Method for producing alkali metal alkoxides

Abstract

The present invention provides a method for producing an alkali metal alkoxide, comprising the steps of: i) providing, in an inert atmosphere, in a reaction vessel, an organic compound having at least one —OH group and a molecular weight of 75 to 750 g / mol; ii) C 1~6 adding an alkali metal alcoholate to obtain a reaction mixture; iii) heating the reaction mixture of step ii) to 25-180°C under stirring to form an alkali metal alkoxide and C 1~6 Obtaining alcohol; and iv) The obtained C 1~6 distilling off the alcohol, wherein at least one non-polar solvent having a boiling point higher than that of the obtained alcohol is added to the mixture continuously or batchwise while distilling. The present invention relates to a method including:

Description

[Technical Field]

[0001] The present invention provides a method for producing an alkali metal alkoxide, comprising the steps of: i) providing, in an inert atmosphere, in a reaction vessel, an organic compound having at least one —OH group and a molecular weight of 75 to 750 g / mol; ii) C 1~6 adding an alkali metal alcoholate to obtain a reaction mixture; iii) heating the reaction mixture of step ii) to 25-180°C under stirring to form an alkali metal alkoxide and C 1~6 Obtaining alcohol; and iv) The obtained C 1~6 distilling off the alcohol, wherein at least one non-polar solvent having a boiling point higher than that of the obtained alcohol is added to the mixture continuously or batchwise while distilling. The present invention relates to a method including:

[0002] Alkali metal alkoxides are used for a variety of purposes, such as aldol addition, esterification / transesterification, malonic ester synthesis, ether formation, and other general uses as bases. They are also widely used in the food industry, for example in margarine production or vitamin A synthesis, in medicinal chemistry, for example in the production of antibiotics, analgesics, chemotherapeutics, and epilepsy drugs, in agricultural chemistry, for example in the production of herbicides and fungicides, and in many other application areas, for example in the production of optical brighteners, UV absorbers, and photoinitiators.

[0003] Various methods for producing alkali metal alkoxides are known in the prior art.

[0004] One known method involves the reaction of alcohols with alkali metals, during which hydrogen is produced, and the release of hydrogen can increase rapidly with low molecular weight alcohols (Roempp Online. Georg Thieme Verlag, accessed May 28, 2020).

[0005] Another alternative involves the reaction of the alcohol with a strong base, such as an alkali amide or alkali hydride. This reaction produces ammonia or hydrogen as a by-product. Because alkali amides are extremely sensitive, product yields vary widely.

[0006] Another alternative process, described in EP 1195369, involves the reaction of an alcohol with an alkali amalgam. After the reaction, the final product is contaminated with hydrogen and mercury. A further development of this process, disclosed in EP 0776995, involves the reaction of the corresponding alcohol with another alcoholate in the liquid phase in the presence of an electric field. Metal ions are introduced under the influence of the electric field to give the required alcoholate, preferably in different zones separated by an ion exchange membrane, where decomposition of the other alcoholate and subsequent introduction of the metal into the alcohol are effected.

[0007] Another alternative method described in U.S. Pat. No. 3,418,383 discloses the preparation of alkali metal alcoholates by an improved exchange reaction between a lower alcoholate of an alkali metal and a higher alcohol, in which the exchange reaction is carried out in the presence of vapors of the higher alcohol passing through the exchange reaction mass, to give a higher alcoholate of an alkali metal. The reaction time for this reaction is very long and a high molar amount of alcohol is required for the reaction.

[0008] However, all known methods result in alkali metal alkoxides containing impurities that can reduce the storage stability of the resulting alkali metal alkoxides, resulting in the need for labor-intensive purification steps or making them undesirable for use as starting materials for pharmaceutical applications.

[0009] It was therefore an object of the present invention to provide an improved process which results in alkali metal oxides having low impurities and which do not require a separate additional purification step.

[0010] This allows for the preparation of C without the need for complex separations as is known in the art. 1~6 Complete conversion of the starting compounds, including alkali metal alcoholates, and thus high purity of the alkali metal alkoxides obtained, are achieved by the process according to the invention.

[0011] In particular, the object is a method for producing an alkali metal alkoxide, comprising the steps of: i) providing, in an inert atmosphere, in a reaction vessel, an organic compound having at least one —OH group and a molecular weight of 75 to 750 g / mol; ii) C 1~6 adding an alkali metal alcoholate to obtain a reaction mixture; iii) heating the reaction mixture of step ii) to 25-180°C under stirring to form an alkali metal alkoxide and C 1~6 Obtaining alcohol; and iv) The obtained C 1~6 distilling off the alcohol, wherein at least one non-polar solvent having a boiling point higher than that of the obtained alcohol is added to the mixture continuously or batchwise while distilling. This is achieved by a method comprising:

[0012] To achieve complete conversion, it is necessary to add, continuously or batchwise, at least one nonpolar solvent with a boiling point higher than that of the resulting alcohol while distilling. The resulting alkali metal alkoxide has high purity and can be isolated as a liquid without further purification or as a crystalline powder with good flow properties that is easy to filter.

