CA2260814A1 - Process for preparing alkyne diols or mixtures of alkyne diols with alkyne monools - Google Patents
Process for preparing alkyne diols or mixtures of alkyne diols with alkyne monools Download PDFInfo
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- CA2260814A1 CA2260814A1 CA002260814A CA2260814A CA2260814A1 CA 2260814 A1 CA2260814 A1 CA 2260814A1 CA 002260814 A CA002260814 A CA 002260814A CA 2260814 A CA2260814 A CA 2260814A CA 2260814 A1 CA2260814 A1 CA 2260814A1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
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Abstract
The invention concerns a process for preparing alkyne diols or mixtures of alkyne diols with alkyne monools by reacting acetylene with more than equimolar amounts of ketones and/or aldehydes in the presence of an alkaline compound, the alkaline compound being used in a molar amount which is less than half the molar amount of the ketone and/or aldehyde to be reacted, in the presence of ammonia and/or at least one reactive primary amine.
Description
PROCESS FOR PREPARING ALKYNE DIOLS OR MIXTURES OF
ALKYNE DIOLS WITH ALKYNE MONOOLS
The present invention relates to a process for preparing alkynediols or mixtures of alkynediols with alkynemonools by reacting acetylene with more than equimolar amounts of ketones and/or aldehydes in the presence of an alkaline compound.
Alkynediols and mixtures of alkynediols with alkynemonools are valuable intermediates in the preparation of, for example, low-foam surfactants, pyrethroids, electroplating auxiliaries or peroxides.
Processes for preparing alkynediols or alkynemonools have been known for a long. In this connection, as a rule the preparation of alkynediols is considerably more elaborate than the preparation of alkynemonools. This is done by reacting ketones or aldehydes with acetylene, with stoichiometric use of a basic compound. The basic compound normally employed is a potassium alcoholate or potassium hydroxide. At least one mol of potassium hydroxide or alcoholate is necessary for reacting 2 mol of ketone or aldehyde with one mol of acetylene. A solvent is normally used for this reaction. There are various prior art embodiments of these processes which differ in the solvent, in the se~uence of addition of ketone or aldehyde, acetylene and the basic condensing agent, and in the nature of the basic condensing agent.
Thus, DE-A-20 08 675 discloses the use of potassium alcoholates of primary or secondary alcohols in hydrocarbon solvents.
DE-A-20 47 446 discloses the conversion of alkynemonools into alkynediols by condensing the monools with aldehydes or ketones.
US-A-21 63 720 discloses the reaction of ketones with solid alkali metal hydroxides and further treatment of the resulting mixture with acetylene at a temperature which avoids base-induced condensation of ketones. The ketone may be present in excess and virtually act as solvent, but this excess may also be replaced by another solvent such as ether. At least a stoichiometric amount of alkali metal hydroxide, based on the ketone to be reacted, is likewise employed. EP-A-285 755 discloses the use of alkyl tert-butyl ethers as solvents in order to reduce the frequently high viscosity of the previously disclosed reaction mixtures.
EP-A-285 755 points out, in column 1, lines 18-20, as does DE-A-20 47 446 in col D 1, line 27 to column 2, line 4, in particular the difficulty of preparing alkynediols, especially the bis-tertiary alkynediols produced by reaction of ketones with acetylene, compared with the preparation of the alkynemonools.
US-A 3 082 260 discloses the preparation of alkynemonools by 5 condensing acetylene with ketones or aldehydes in liquid ~mmo~ia as solvent using about 5 - 25 mol% of alkali metal hydroxide, based on the ketone or aldehyde, as catalyst. The subsequent distillation of the monools results in a small residue which, apart from by-products, also contains the corresponding diol.
US-A 32 83 014 discloses the preparation of alkynemonools with avoidance of the formation of alkynediols by reacting ketones with acetylene in an aqueous solution of alkali metal hydroxide 15 as catalyst. The alkali metal hydroxide is in this case used in an amount of 0.5 - 10 mol% based on the ketone. The solvent is ;~ mmon; a.
The main disadvantage of the known processes for preparing 20 alkynediols is the stoichiometric use of the alkaline compound.
The potassium alcoholates or potassium. hydroxide which are preferably employed are relatively costly, must be employed essentially anhydrous and, after the usual aqueous workup of the discharge from the reaction, result in the form of a dilute 25 aqueous solution of potassium hydroxide. Although it is technically possible to work up the base by evaporating the solution, purifying the residue and, where apppropriate, converting it into an alcoholate, this is comparatively complicated, time-consuming and, in particular, uneconomic owing 30 to the high energy input for evaporating off the water.
It i8 an object of the present invention to find a process for preparing alkynediols or mixtures of alkynediols with alkyn~mo~ools by reacting ketones and/or aldehydes with acetylene 35 which does not require stoichiometric use of alkali metal hydroxide or alcoholate.
