f: a 0 to 200, preferably 0 to 2.5, in particular 0 to 0.25;
  • Zinc may be present in an excess or excess of up to 25%, based on the stoichiometric composition; (iii) Catalysts made by applying a decomposable
  • Zinc or cadmium salt of an inorganic oxo acid on amorphous silica and formation of the catalyst in the presence of water, an alcohol or a carboxylic acid are available.
  • the reaction takes place in the presence of the heterogeneously present catalyst in the gas phase either on a fixed bed or in a fluidized bed at temperatures generally from 50 to 400 ° C., preferably 100 to 250 ° C. and particularly preferably 120 to 200 ° C., at pressures in general of 0.1 to 100 bar, preferably 0.8 to 20 bar.
  • the reaction mixture can be diluted with inert gases such as nitrogen, argon, low molecular weight alkanes or olefins for reasons of operational safety and better heat dissipation.
  • inert gases such as nitrogen, argon, low molecular weight alkanes or olefins for reasons of operational safety and better heat dissipation.
  • a propyne / Allen mixture is used, this can e.g. B. be diluted with propene, the content of propyne / allen being less than 70% by weight and typically about 30% by weight. It has proven useful to determine the propyne / allen content in the mixture continuously or periodically, e.g. B. by infrared spectroscopy or determination of the absorption in characteristic wavelength ranges, and the metering of the alcohol, in particular methanol, in accordance with the determined content.
  • reaction gases After leaving the reactor, the reaction gases are usually subjected to partial condensation.
  • the non-condensable components such as the inert gases used in particular, are removed from the system.
  • the gas stream which still contains small amounts of unreacted alkyne of the formula III and / or all of the formula IV can also be recycled in whole or in part to step a).
  • the condensate can be fed directly to step c) or subjected to a distillation in accordance with step b).
  • At least one fraction is obtained in the distillation according to step b). If the alcohol forms an azeotrope with the enol ether of the formula ii, this fraction generally has the composition of the azeotrope within a fluctuation range of 20%.
  • the distillation can be carried out in successive distillation columns in which the fractions mentioned are removed overhead in the order of their volatility. It is also advantageous to use a dividing wall column which contains internals in a region located between the top and bottom of the column in order to avoid cross-mixing of condensate and / or vapors, at least one medium-low fraction, eg. B. the enol ether pure fraction is removed as a side draw.
  • a medium-low fraction eg. B. the enol ether pure fraction is removed as a side draw.
  • the enol ether pure fraction can, if desired, be completely or partially converted to the ketal of the formula I in a manner analogous to step c).
  • heterogeneous catalysts with an acidic character can be used. Which includes:
  • Cation exchangers in acid form e.g. B. Amberlyst A-15,
  • Clay minerals e.g. B. kaolins, bentonites, attapulgite or montmorillonites, which can be acid-activated (so-called lead stoves),
  • Zeolites such as B. zeolite A, mordenite, zeolite ZSM-5, ⁇ -zeolite, zeolite ZSM-22, zeolite MCM-22, zeolite ZBM 11, zeolite ZBM 10, ferrierite, chabasite, faujasite and meta-aluminum phosphates,
  • Carried acids such as B. S ⁇ hsefelklare, phosphoric acid or acetic acid on support materials such.
  • Metal oxides or sulfides such.
  • - metal salts such as B. sulfates, phosphates or halides of magnesium, calcium, strontium, barium, copper, zinc, cadmium, aluminum, iron, cobalt, nickel, chromium, potassium, boron, titanium, tin or silver,
  • a catalyst which is homogeneously soluble in the liquid phase is used.
  • This is secondarily selected from mineral acids, such as hydrochloric acid, sulfuric acid or phosphoric acid, and organic acids, in particular sulfonic acids, such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, or carboxylic acids.
  • any reactors known to the company are suitable for converting a liquid reaction partner - depending on the acid catalyst chosen - in a homogeneous phase or on a heterogeneous catalyst.
  • the temperature is generally 0 to 300 ° C, preferably 50 to 200 ° C; the contact time of the mixture with the acid catalyst 10 -3 to 60 min, preferably 10 ⁇ 2 to 5 min.
  • the reaction mixture obtained in step c) can advantageously be used with an anion exchanger in hydroxyl form, such as, for example, B. Lewatit MP 62, Amberlyte IRA 96.
  • an anion exchanger in hydroxyl form
  • organic bases e.g. B. amines, pyridines or imidazoles, or inorganic bases, for. B. neutralize alkali metal or alkaline earth metal hydroxides, carbonates or hydrogen carbonates.
  • the reaction product obtained in step ⁇ ), which, depending on the selected conditions, contains a mixture of the enol ether of the formula II and the ketal of the formula I or essentially pure ketal, can be worked up in a manner known per se, generally by distillation, preferably using a dividing wall column from which the ketal of the formula I and the enol ether of the formula II are separated from one another as side draws in high purity of e.g. B. more than 99 wt .-% can be obtained.
  • the catalytic conversion of propyne / allen (30% by weight in propene) was carried out in a gas-phase jacketed reactor with a volume of about 5 l at a pressure of 3.5 bar.
  • a heterogeneous catalyst with an active composition of ZnO / SiO 2 (produced according to EP-0 887 330) in the form of shaped bodies (about 4 mm) was used as the catalyst.
  • Methanol and MAPD were gaseous via a separate pre-evaporator. Mis ⁇ her passed into the reactor.
  • the concentration of the propyne / allen mixture used in propene was continuously monitored via an online IR measurement.
  • the reactor temperature was between 180 ° C and 200 ° C and was controlled by a double jacket thermostat.
  • the molar ratio of methanol to MAPD was 1: 1.
  • the reactor outlet was connected to an expansion device, the product stream being continuously expanded into a condenser heated to -10 to 0 ° C.
  • the condensed liquid components were collected at normal pressure and room temperature.
  • the reaction discharge typically showed the following composition:
  • DMP 2,2-dimethoxypropane
  • 1,1-dimethoxypropane 1.1% by weight acetone: 0.8% by weight
  • product mixture 1 This mixture is referred to below as product mixture 1.
  • product mixture 2 This mixture is referred to below as product mixture 2.
  • the product mixture 2 was largely freed from the components methanol and acetone by means of a wash with distilled water.
  • the ratio of organic phase to aqueous phase was about 2: 1 (vol / vol); the washing process was repeated.
  • the organic phase was separated and showed the following composition:
  • product mixture 3 This mixture is hereinafter referred to as product mixture 3.
  • An apparatus consisting of a tubular reactor with a volume of about 100 ml with a held micro-mixing nozzle (volume ⁇ 0.1 ml) was immersed in a thermostattable water bath. The end of the reactor was connected to a neutralization reactor.
  • the neutralization reactor with a volume of about 300 ml was filled with 140 g of basic ion exchanger (Lewatit MP 62).
  • Product mixture 1, 2 or 3 was used as feed 1.
  • Methanol 2 was used as feed 2, which contained 25 mmol / 1 sulfuric acid.
  • the liquid feeds were metered into the mixing nozzle separately at room temperature using HPLC pumps. 600 to 900 g / h of the respective product mixture were metered in. The amount of methanol was varied, various 2 MP / DMP ratios being obtained in the discharge. The discharges were checked and collected by means of chemical analysis with regard to acidity.
  • 900 g / h of the product mixture 1 were metered into the mixture nozzle together with 200 g / h of MeOH / H 2 SO 4 .
  • the temperature of the cooling medium was set at 30 ° C. After neutralization, the overage was collected and analyzed over 4 hours (data in% by weight).