[0013] Distillation can be any common distillation method known in the art, preferably azeotropic distillation, reactive distillation, vacuum distillation, or fractional distillation, or a combination of at least two of the aforementioned techniques.

[0014] During the distillation, an inert gas stream, preferably a nitrogen stream, can be applied at a flow rate of preferably 10 to 300 NL / h, more preferably 50 to 200 NL / h.

[0015] "At least one" means one or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or more. As used herein with respect to any component, "at least one" refers to the number of chemically distinct molecules, i.e., the number of different types of the referenced species, and not the total number of molecules. For example, "at least one nonpolar solvent" means that at least one type of molecule included in the definition of nonpolar solvent is used, and also means that two or more different types of nonpolar solvent included in this definition can also be present, but does not mean that only one or more molecules of one type of nonpolar solvent are present.

[0016] In particular, the present invention refers to: Item 1. A method for producing an alkali metal alkoxide, more preferably a potassium alkoxide, comprising the following steps: i) providing an organic compound having at least one —OH group and a molecular weight of 75 to 750 g / mol, preferably 75 to 350 g / mol, in a reaction vessel in an inert atmosphere; ii) C 1~6 Alkali metal alcoholates, more preferably C 1~4 Alkali metal alcoholates, more preferably C 1~4 adding potassium alcoholate to obtain a reaction mixture; iii) heating the reaction mixture of step ii) under stirring to 25-180°C, preferably 60-170°C, to form an alkali metal alkoxide and C 1~6 Alcohol, preferably C 1~4Obtaining alcohol; and iv) The obtained C 1~6 Alcohol, preferably C 1~4 a step of distilling off the alcohol, wherein while distilling, at least one non-polar solvent having a boiling point higher than the obtained alcohol, of at least 138°C, more preferably between 138°C and 300°C, is added to the mixture continuously or batchwise, preferably in up to 4 batches. A method comprising or consisting of:

[0017] If step iii) is carried out at a temperature of 170° C. or less, the purity of the resulting alkali metal alkoxide is further increased.

[0018] Item 2. The organic compound having at least one -OH group is selected from substituted or unsubstituted aliphatic or aromatic hydrocarbons, silyl ethers, polyols, ethers, and polyethers, or mixtures thereof. Preferably, the organic compound is selected from phenol, benzyl alcohol, 2-alkoxyethanol, 2-aryloxyethanol, 2-siloxyethanol, 2-(2-alkoxyethoxy)ethanol, 2-(2-aryloxyethoxy)ethanol, 2-(2-silanyloxyethoxy)ethanol, 3-alkoxypropanol, 3-aryloxypropanol, 3-siloxypropanol, 2-(2-alkoxyethoxy)ethanol, 2-(2-aryloxyethoxy)ethanol, 2-(2-silanyloxyethoxy)ethanol, diols, triols, and tetraols. More preferably, the organic compound is selected from phenol, benzyl alcohol, 2-alkoxyethanol, 2-aryloxyethanol, 2-siloxyethanol, 2-(2-alkoxyethoxy)ethanol, 2-(2-aryloxyethoxy)ethanol, 2-(2-silanyloxyethoxy)ethanol, diols, triols, and tetraols. Preferably, the compound is selected from 2-benzyloxyethanol, 2-methoxyethanol, diethylene glycol monobenzyl ether, 2-tert-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(tert-butyl-dimethylsilanyloxy)ethanol, 2-(tert-butyldiphenylsilanyloxy)ethanol, 2-(2-(tert-butyldimethylsilylethoxy)ethanol, 2-(2-tert-butyldiphenylsilylethoxy)ethanol, pentaerythritol, triethylene glycol, tetraethylene glycol, 2,2'-((2-((2-hydroxyethoxy)methyl)-2-(hydroxymethyl)propane-1,3-diyl)bis(oxy))bis(ethan-1-ol), 3-methoxypropanol, or a mixture thereof.Preferably, the organic compound having at least one -OH group is selected from phenol, benzyl alcohol, 2-alkoxyethanol, 2-aryloxyethanol, 2-siloxyethanol, 2-(2-alkoxyethoxy)ethanol, 2-(2-aryloxyethoxy)ethanol, 2-(2-silanyloxyethoxy)ethanol, 3-alkoxypropanol, 3-aryloxypropanol, 3-siloxypropanol, 2-(2-alkoxyethoxy)ethanol, 2-(2-aryloxyethoxy)ethanol, 2-(2-silanyloxyethoxy)ethanol, diols, triols, tetraols. More preferably, the organic compound having at least one -OH group is selected from 2-benzyloxyethanol, 2-methoxyethanol, diethylene glycol monobenzyl ether, 2-tert-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(tert-butyl-dimethylsilanyloxy)ethanol, 2-(tert-butyldiphenylsilanyloxy)ethanol, 2-(2-(tert-butyldimethylsilylethoxy)ethanol, 2-(2-tert-butyldiphenylsilylethoxy)ethanol, pentaerythritol, triethylene glycol, tetraethylene glycol, 2,2'-((2-((2-hydroxyethoxy)methyl)-2-(hydroxymethyl)propane-1,3-diyl)bis(oxy))bis(ethan-1-ol), 3-methoxypropanol.