We have found that this object is achieved by a process for preparing alkynediols or mixtures of alkynediols with 40 alkynPmonools by reacting acetylene with more than equimolar amounts of ketones and/or aldehydes in the presence of an alkaline compound, wherein the molar amount of the alkaline compound used is less than half the molar amount of the ketone and/or aldehyde to be reacted, in the presence of ~mmQnia and/or 45 at least one reactive primary amine.
, . . .
Suitable catalyzing alkaline compounds are compounds of sodium, potassium, rubidium and cesium, in particular of sodium and potassium. Alkali metal hydroxides and/or alkali metal alcoholates are preferably employed. Examples of catalysts which 5 can be used according to the invention, alone or in a mixture, are sodium hydroxide and potassium hydroxide, sodium methanolate, sodium ethanolate, sodium propanolate, sodium isopropanolate, sodium butanolate, sodium isobutanolate, sodium tert-butanolate and sodium tert-pentoxide, potassium methanolate, potassium 10 ethanolate, potassium propanolate, potassium isopropanolate, potassium butanolate, potassium isobutanolate, potassium tert-butanolate and potassium tert-pentoxide. The potassium compounds are preferably used, particularly preferably potassium hydroxide and potassium methanolate.
The alkaline compound can be used in solid form or as solution or suspension in a solvent or suspending agent. As a rule, solutions or suspensions are easier to handle and easier to meter in accurate amounts than are solids, which is why use of a solution 20 or suspension of the alkaline compound is generally preferred to use of the alkaline compound as solid. In general, the difference between solution and suspension is not marked and, depending on the solubility of the alkaline compound in the chosen solvent, part of the alkaline compound can be dissolved and the rem~;n~er 25 can be present in suspension. The choice of this solvent or suspending agent is in general not critical and is subject only to the condition that it must be inert towards the reactants.
Examples of solvents or suspending agents which can be employed for the alkaline compound are monoalcohols such methanol, 30 ethanol, n-propanol, isopropanol, l-butanol, 2-butanol, 2-methyl-1-propanol, tert-butanol or diols such as glycol, propylene glycol, alkynemonools, alkynediols or mixtures of alkynediols with alkynemonools like the products of the process according to the invention. Water can likewise be employed as 35 solvent, in which case the concentration of the alkaline compound in water is preferably chosen so that the amount of water which is finally present in the actual reaction mixture is not more than 10 % of the weight of the reaction mixture. Ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, methyl tert-butyl 40 ether or ethyl tert-butyl ether can be used just as much as hydrocarbons, for example pentane, hexane, heptane, cyclopentane or cyclohexane or mixtures thereof. It is likewise possible to use strongly polar aprotic solvents, examples thereof being dimethyl sulfoxide (DMSO), sulfolane and N-methylpyrrolidone.
45 Li~uid ~mmnn;a can likewise be used. The reaction product is .. ~ ~.. .. .
preferably employed as solvent or suspending agent for the alkaline compound.
The molar amount of alkaline compound employed in the reaction 5 mixture is less than half the molar amount of the ketone and/or aldehyde to be reacted. In general, 0.1 - 5 mol% of alkaline compound, based on the ketone and/or aldehyde to be reacted, is added. Preferably 0.2 -1 mol% of alkaline compound, based on the ketone and/or aldehyde to be reacted, is added. Although it is 10 technically possible to use larger amounts of alkali, it generally becomes increasingly less economically advantageous as the amount of alkali increases, because of the increasing alkali consumption and/or the cost of working it up again. It is likewise technically possible to use smaller amounts of alkali, 15 but this is generally not econom;cally advantageous because of the long reaction times.
The reaction mixture contains Ammo~;a and/or at least one 20 reactive primary amine as cocatalyst. The amount of cocatalyst is generally at least equimolar with the amount of alkaline compound(s) employed. Preferably, the amount of Ammonia or primary amine employed is at least twice that equimolar with the amount of alkaline compound(s) employed, and is particularly preferably at least five times. It is possible to employ as primary amine, for example, amino-substituted alkanes having 1 to 4 carbon atoms.
Examples of primary amines which can be employed according to the 30 invention are low molecular weight alkylamines, eg. alkylAm;nes having 1 to 4 carbon atoms such as methylamine, ethylamine, 1-propylamine, 2-propylamine, 1-butylamine, 2-butylamine, 2-methyl-1-propylamine and 1,1-dimethylethylamine. Mixtures of at least two amines or mixtures of at least one amine with ~mmon;a 35 can likewise be used. Ammo~ia and/or methylamine are preferably employed, very particularly preferably Ammonia The process can in principle be carried out without any other solvent. The process can likewise be carried out only in the 40 presence of the solvent or suspending agent for the solution or suspension of the alkaline compound when the alkaline compound is added in a solvent or suspending agent. However, the process can also be carried out in the presence of a solvent which is specifically used for the reaction and the choice of which is 45 subject to the same condition as the choice of the solvent or suspending agent for the alkaline compound. Suitable examples of solvents in this case are in addition all solvents which dissolve . _ , acetylene, such as N-methylpyrrolidone, dioxane, dimethyl sulfoxide (DMSO), sulfolane or THF, and ~mm~n;a or primary amines. The primary amines which can be used as solvents can be chosen like the primary amines which can be used as cocatalyst.