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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 un procédé pour produire des cétals et éventuellement des éthers d'énol, ledit procédé consistant à a) faire réagir un alcyne et/ou un allène avec un alcool dans la phase gazeuse, sur un catalyseur contenant de l'oxyde de zinc et/ou de l'oxyde de cadmium, pour permettre l'obtention d'un mélange réactionnel qui contient de l'alcool n'ayant pas réagi, de l'éther d'énol et du cétal ; b) éventuellement séparer par distillation une fraction contenue dans le mélange réactionnel, contenant l'alcool n'ayant pas réagi et au moins une partie de l'éther d'énol ; et c) soumettre la fraction de l'étape b), éventuellement en ajoutant un alcool supplémentaire, à une réaction ultérieure en phase liquide en présence d'un catalyseur acide.
PCT/EP2003/007938 2002-07-22 2003-07-21 Procede pour produire des cetals et des ethers d'enol WO2004009523A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10233231.2 2002-07-22
DE2002133231 DE10233231A1 (de) 2002-07-22 2002-07-22 Verfahren zur Herstellung von Ketalen und Enolethern

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Publication Number Publication Date
WO2004009523A1 true WO2004009523A1 (fr) 2004-01-29

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PCT/EP2003/007938 WO2004009523A1 (fr) 2002-07-22 2003-07-21 Procede pour produire des cetals et des ethers d'enol

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WO (1) WO2004009523A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004021129A1 (de) 2004-04-29 2005-11-24 Degussa Ag Verfahren zur Isolierung von hochreinem 2-Methoxypropen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0887332A1 (fr) * 1997-06-23 1998-12-30 Basf Aktiengesellschaft Procédé pour l'addition de composés contenant un groupe hydroxyle sur les alcynes ou les allènes
EP0887330A1 (fr) * 1997-06-23 1998-12-30 Basf Aktiengesellschaft Procédé pour l'addition de composés contenant un groupe hydroxyle sur les alcynes ou les allènes
DE19841552A1 (de) * 1998-09-11 2000-03-16 Basf Ag Verfahren zur Herstellung von Enolethern

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0887332A1 (fr) * 1997-06-23 1998-12-30 Basf Aktiengesellschaft Procédé pour l'addition de composés contenant un groupe hydroxyle sur les alcynes ou les allènes
EP0887330A1 (fr) * 1997-06-23 1998-12-30 Basf Aktiengesellschaft Procédé pour l'addition de composés contenant un groupe hydroxyle sur les alcynes ou les allènes
DE19841552A1 (de) * 1998-09-11 2000-03-16 Basf Ag Verfahren zur Herstellung von Enolethern

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