[0019] Item 3.C 1~6 The method of any of the preceding items, wherein the alkali metal alcoholate is selected from potassium methanolate, potassium ethanolate, potassium 2-methylpropan-2-olate, potassium propan-2-olate, potassium propan-1-olate, potassium butan-2-olate, and potassium tert-butoxide.

[0020] Item 4. The method of any of the preceding items, wherein the at least one non-polar solvent is selected from toluene, dodecane, tetradecane, xylene, or tetraethylene glycol dimethyl ether, or a mixture thereof. Preferably, the at least one solvent is selected from toluene, xylene, cumene, biphenyl, octane, nonane, C 10~20 Alkanes and their isomers, C 10~20 It is selected from decane and its isomers, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, or mixtures thereof.

[0021] Item 5. The reactor is equipped with a rotating element for stirring; preferably 10. The method of claim 1, wherein the at least one non-polar solvent is added when the moment of force M of the rotating element increases by at least 1.5 times, and wherein after the addition of the at least one non-polar solvent, the moment of force M decreases by at least 1.5 times.

[0022] Item 6. The method according to any one of the preceding items, wherein the at least one non-polar solvent is present in an amount of between 1 ml and 20 ml, preferably between 1 ml and 10 ml, per 1 mmol of the organic compound having at least one —OH group and having a molecular weight of 75 to 750 g / mol, preferably 75 to 350 g / mol.

[0023] Item 7. The method of any one of the preceding items, wherein the reaction time is at least 3 hours, preferably at least 24 hours, for batch addition, or at least 0.5 hours, preferably 6 hours, for continuous addition.

[0024] Item 8. The method of any one of the preceding items, wherein at least one non-polar solvent is washed off after reaction with a volatile non-polar solvent, preferably the volatile non-polar solvent is selected from methyl tert-butyl ether and n-pentane.

[0025] Item 9. An organic compound having at least one -OH group and a molecular weight of 75 to 750 g / mol, preferably 75 to 350 g / mol, and C 1~6 Alkali metal alcoholates, C 1~4 10. The method of any one of the preceding items, wherein the alkali metal alcoholate is present in a molar ratio of 2:1 to 1:1.

[0026] In one embodiment of the invention, the reaction vessel comprises a rotating element, - at least one non-polar solvent is added when the moment of force M of the rotating element increases by at least 1.5 times, - after the addition of at least one non-polar solvent, the moment of force M is reduced by at least 1.5 times.

[0027] In one embodiment of the present invention, the at least one non-polar solvent is present in an amount between 1 ml / mmol and 20 ml / mmol, preferably between 1 ml / mmol and 10 ml / mmol.

[0028] In another embodiment, at least one solvent is non-polar and aprotic, preferably selected from aromatic hydrocarbons, aliphatic hydrocarbons, ether solvents, or mixtures thereof.

[0029] In a preferred embodiment, the at least one non-polar solvent is a hydrocarbon having at least 4 carbon atoms, preferably selected from toluene, dodecane, tetradecane, xylene, tetraethylene glycol dimethyl ether, or a silane or siloxane.

[0030] In another preferred embodiment, the reaction time is at least 12 hours, preferably at least 24 hours. In one preferred embodiment, step iv) is carried out for 4-5 hours.

[0031] In another embodiment, the reaction after the reaction time is cooled to room temperature with a cooling ramp of approximately 1 K / min.

[0032] In another preferred embodiment, the at least one non-polar solvent is washed off after reaction with a volatile non-polar solvent, which is preferably an aprotic solvent, more preferably selected from MTBE, toluene, pentane, or hexane.

[0033] In another embodiment, the resulting alkali metal alkoxide is dried under an inert atmosphere and applied vacuum at room temperature for 5 hours or more.

[0034] The resulting alkali metal alkoxide may have an assay of at least 90%, preferably at least 95%, and more preferably at least 99%, as determined by titration.

[0035] Example Organic compounds with at least one -OH group and C 1~6 Preparation of alkali metal alkoxides by reaction with alkali metal alcoholates.

[0036] Common methods: The reactor is inerted with an inert gas and kept free of water before carrying out the reaction. An organic compound (1 equivalent) having at least one -OH group is charged to the reactor, and at least one C 1~6 An alkali metal alcoholate, e.g., methanolate (1 equivalent), is added, and handling under an inert atmosphere is essential. To initiate the reaction, an inert gas is introduced into the mass and the flask is heated. The gas flow is maintained throughout the reaction.

[0037] Then, the obtained C 1~6The alcohol is distilled off for complete conversion (IPC). IPC:C 1~6 NMR of alcohols.

[0038] During the distillation, the viscosity becomes so high (as indicated by an increase in stirrer torque) that stirring becomes difficult. The viscosity is reduced by adding at least one non-polar solvent, either continuously or batchwise. After the distillation step, a slurry containing the alkali metal alkoxide is obtained.