5 A~nn i ~ iS preferably employed as solvent.
The ketones or aldehydes employed for the purpose of the present invention are compounds of the formula I:
o ~ Il ~ C ~ (I) Rl R2 Confirming the choice of the radicals, there is no restriction per se so that all inert organic radicals, for example those having 1 to 50 carbon and/or heteroatoms, are suitable. For 20 example, Rl and R2 in this formula are, independently of one another, alkyl, alkenyl, aryl, alkylaryl, arylalkyl or arylalkenyl radicals which can be straight-chain or branched, open-chain or cyclic, substituted or unsubstituted. The term aryl means, for example, phenyl or naphthyl. In place of.aryl 25 radicals, it is also possible for heteroaromatic groups to be present, such as heteroaromatic rings which may contain one or more heteroatoms such as nitrogen, oxygen or sulfur. It is equally possible for the radicals to be aliphatic or cycloaliphatic, in particular both saturated and olefinically 30 unsaturated. These aliphatic or cycloaliphatic radicals may also contain one or more heteroatoms such as nitrogen, oxygen or sulfur. In addition, the radicals Rl and R2 may be connected together and form, together with the carbonyl group, a ring system which may also be olefinically unsaturated and may also 35 contain heteroatoms such as nitrogen, oxygen or sulfur. All said radicals may have inert substituents such as alkyl or alkoxy radicals or halogen atoms such as fluorine, chlorine, bromine or iodine. R2 is hydrogen in the case of aldehydes, and both Rl and R2 are hydrogen in the specific case of formaldehyde.
Examples of ketones which may be mentioned are acetone, methyl isobutyl ketone, methyl ethyl ketone, methylhept~nsne, methylheptenone, methyl norbornyl ketone, trimethylcyclopent~no~e, acetophenone, benzoph~none, methyl vinyl 45 ketone and ionone.
Examples of suitable aldehydes are formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, iso-butyraldehyde, 2-ethylhexAn~l, benzaldehyde or substituted benzaldehydes such as 4-tert-butylbenzaldehyde.
It is generally expedient to employ only one ketone or aldehyde, but it is possible in principle just as well to employ mixtures of at least two ketones, mixtures of at least two aldehydes or else mixtures of at least one ketone with at least one aldehyde.
10 In this case, mixtures of products are obtained and may be subsequently worked up together and used further as mixtures or be fractionated into the individual components during the workup.
It is likewise possible for the product mixture which results in the reaction of acetylene with various ketones and/or aldehydes 15 to be fractionated, eg. by physical methods, for example by distillation, into cuts or fractions, ie. to obtain not the individual compounds but new mixtures of products whose composition differs from that of the original mixture, and for these cuts or fractions to be used further.
The concentrations of the reactants and the amount of solvent can be chosen relatively freely according to the requirements of satisfactory operation of the process (the criteria may be, for 25 example, the viscosity of the reaction mixture, the reguired, eco~omically optimal space-time yield, the selectivity or the - amount of acetylene which can be handled safely). The amounts of ketone, aldehyde, acetylene and solvent optimal for the products required in the individual case and the precursors employed 30 therefor may vary in each case. However, to obtain a satisfactory yield of alkynediols, it is necessary for the molar ratio of ketone and/or aldehyde to acetylene to be greater than 1:1. Is is preferably at least 1.2 : 1. If it is required to prepare pure alkynediols or a mixture in which alkynediols predom;nAte over 35 monools, this ratio is preferably 1.5 : 1 and, particularly preferably, at least 2 : 1. The ratio can then be, for example, 2 : 1, 4 : 1 or 6 : 1. If a smaller proportion of ketone and/or aldehyde is employed, part of the acetylene does not react to give alkynediol but, on the contrary, for this part the reaction 40 stays at the stage of the alkynemonool, ie. of a 1-substituted or 1,1-disubstituted propargyl alcohol. Mixtures of alkynediol and alkyne~onool are obtained in this case. Experience has shown that large amounts of Ammon;a as solvent likewise lead to an increased formation of propargyl alcohol. Ratio by volume of ~mmon;a to the 45 ketone or aldehyde employed should therefore generally not exceed 30 : 1 to obtain an optimal yield of pure alkynediols, and it should preferably be below 20 : 1, in particular below 10 : 1.
It may in fact be advantageous for the ratio by volume to be below 2:1 or 1:1.
If it is wished to prepare a mixture of alkynPmonool and 5 alkynediol, it is also possible to use a larger excess of Ammon;a, for example a ratio by volume to the ketone or aldehyde employed of below 50 : 1, preferably below 40 : 1.
.
10 The temperature of the reaction for preparing pure alkynediols or mixtures in which the alkynediol content predominates is generally from 10 ~C to 140 ~C, preferably from 40 to 120 ~C and, particularly preferably, from 50 to 100 ~C. If the lower temperature is chosen, for example below 50 ~C, part of the acetylene does not react to give alkynediol but, on the contrary, for this part the reaction stays at the stage of the propargyl alcohol. Mixtures of alkynediol and propargyl alcohol are obtained in this case.
20 The process can in principle be carried out under atmospheric pressure or elevated pressure. If Ammon;a or another volatile substance is chosen as solvent, it will generally be expedient to choose a pressure such that the solvent is in liquid form at the reaction temperature. In the case of Ammonia as solvent, an 25 example of a pressure which is possible and suitable is 20 bar.
The process can be carried out, for example, in such a way that the ketone or aldehyde to be reacted is saturated with acetylene.
The alkaline compound and the cocatalyst and, if required, the 30 solvent are then added and the mixture is reacted in a reactor.
The reactor used is generally not critical and can be, for example, a tube reactor, a loop reactor, a stirred vessel reactor or else a cascade of stirred vessel reactors. The mixture can be worked up in a conventional way after the reaction is complete.
35 If a volatile solvent is used, this is evaporated off and the product is then obtained by distillation, for example. The reaction mixture or the residue after removal of the solvent can be washed with water and the phases be separated to remove the alkaline catalyst before the product is obtained. It is equally 40 possible for any water present in the reaction mixture to be removed, if this interferes with the further workup, by phase separation before removal of a solvent or obtA;ning the product.
.. . . .
Examples A liquid mixture of acetone with acetylene, liquid ~mmonia and, each hour, 6 ml of a 10 % by weight solution of potassium 5 hydroxide in methanol were conveyed under pressure into a heated tubular reactor (diameter 9 mm, length 500 mm) which was operated with a pump as loop reactor with external liquid recycling. The product was removed from the circulation under pressure control so that the pressure in the reactor was at a constant 20 bar.
10 After constituents which were volatile at room temperature and atmospheric pressure had evaporated off, the product was analyzed by gas chromatography, and the amounts of methylbutynol (MBI) and 2,5-dimethyl-3-hexyne-2,5-diol (DMHD) produced, and the amount of unconsumed acetone were determined. The acetone conversion and 15 the yields of MBI and DMHD were calculated therefrom.
The results are shown in Table 1.
20 Examples 1 to 3 show that the alkynediol can be prepared with excellent selectivity, ie. without measurable production of alkynemonool, with the process according to the invention.
Examples 4 and 5 show embodiments in which mixtures of the 25 alkynediol and the alkyn~ ool are obtained.
Example 6 is a comparative example similar to US-A 3 082 260, which shows that with a reaction procedure which differs in several points from that according to the invention (temperature 30 too low, amount of ~mmo~;a and excess of acetylene too high), as disclosed in US-A 3 082 260, exclusively the alkynemonool is produced.
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ALKYNE DIOLS WITH ALKYNE MONOOLS
The present invention relates to a process for preparing alkynediols or mixtures of alkynediols with alkynemonools by reacting acetylene with more than equimolar amounts of ketones and/or aldehydes in the presence of an alkaline compound.
Alkynediols and mixtures of alkynediols with alkynemonools are valuable intermediates in the preparation of, for example, low-foam surfactants, pyrethroids, electroplating auxiliaries or peroxides.
Processes for preparing alkynediols or alkynemonools have been known for a long. In this connection, as a rule the preparation of alkynediols is considerably more elaborate than the preparation of alkynemonools. This is done by reacting ketones or aldehydes with acetylene, with stoichiometric use of a basic compound. The basic compound normally employed is a potassium alcoholate or potassium hydroxide. At least one mol of potassium hydroxide or alcoholate is necessary for reacting 2 mol of ketone or aldehyde with one mol of acetylene. A solvent is normally used for this reaction. There are various prior art embodiments of these processes which differ in the solvent, in the se~uence of addition of ketone or aldehyde, acetylene and the basic condensing agent, and in the nature of the basic condensing agent.
Thus, DE-A-20 08 675 discloses the use of potassium alcoholates of primary or secondary alcohols in hydrocarbon solvents.
DE-A-20 47 446 discloses the conversion of alkynemonools into alkynediols by condensing the monools with aldehydes or ketones.
US-A-21 63 720 discloses the reaction of ketones with solid alkali metal hydroxides and further treatment of the resulting mixture with acetylene at a temperature which avoids base-induced condensation of ketones. The ketone may be present in excess and virtually act as solvent, but this excess may also be replaced by another solvent such as ether. At least a stoichiometric amount of alkali metal hydroxide, based on the ketone to be reacted, is likewise employed. EP-A-285 755 discloses the use of alkyl tert-butyl ethers as solvents in order to reduce the frequently high viscosity of the previously disclosed reaction mixtures.