[0039] A cooling ramp (for laboratory tests) is maintained at -0.1 to 1 K / min down to room temperature. The cooling procedure must be adapted to the device under consideration and is well within the scope of the skilled person's general knowledge.

[0040] For washing, the slurry is pressed onto a filter and the filter cake is washed twice with a non-polar solvent. The final product is dried under vacuum with an inert gas.

[0041] Reaction of potassium benzyloxyethanol with benzyloxyethanol in the presence of n-dodecane [ka]

[0042] The desired reactor was inerted with inert gas and kept free of water before carrying out the reaction. 627.7 g (99%; 4 mol; 1 eq.) of benzyloxyethanol was charged to the reactor, and 166.8 g (98.95; 4 mol; 1 eq.) of potassium methanolate was added under an inert (dry) atmosphere. (Re)-inerting of the reactor after the addition of the raw materials. The reaction mass was heated to 110 °C with constant stirring, and nitrogen was introduced into the mass. A three-blade propeller stirring shaft with a total blade diameter of 75 mm was used. The nitrogen flow was maintained at approximately 100 L / h of dry nitrogen throughout the entire distillation period. Methanol was distilled off over a reaction time of approximately 160 h.

[0043] Complete conversion is confirmed by NMR with residual methanol content.

[0044] During distillation, the viscosity becomes so high that stirring (100 rpm) becomes difficult. The torque increases from 0-4 Ncm to 15-30 Ncm. The viscosity can be reduced by adding n-dodecane (0.1-0.2 L) to the homogeneous reaction mixture, which reduces the torque to 2-6 Ncm. The n-dodecane is carried into the reactor head as an aerosol during the reaction and must be replenished in several portions. The total amount of n-dodecane (100%; 0.25 L; 1.1 mol)

[0045] At the end of the distillation, 250 mL of (anhydrous / 100%) toluene was added (at approximately 100° C. and full stirring) to prepare a slurry. The toluene must be dried to a low water content (e.g., using molsieve, AlOx, or another suitable method) before addition, or purchased in anhydrous form.

[0046] A cooling ramp (for laboratory tests) is maintained at -0.1 to 1 K / min down to a minimum of 20°C. The cooling procedure must be adapted to the equipment under consideration.

[0047] For washing, the slurry is pressed onto a filter. The residue is transferred onto the cake with 200 mL of toluene (anhydrous) and the filter cake is washed twice with 125 mL of toluene (anhydrous) each time. The filter cake is then washed twice with 200 mL of dry MTBE each time. The final product is dried under vacuum at room temperature with application of inert gas. Yield: 91.3%. Purity titration: 98.9% by weight.

[0048] Reaction of potassium benzyloxyethanol with benzyloxyethanol in the presence of n-tetradecane [ka]

[0049] The desired reactor was inerted and kept free of water before carrying out the reaction. 310.6 g (99%; 2 mol; 1 eq.) of benzyloxyethanol was charged to the reactor, and 144.6 g (98.95%; 2 mol; 1 eq.) of potassium methanolate was added under an inert (dry) atmosphere. (Re)-inerting the reactor after the addition of the raw materials. The reaction mass was heated to 120 °C with constant stirring, and nitrogen was introduced into the mass. A three-blade propeller stirring shaft with a total blade diameter of 75 mm was used. The nitrogen flow was maintained at approximately 100 L / h of dry nitrogen throughout the entire distillation period. Methanol was distilled off over a reaction time of approximately 168 h.

[0050] Complete conversion is confirmed by NMR with residual methanol content.

[0051] During distillation, the viscosity becomes so high that stirring (rpm 100) becomes difficult. The torque increases from 0-5 Ncm to 10-18 Ncm. The viscosity can be reduced by adding n-tetradecane (0.1-0.2 L) to the homogeneous reaction mixture, and the torque decreases to 2-4 Ncm upon addition. n-tetradecane is carried into the reactor head as an aerosol during the reaction time and must be replenished in several portions. The total amount of n-tetradecane (100%; 0.45 L; 1.7 mol)

[0052] At the end of the distillation, 50 mL of (anhydrous / 100%) toluene was added (at approximately 100°C and full stirring) to prepare a slurry. The toluene must be dried to a low water content (e.g., using molsieve, AlOx, or another suitable method) before addition, or purchased in anhydrous form.

[0053] A cooling ramp (for laboratory tests) is maintained at -0.1 to 1 K / min down to a minimum of 20°C. The cooling procedure must be adapted to the equipment under consideration.

[0054] For washing, the slurry is pressed onto a filter. The residue is transferred onto the cake with 25 mL of toluene (anhydrous) and the filter cake is washed three times with 25 mL of toluene (anhydrous) each. The filter cake is then washed twice with 200 mL of dry MTBE each. The final product is dried under vacuum at room temperature with application of inert gas. Yield: 92.4%. Purity titration: 98.5% by weight.

[0055] Reaction of benzyloxyethanol with potassium benzyloxyethanolate in the presence of o-xylene [ka]

[0056] The desired reactor was inerted and kept free of water before carrying out the reaction. 415.6 g (99%; 2.7 mol; 1 eq.) of benzyloxyethanol was charged to the reactor, and 193.4 g (98.95%; 2.7 mol; 1 eq.) of potassium methanolate was added under an inert (dry) atmosphere. (Re)-inerting the reactor after the addition of the raw materials. The reaction mass was heated to 120 °C with constant stirring, and nitrogen was introduced into the mass. A three-blade propeller stirring shaft with a total blade diameter of 75 mm was used. The nitrogen flow was maintained at approximately 100 L / h of dry nitrogen throughout the entire distillation period. Methanol was distilled off over a reaction time of approximately 360 h.

[0057] Complete conversion is confirmed by NMR with residual methanol content.

[0058] During the distillation, the viscosity becomes so high that stirring (100 rpm) becomes difficult. The torque increases from 0-5 Ncm to 10-22 Ncm. The viscosity can be reduced by adding o-xylene (0.1-0.4 L) to the homogeneous reaction mixture; the torque decreases to 5-7 Ncm. The o-xylene runs off the reactor head as an aerosol during the reaction and must be replenished in several portions. The total amount of o-xylene (100%; 1.0 L; 8.3 mol)

[0059] At the end of the distillation, 50 mL of (anhydrous / 100%) toluene was added (at approximately 100°C and full stirring) to prepare a slurry. The toluene must be dried to a low water content (e.g., using molsieve, AlOx, or another suitable method) before addition, or purchased in anhydrous form.

[0060] A cooling ramp (for laboratory tests) is maintained at -0.1 to 1 K / min down to a minimum of 20°C. The cooling procedure must be adapted to the equipment under consideration.

[0061] For washing, the slurry is pressed onto a filter. The residue is transferred onto the cake with 25 mL of toluene (anhydrous) and the filter cake is washed three times with 25 mL of toluene (anhydrous) each. The filter cake is then washed twice with 100 mL of MTBE (dry, moisture content <10 ppm) each. The final product is dried under vacuum (room temperature to 35°C, p = 0.05 bara, t = 20 h) by applying inert gas. Yield: 92.8%. Purity titration: 98.7% by weight.

[0062] Reaction of benzyloxyethanol with potassium benzyloxyethanolate in the presence of tetraglyme [ka]

[0063] The desired reactor was inerted and kept free of water before carrying out the reaction. 311.2 g (99%; 2.0 mol; 1 eq.) of benzyloxyethanol was charged to the reactor, and 143.4 g (98.95%; 2.0 mol; 1 eq.) of potassium methanolate was added under an inert (dry) atmosphere. (Re)-inerting the reactor after the addition of the raw materials. The reaction mass was heated to 120°C with constant stirring, and nitrogen was introduced into the mass. A three-blade propeller stirring shaft with a total blade diameter of 75 mm was used. The nitrogen flow was maintained at approximately 100 L / h dry nitrogen throughout the entire distillation period. Methanol was distilled off over a reaction time of approximately 264 hours.

[0064] Complete conversion is confirmed by NMR with residual methanol content.

[0065] During the distillation, the viscosity becomes so high that stirring (100 rpm) becomes difficult. The torque increases from 0-6 Ncm to 10-26 Ncm. The viscosity can be reduced by adding tetraglyme (0.1 L) to the homogeneous reaction mixture; the torque decreases to 7-14 Ncm. The tetraglyme is carried into the reactor head as an aerosol during the reaction and must be replenished in several portions. The total amount of tetraglyme is (100%; 0.6 L; 2.1 mol).

[0066] At the end of the distillation, 50 mL of (anhydrous / 100%) toluene was added (at approximately 100°C and full stirring) to prepare a slurry. The toluene must be dried to a low water content (e.g., using molsieve, AlOx, or another suitable method) before addition, or purchased in anhydrous form.

[0067] A cooling ramp (for laboratory tests) is maintained at -0.1 to 1 K / min down to a minimum of 20°C. The cooling procedure must be adapted to the equipment under consideration.

[0068] For washing, the slurry is pressed onto a filter. The residue is transferred onto the cake with 50 mL of toluene (anhydrous) and the filter cake is washed twice with 100 mL of toluene (anhydrous) each time. The filter cake is then washed twice with 300 mL of dry MTBE each time. The final product is dried under vacuum with application of inert gas. Yield: 99.65%. Purity titration: 87.9% by weight.

[0069] Reaction of benzyloxyethanol with potassium tert-butoxide to potassium benzyloxyethanolate [ka]

[0070] The desired reactor was inerted and kept free of water before carrying out the reaction. 264.5 g (99%; 1.7 mol; 1 eq.) of benzyloxyethanol was charged to the reactor, and 195.0 g (98%; 1.7 mol; 1 eq.) of potassium tert-butoxide was added under an inert (dry) atmosphere. (Re)-inerting the reactor after the addition of the raw materials. The reaction mass was heated to 110 °C with constant stirring, and nitrogen was introduced into the mass. A three-blade propeller stirring shaft with a total blade diameter of 75 mm was used. The nitrogen flow was maintained at approximately 100 L / h of dry nitrogen throughout the entire distillation period. The tert-butyl alcohol was distilled off over a reaction time of approximately 120 h.