EP-A-285 755 points out, in column 1, lines 18-20, as does DE-A-20 47 446 in col D 1, line 27 to column 2, line 4, in particular the difficulty of preparing alkynediols, especially the bis-tertiary alkynediols produced by reaction of ketones with acetylene, compared with the preparation of the alkynemonools.
US-A 3 082 260 discloses the preparation of alkynemonools by 5 condensing acetylene with ketones or aldehydes in liquid ~mmo~ia as solvent using about 5 - 25 mol% of alkali metal hydroxide, based on the ketone or aldehyde, as catalyst. The subsequent distillation of the monools results in a small residue which, apart from by-products, also contains the corresponding diol.
US-A 32 83 014 discloses the preparation of alkynemonools with avoidance of the formation of alkynediols by reacting ketones with acetylene in an aqueous solution of alkali metal hydroxide 15 as catalyst. The alkali metal hydroxide is in this case used in an amount of 0.5 - 10 mol% based on the ketone. The solvent is ;~ mmon; a.
The main disadvantage of the known processes for preparing 20 alkynediols is the stoichiometric use of the alkaline compound.
The potassium alcoholates or potassium. hydroxide which are preferably employed are relatively costly, must be employed essentially anhydrous and, after the usual aqueous workup of the discharge from the reaction, result in the form of a dilute 25 aqueous solution of potassium hydroxide. Although it is technically possible to work up the base by evaporating the solution, purifying the residue and, where apppropriate, converting it into an alcoholate, this is comparatively complicated, time-consuming and, in particular, uneconomic owing 30 to the high energy input for evaporating off the water.
It i8 an object of the present invention to find a process for preparing alkynediols or mixtures of alkynediols with alkyn~mo~ools by reacting ketones and/or aldehydes with acetylene 35 which does not require stoichiometric use of alkali metal hydroxide or alcoholate.
We have found that this object is achieved by a process for preparing alkynediols or mixtures of alkynediols with 40 alkynPmonools by reacting acetylene with more than equimolar amounts of ketones and/or aldehydes in the presence of an alkaline compound, wherein the molar amount of the alkaline compound used is less than half the molar amount of the ketone and/or aldehyde to be reacted, in the presence of ~mmQnia and/or 45 at least one reactive primary amine.
, . . .
Suitable catalyzing alkaline compounds are compounds of sodium, potassium, rubidium and cesium, in particular of sodium and potassium. Alkali metal hydroxides and/or alkali metal alcoholates are preferably employed. Examples of catalysts which 5 can be used according to the invention, alone or in a mixture, are sodium hydroxide and potassium hydroxide, sodium methanolate, sodium ethanolate, sodium propanolate, sodium isopropanolate, sodium butanolate, sodium isobutanolate, sodium tert-butanolate and sodium tert-pentoxide, potassium methanolate, potassium 10 ethanolate, potassium propanolate, potassium isopropanolate, potassium butanolate, potassium isobutanolate, potassium tert-butanolate and potassium tert-pentoxide. The potassium compounds are preferably used, particularly preferably potassium hydroxide and potassium methanolate.
The alkaline compound can be used in solid form or as solution or suspension in a solvent or suspending agent. As a rule, solutions or suspensions are easier to handle and easier to meter in accurate amounts than are solids, which is why use of a solution 20 or suspension of the alkaline compound is generally preferred to use of the alkaline compound as solid. In general, the difference between solution and suspension is not marked and, depending on the solubility of the alkaline compound in the chosen solvent, part of the alkaline compound can be dissolved and the rem~;n~er 25 can be present in suspension. The choice of this solvent or suspending agent is in general not critical and is subject only to the condition that it must be inert towards the reactants.
Examples of solvents or suspending agents which can be employed for the alkaline compound are monoalcohols such methanol, 30 ethanol, n-propanol, isopropanol, l-butanol, 2-butanol, 2-methyl-1-propanol, tert-butanol or diols such as glycol, propylene glycol, alkynemonools, alkynediols or mixtures of alkynediols with alkynemonools like the products of the process according to the invention. Water can likewise be employed as 35 solvent, in which case the concentration of the alkaline compound in water is preferably chosen so that the amount of water which is finally present in the actual reaction mixture is not more than 10 % of the weight of the reaction mixture. Ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, methyl tert-butyl 40 ether or ethyl tert-butyl ether can be used just as much as hydrocarbons, for example pentane, hexane, heptane, cyclopentane or cyclohexane or mixtures thereof. It is likewise possible to use strongly polar aprotic solvents, examples thereof being dimethyl sulfoxide (DMSO), sulfolane and N-methylpyrrolidone.