[0071] Complete conversion is confirmed by NMR with residual methanol content.

[0072] During distillation, the viscosity becomes so high that stirring (rpm 100) becomes difficult. The torque increases from 3-8 Ncm to 15-30 Ncm. The viscosity can be reduced by adding n-dodecane (0.1-0.2 L) to the homogeneous reaction mixture, and the torque decreases to 1-8 Ncm upon addition. n-Dodecane runs into the reactor head as an aerosol during the reaction time and must be replenished in several portions. The total amount of n-dodecane (100%; 0.75 L; 3.3 mol)

[0073] At the end of the distillation, 50 mL of (anhydrous / 100%) toluene was added (at approximately 100°C and full stirring) to prepare a slurry. The toluene must be dried to a low water content (e.g., using molsieve, AlOx, or another suitable method) before addition, or purchased in anhydrous form.

[0074] A cooling ramp (for laboratory tests) is maintained at -0.1 to 1 K / min down to a minimum of 20°C. The cooling procedure must be adapted to the equipment under consideration.

[0075] For washing, the slurry is pressed onto a filter. The residue is transferred onto the cake with 50 mL of toluene (anhydrous) and the filter cake is washed twice with 50 mL of toluene (anhydrous) each. The filter cake is then washed twice with 200 mL of dry MTBE each. The final product is dried under vacuum with application of inert gas. Yield: 90.5%. Purity titration: 98.9% by weight.

[0076] Reaction of potassium-diethylene glycol monobenzyl ether with diethylene glycol monobenzyl ether The desired reactor was inerted and kept free of water before carrying out the reaction. 277.0 g (99%; 1.4 mol; 1 eq.) of diethylene glycol monobenzyl ether was charged to the reactor, and 98.0 g (98%; 1.4 mol; 1 eq.) of potassium methanolate was added under an inert (dry) atmosphere. (Re)-inerting the reactor after the addition of the raw materials. The reaction mass was heated to 110°C with constant stirring, and nitrogen was introduced into the mass. A three-blade propeller stirring shaft with a total blade diameter of 75 mm was used. The nitrogen flow was maintained at approximately 100 L / h of dry nitrogen throughout the entire distillation period. Methanol was distilled off over a reaction time of approximately 72 hours.

[0077] Complete conversion is confirmed by NMR with residual methanol content.

[0078] During distillation, the stirred (100 rpm) reaction mass is a viscous liquid. The torque increases from 1-2 Ncm to 6-8 Ncm. The viscosity can be reduced by adding n-dodecane (0.1-0.2 L) to the homogeneous reaction mixture; the torque decreases to 1-5 Ncm. The n-dodecane runs into the reactor head as an aerosol during the reaction and must be replenished in several portions. The total amount of n-dodecane (100%; 0.75 L; 3.3 mol)

[0079] After the reaction, the product exists as a dark red, highly viscous liquid. Yield: 74.8%. Purity NMR: 91.3% by weight.

[0080] Reaction of 2-tert-butoxyethanol to potassium 2-tert-butoxyethanol using a change in impeller for potassium tert-butoxide + anchor stirrer [ka]

[0081] The desired reactor was inerted and kept free of water before carrying out the reaction. 241.1 g (98%; 2.0 mol; 1 eq.) of 2-tert-butoxyethanol was charged to the reactor, and 250.4 g (98%; 2.0 mol; 1 eq.) of potassium tert-butoxide was added under an inert (dry) atmosphere. (Re)-inerting the reactor after the addition of the raw materials. The reaction mass was heated to 110°C with constant stirring, and nitrogen was introduced into the mass. An anchor stirrer with a total impeller diameter of 95 mm was used. The nitrogen flow was maintained at approximately 100 L / h dry nitrogen throughout the entire distillation period. The tert-butyl alcohol was distilled off over a reaction time of approximately 26 hours.

[0082] Complete conversion is confirmed by NMR with residual methanol content.

[0083] During distillation, the viscosity becomes so high that stirring (rpm 100) becomes difficult. The torque increases from 10-15 Ncm to 30-50 Ncm. The viscosity can be reduced by adding n-dodecane (0.1-0.2 L) to the homogeneous reaction mixture, and the torque decreases to 2-4 Ncm upon addition. n-Dodecane is carried into the reactor head as an aerosol during the reaction time and must be replenished in several portions. The total amount of n-dodecane (100%; 0.4 L; 1.8 mol)

[0084] At the end of the distillation, 50 mL of (anhydrous / 100%) toluene was added (at approximately 100 °C and full stirring) to prepare a slurry. The toluene must be dried to a low water content (e.g., using molsieve, AlOx, or another suitable method) before addition, or purchased in anhydrous form. The toluene content must also be adapted to the existing filtration equipment, as sufficient dilution with toluene is required for transfer to the filtration equipment.

[0085] A cooling ramp (for laboratory tests) is maintained at -0.1 to 1 K / min down to a minimum of 20°C. The cooling procedure must be adapted to the equipment under consideration.

[0086] For washing, the slurry is pressed onto a filter. The residue is transferred onto the cake with 50 mL of toluene (anhydrous) and the filter cake is washed twice with 100 mL of toluene (anhydrous) each time. The filter cake is then washed twice with 200 mL of dry MTBE each time. The final product is dried under vacuum by applying an inert gas. Yield: 86.2%. Purity titration: 99.0% by weight.

[0087] Reaction of triethylene glycol to dipotassium triethylene glycolate using a change in impeller to potassium tert-butoxide + anchor stirrer [ka]

[0088] The desired reactor was inerted and kept free of water before carrying out the reaction. 379.2 g (99%; 2.5 mol; 1 eq.) of triethylene glycol was charged to the reactor, and 572.2 g (98%; 5.0 mol; 2 eq.) of potassium tert-butoxide was added under an inert (dry) atmosphere. (Re)-inerting the reactor after adding the raw materials. The reaction mass was heated to 110°C with constant stirring, and nitrogen was introduced into the mass. An anchor stirrer with a total impeller diameter of 95 mm was used. The nitrogen flow was maintained at approximately 100 L / h of dry nitrogen throughout the entire distillation period. The tert-butyl alcohol was distilled off over a reaction time of approximately 77 hours.

[0089] Complete conversion is confirmed by NMR with residual methanol content.

[0090] During distillation, the viscosity becomes so high that stirring (100 rpm) becomes difficult. The torque increases from 3-15 Ncm to 15-37 Ncm. The viscosity can be reduced by adding a 50 / 50 mixture of n-dodecane and tetraglyme (v / v) (0.1-0.2 L) to the homogeneous reaction mixture; the torque decreases to 15-20 Ncm. The mixture is run as an aerosol at the reactor head during the reaction time and must be replenished in several portions. The total amount of n-dodecane (100%; 0.4 L)

[0091] At the end of the distillation, 50 mL of (anhydrous / 100%) toluene was added (at approximately 100 °C and full stirring speed) to prepare a slurry. The toluene must be dried to a low water content before addition (e.g., using molsieve, AlOx, or another suitable method) or purchased in anhydrous form. A cooling ramp (for laboratory tests) was maintained at -0.1 to 1 K / min down to a minimum of 20 °C. The cooling procedure must be adapted to the equipment under consideration.

[0092] For washing, the slurry is pressurized onto the filter (7-14 cm resulting in a filter cake height of 16-18 cm). 2(filter area of ​​10 ...

[0093] Reaction of 2-methoxyethanol with potassium tert-butoxide to potassium 2-methoxyethanolate [ka]

[0094] The desired reactor was inerted and kept free of water before carrying out the reaction. 305.0 g (99%; 4.0 mol; 1 eq.) of triethylene glycol was charged to the reactor, and 458.0 g (98%; 4.0 mol; 1 eq.) of potassium tert-butoxide was added under an inert (dry) atmosphere. (Re)-inerting the reactor after the addition of the raw materials. The reaction mass was heated to 120 °C with constant stirring, and nitrogen was introduced into the mass. A three-blade propeller stirring shaft with a total blade diameter of 95 mm was used. The nitrogen flow was maintained at approximately 100 L / h of dry nitrogen throughout the entire distillation period. The tert-butyl alcohol was distilled off over a reaction time of approximately 50 hours.

[0095] Complete conversion is confirmed by NMR with residual methanol content.

[0096] During distillation, the viscosity becomes so high that stirring (100 rpm) becomes difficult. The torque increases from 3-5 Ncm to 15-20 Ncm. The viscosity can be reduced by adding n-dodecane (0.1-0.2 L) to the homogeneous reaction mixture, which reduces the torque to 2-5 Ncm. The mixture runs as an aerosol at the reactor head during the reaction time and must be replenished in several portions. The total amount of n-dodecane (100%; 0.5 L)

[0097] At the end of the distillation, 50 mL of (anhydrous / 100%) toluene was added (at approximately 100°C and full stirring) to prepare a slurry. The toluene must be dried to a low water content (e.g., using molsieve, AlOx, or another suitable method) before addition, or purchased in anhydrous form.

[0098] A cooling ramp (for laboratory tests) is maintained at -0.1 to 1 K / min down to a minimum of 20°C. The cooling procedure must be adapted to the equipment under consideration.

[0099] For washing, the slurry is pressed onto a filter. The residue is transferred onto the cake with 50 mL of toluene (anhydrous) and the filter cake is washed twice with 50 mL of toluene (anhydrous) each. The filter cake is then washed twice with 200 mL of dry MTBE each. The final product is dried under vacuum with application of inert gas. Yield: 93.7%. Purity titration: 97.1% by weight.