45 Li~uid ~mmnn;a can likewise be used. The reaction product is .. ~ ~.. .. .
preferably employed as solvent or suspending agent for the alkaline compound.
The molar amount of alkaline compound employed in the reaction 5 mixture is less than half the molar amount of the ketone and/or aldehyde to be reacted. In general, 0.1 - 5 mol% of alkaline compound, based on the ketone and/or aldehyde to be reacted, is added. Preferably 0.2 -1 mol% of alkaline compound, based on the ketone and/or aldehyde to be reacted, is added. Although it is 10 technically possible to use larger amounts of alkali, it generally becomes increasingly less economically advantageous as the amount of alkali increases, because of the increasing alkali consumption and/or the cost of working it up again. It is likewise technically possible to use smaller amounts of alkali, 15 but this is generally not econom;cally advantageous because of the long reaction times.
The reaction mixture contains Ammo~;a and/or at least one 20 reactive primary amine as cocatalyst. The amount of cocatalyst is generally at least equimolar with the amount of alkaline compound(s) employed. Preferably, the amount of Ammonia or primary amine employed is at least twice that equimolar with the amount of alkaline compound(s) employed, and is particularly preferably at least five times. It is possible to employ as primary amine, for example, amino-substituted alkanes having 1 to 4 carbon atoms.
Examples of primary amines which can be employed according to the 30 invention are low molecular weight alkylamines, eg. alkylAm;nes having 1 to 4 carbon atoms such as methylamine, ethylamine, 1-propylamine, 2-propylamine, 1-butylamine, 2-butylamine, 2-methyl-1-propylamine and 1,1-dimethylethylamine. Mixtures of at least two amines or mixtures of at least one amine with ~mmon;a 35 can likewise be used. Ammo~ia and/or methylamine are preferably employed, very particularly preferably Ammonia The process can in principle be carried out without any other solvent. The process can likewise be carried out only in the 40 presence of the solvent or suspending agent for the solution or suspension of the alkaline compound when the alkaline compound is added in a solvent or suspending agent. However, the process can also be carried out in the presence of a solvent which is specifically used for the reaction and the choice of which is 45 subject to the same condition as the choice of the solvent or suspending agent for the alkaline compound. Suitable examples of solvents in this case are in addition all solvents which dissolve . _ , acetylene, such as N-methylpyrrolidone, dioxane, dimethyl sulfoxide (DMSO), sulfolane or THF, and ~mm~n;a or primary amines. The primary amines which can be used as solvents can be chosen like the primary amines which can be used as cocatalyst.
5 A~nn i ~ iS preferably employed as solvent.
The ketones or aldehydes employed for the purpose of the present invention are compounds of the formula I:
o ~ Il ~ C ~ (I) Rl R2 Confirming the choice of the radicals, there is no restriction per se so that all inert organic radicals, for example those having 1 to 50 carbon and/or heteroatoms, are suitable. For 20 example, Rl and R2 in this formula are, independently of one another, alkyl, alkenyl, aryl, alkylaryl, arylalkyl or arylalkenyl radicals which can be straight-chain or branched, open-chain or cyclic, substituted or unsubstituted. The term aryl means, for example, phenyl or naphthyl. In place of.aryl 25 radicals, it is also possible for heteroaromatic groups to be present, such as heteroaromatic rings which may contain one or more heteroatoms such as nitrogen, oxygen or sulfur. It is equally possible for the radicals to be aliphatic or cycloaliphatic, in particular both saturated and olefinically 30 unsaturated. These aliphatic or cycloaliphatic radicals may also contain one or more heteroatoms such as nitrogen, oxygen or sulfur. In addition, the radicals Rl and R2 may be connected together and form, together with the carbonyl group, a ring system which may also be olefinically unsaturated and may also 35 contain heteroatoms such as nitrogen, oxygen or sulfur. All said radicals may have inert substituents such as alkyl or alkoxy radicals or halogen atoms such as fluorine, chlorine, bromine or iodine. R2 is hydrogen in the case of aldehydes, and both Rl and R2 are hydrogen in the specific case of formaldehyde.
Examples of ketones which may be mentioned are acetone, methyl isobutyl ketone, methyl ethyl ketone, methylhept~nsne, methylheptenone, methyl norbornyl ketone, trimethylcyclopent~no~e, acetophenone, benzoph~none, methyl vinyl 45 ketone and ionone.
Examples of suitable aldehydes are formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, iso-butyraldehyde, 2-ethylhexAn~l, benzaldehyde or substituted benzaldehydes such as 4-tert-butylbenzaldehyde.
It is generally expedient to employ only one ketone or aldehyde, but it is possible in principle just as well to employ mixtures of at least two ketones, mixtures of at least two aldehydes or else mixtures of at least one ketone with at least one aldehyde.
10 In this case, mixtures of products are obtained and may be subsequently worked up together and used further as mixtures or be fractionated into the individual components during the workup.
It is likewise possible for the product mixture which results in the reaction of acetylene with various ketones and/or aldehydes 15 to be fractionated, eg. by physical methods, for example by distillation, into cuts or fractions, ie. to obtain not the individual compounds but new mixtures of products whose composition differs from that of the original mixture, and for these cuts or fractions to be used further.
The concentrations of the reactants and the amount of solvent can be chosen relatively freely according to the requirements of satisfactory operation of the process (the criteria may be, for 25 example, the viscosity of the reaction mixture, the reguired, eco~omically optimal space-time yield, the selectivity or the - amount of acetylene which can be handled safely). The amounts of ketone, aldehyde, acetylene and solvent optimal for the products required in the individual case and the precursors employed 30 therefor may vary in each case. However, to obtain a satisfactory yield of alkynediols, it is necessary for the molar ratio of ketone and/or aldehyde to acetylene to be greater than 1:1. Is is preferably at least 1.2 : 1. If it is required to prepare pure alkynediols or a mixture in which alkynediols predom;nAte over 35 monools, this ratio is preferably 1.5 : 1 and, particularly preferably, at least 2 : 1. The ratio can then be, for example, 2 : 1, 4 : 1 or 6 : 1. If a smaller proportion of ketone and/or aldehyde is employed, part of the acetylene does not react to give alkynediol but, on the contrary, for this part the reaction 40 stays at the stage of the alkynemonool, ie. of a 1-substituted or 1,1-disubstituted propargyl alcohol. Mixtures of alkynediol and alkyne~onool are obtained in this case. Experience has shown that large amounts of Ammon;a as solvent likewise lead to an increased formation of propargyl alcohol. Ratio by volume of ~mmon;a to the 45 ketone or aldehyde employed should therefore generally not exceed 30 : 1 to obtain an optimal yield of pure alkynediols, and it should preferably be below 20 : 1, in particular below 10 : 1.
It may in fact be advantageous for the ratio by volume to be below 2:1 or 1:1.
If it is wished to prepare a mixture of alkynPmonool and 5 alkynediol, it is also possible to use a larger excess of Ammon;a, for example a ratio by volume to the ketone or aldehyde employed of below 50 : 1, preferably below 40 : 1.
.
10 The temperature of the reaction for preparing pure alkynediols or mixtures in which the alkynediol content predominates is generally from 10 ~C to 140 ~C, preferably from 40 to 120 ~C and, particularly preferably, from 50 to 100 ~C. If the lower temperature is chosen, for example below 50 ~C, part of the acetylene does not react to give alkynediol but, on the contrary, for this part the reaction stays at the stage of the propargyl alcohol. Mixtures of alkynediol and propargyl alcohol are obtained in this case.
20 The process can in principle be carried out under atmospheric pressure or elevated pressure. If Ammon;a or another volatile substance is chosen as solvent, it will generally be expedient to choose a pressure such that the solvent is in liquid form at the reaction temperature. In the case of Ammonia as solvent, an 25 example of a pressure which is possible and suitable is 20 bar.
The process can be carried out, for example, in such a way that the ketone or aldehyde to be reacted is saturated with acetylene.
The alkaline compound and the cocatalyst and, if required, the 30 solvent are then added and the mixture is reacted in a reactor.
The reactor used is generally not critical and can be, for example, a tube reactor, a loop reactor, a stirred vessel reactor or else a cascade of stirred vessel reactors. The mixture can be worked up in a conventional way after the reaction is complete.
35 If a volatile solvent is used, this is evaporated off and the product is then obtained by distillation, for example. The reaction mixture or the residue after removal of the solvent can be washed with water and the phases be separated to remove the alkaline catalyst before the product is obtained. It is equally 40 possible for any water present in the reaction mixture to be removed, if this interferes with the further workup, by phase separation before removal of a solvent or obtA;ning the product.
.. . . .
Examples A liquid mixture of acetone with acetylene, liquid ~mmonia and, each hour, 6 ml of a 10 % by weight solution of potassium 5 hydroxide in methanol were conveyed under pressure into a heated tubular reactor (diameter 9 mm, length 500 mm) which was operated with a pump as loop reactor with external liquid recycling. The product was removed from the circulation under pressure control so that the pressure in the reactor was at a constant 20 bar.
10 After constituents which were volatile at room temperature and atmospheric pressure had evaporated off, the product was analyzed by gas chromatography, and the amounts of methylbutynol (MBI) and 2,5-dimethyl-3-hexyne-2,5-diol (DMHD) produced, and the amount of unconsumed acetone were determined. The acetone conversion and 15 the yields of MBI and DMHD were calculated therefrom.
The results are shown in Table 1.
20 Examples 1 to 3 show that the alkynediol can be prepared with excellent selectivity, ie. without measurable production of alkynemonool, with the process according to the invention.
Examples 4 and 5 show embodiments in which mixtures of the 25 alkynediol and the alkyn~ ool are obtained.
Example 6 is a comparative example similar to US-A 3 082 260, which shows that with a reaction procedure which differs in several points from that according to the invention (temperature 30 too low, amount of ~mmo~;a and excess of acetylene too high), as disclosed in US-A 3 082 260, exclusively the alkynemonool is produced.
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Claims (9)
1. A process for preparing alkynediols or mixtures of alkynediols with alkynemonools by reacting acetylene with more than equimolar amounts of ketones and/or aldehydes in the presence of an alkaline compound, wherein the molar amount of the alkaline compound used is less than half the molar amount of the ketone and/or aldehyde to be reacted, in the presence of ammonia and/or at least one reactive primary amine.
2. A process for preparing alkynediols by reacting acetylene with at least twice the molar amount of ketones and/or aldehydes, wherein the molar amount of the alkaline compound used is less than half the molar amount of the ketone and/or aldehyde to be reacted, in the presence of ammonia and/or at least one reactive primary amine.
3. A process as claimed in claim 1 or 2, wherein the alkaline compound is used in an amount of from 0.1 to 5 mol%, based on the ketone and/or aldehyde to be reacted.
4. A process as claimed in claim 3, wherein the alkaline compound is potassium hydroxide and/or potassium methanolate.
5. A process as claimed in any of claims 1 to 4, wherein the molar amount of ammonia and/or amine is at least as large as that of the alkaline compound employed.
6. A process as claimed in claim 5, wherein ammonia is used as solvent.
7. A process as claimed in claim 1, wherein the molar ratio of ketone and/or aldehyde to acetylene is greater than 1.5 : 1.
8. A process as claimed in any of claims 1 to 7, wherein the reaction is carried out at from 10 to 140°C.
9. A process as claimed in any of claims 1 to 8, wherein the reaction is carried out under elevated pressure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19635703.9 | 1996-09-03 | ||
| DE19635703A DE19635703A1 (en) | 1996-09-03 | 1996-09-03 | Process for the preparation of alkynediols or mixtures of alkynediols with alkyne monools |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2260814A1 true CA2260814A1 (en) | 1998-03-12 |
Family
ID=7804490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002260814A Abandoned CA2260814A1 (en) | 1996-09-03 | 1997-08-21 | Process for preparing alkyne diols or mixtures of alkyne diols with alkyne monools |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0929505A1 (en) |
| JP (1) | JP2000517326A (en) |
| KR (1) | KR20000068405A (en) |
| CA (1) | CA2260814A1 (en) |
| DE (1) | DE19635703A1 (en) |
| WO (1) | WO1998009932A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19924020A1 (en) * | 1999-05-26 | 2000-11-30 | Basf Ag | Process for the preparation of alkynediols |
| DE19933289A1 (en) * | 1999-07-15 | 2001-01-18 | Basf Ag | Process for the production of granules from a melt |
| DE10123066A1 (en) | 2001-05-11 | 2002-11-14 | Basf Ag | Process for the production of higher alpha, beta-unsaturated alcohols |
| JP4780959B2 (en) * | 2002-08-16 | 2011-09-28 | ディーエスエム アイピー アセッツ ビー．ブイ． | Ethynylation method |
| EP1808426A1 (en) * | 2006-01-16 | 2007-07-18 | DSMIP Assets B.V. | Process for the preparation of alkynediols |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3283014A (en) * | 1966-11-01 | Acetylenic alcohols from ketones and acetylene using aqueous alkaline hy- droxide catalyst | ||
| US3082260A (en) * | 1959-05-20 | 1963-03-19 | Air Reduction | Preparation of acetylenic alcohols |
| DE2008675A1 (en) * | 1970-02-25 | 1971-09-09 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | Process for the production of tertiary acetylene glycols by reacting acetylene with ketones |
| DE2047446C3 (en) * | 1970-09-26 | 1973-10-31 | Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen | Process for the production of acetylene glycols |
-
1996
- 1996-09-03 DE DE19635703A patent/DE19635703A1/en not_active Withdrawn
-
1997
- 1997-08-21 CA CA002260814A patent/CA2260814A1/en not_active Abandoned
- 1997-08-21 JP JP10512175A patent/JP2000517326A/en active Pending
- 1997-08-21 KR KR1019997001744A patent/KR20000068405A/en not_active Application Discontinuation
- 1997-08-21 EP EP97944774A patent/EP0929505A1/en not_active Withdrawn
- 1997-08-21 WO PCT/EP1997/004549 patent/WO1998009932A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0929505A1 (en) | 1999-07-21 |
| WO1998009932A1 (en) | 1998-03-12 |
| JP2000517326A (en) | 2000-12-26 |
| DE19635703A1 (en) | 1998-03-05 |
| KR20000068405A (en) | 2000-11-25 |
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