[0100] Reaction of pentaerythritol with tetrapotassium pentaerythritol using potassium methoxide [ka]

[0101] The desired reactor was inerted and kept free of water before carrying out the reaction. 277.8 g (99%; 2.0 mol; 1 eq.) of pentaerythritol was charged to the reactor, and 567.0 g (98%; 8.1 mol; 4 eq.) of potassium tert-butoxide was added under an inert (dry) atmosphere. (Re)-inerting the reactor after the addition of the raw materials. The reaction mass was heated to 145 °C with constant stirring, and nitrogen was introduced into the mass. A three-blade propeller stirring shaft with a total blade diameter of 95 mm was used. The nitrogen flow was maintained at approximately 100 L / h dry nitrogen throughout the entire distillation period. Methanol was distilled off over a reaction time of approximately 390 h.

[0102] Complete conversion is confirmed by NMR with residual methanol content.

[0103] During distillation, the viscosity becomes so high that stirring (100 rpm) becomes difficult. The torque increases from 3-5 Ncm to 15-20 Ncm. The viscosity can be reduced by adding a 50 / 50 mixture of n-dodecane and diglyme (v / v) (0.1-0.3 L) to the homogeneous reaction mixture; the torque decreases to 2-8 Ncm. The mixture is run as an aerosol at the reactor head during the reaction time and must be replenished in several portions. The total amount of n-dodecane (100%; 1.6 L)

[0104] At the end of the distillation, 50 mL of (anhydrous / 100%) toluene was added (at approximately 100°C and full stirring) to prepare a slurry. The toluene must be dried to a low water content (e.g., using molsieve, AlOx, or another suitable method) before addition, or purchased in anhydrous form.

[0105] A cooling ramp (for laboratory tests) is maintained at -0.1 to 1 K / min down to a minimum of 20°C. The cooling procedure must be adapted to the equipment under consideration.

[0106] For washing, the slurry is pressed onto a filter. The residue is transferred onto the cake with 50 mL of toluene (anhydrous) and the filter cake is washed three times with 50 mL of toluene (anhydrous) each. The filter cake is then washed twice with 200 mL of dry MTBE each. The final product is dried under vacuum with application of inert gas. Yield: 55.2%. Purity titration: 69.4% by weight.

[0107] For washing, the slurry is pressed onto a filter and the filter cake is washed twice with a non-polar solvent. The final product is dried under vacuum with application of an inert gas.

[0108] Reaction of benzyloxyethanol to benzyloxyethanolate in the presence of n-dodecane [ka]

[0109] The desired reactor was inerted and kept free of water before carrying out the reaction. 627.7 g (98%; 4 mol; 1 eq.) of benzyloxyethanol was charged to the reactor, and 166.8 g (98.95%; 4; 1 eq.) of potassium methanolate was added under an inert (dry) atmosphere. (Re)-inerting of the reactor after the addition of the raw materials. The reaction was heated to 110°C, and nitrogen was introduced into the melt. The nitrogen flow was maintained at approximately 100 L / h dry nitrogen throughout the entire distillation period. Methanol was distilled off over a reaction time of approximately 44 hours.

[0110] Complete conversion is confirmed by NMR with residual methanol content.

[0111] During the distillation, the viscosity becomes very high (indicated by an increase in stirrer torque), making stirring difficult. The viscosity can be reduced by adding n-dodecane (100%; 0.16 kg, 0.215 L) to the resulting homogeneous reaction mixture. The n-dodecane runs into the reactor head as an aerosol during the reaction and must be replenished in several portions. Total amount of n-dodecane (100%; 250 ml; 1.1 mol; 1.1 equivalents)

[0112] At the end of the distillation, 250 mL of (anhydrous / 100%) toluene was added (at approximately 100 °C and full stirring) to prepare a slurry. The toluene must be dried to a low water content (e.g., using molsieve, AlOx, or another suitable method) before addition, or purchased in anhydrous form. The toluene content must also be adapted to the existing filtration equipment, as sufficient dilution with toluene is required for transfer to the filtration equipment.

[0113] A cooling ramp (for laboratory tests) is maintained at -0.1 to 1 K / min down to a minimum of 20°C. The cooling procedure must be adapted to the equipment under consideration.

[0114] For washing, the slurry is pressed onto a filter. The residue is transferred onto the cake with 125 mL of toluene (anhydrous), and the filter cake is washed twice with 125 mL of toluene (anhydrous) each. The filter cake is then washed twice with 200 mL of dry MTBE each. The final product is dried under vacuum with the application of inert gas.

[0115] The bulk density (dry product) is approximately 0.94 kg / l.

[0116] Reaction of benzyloxyethanol to potassium benzyloxyethanolate with potassium tert-butoxide in continuous distillation [ka]

[0117] The desired reactor was inerted and kept free of water before carrying out the reaction. 232.7 g (99%; 1.5 mol; 1 eq.) of benzyloxyethanol was charged to the reactor, and 191.6 g (98%; 1.5 mol; 1 eq.) of potassium tert-butoxide was added under an inert and dry atmosphere, followed by inerting the reactor. The reaction mass was heated to 110 °C with constant stirring, and nitrogen was introduced into the mass. An anchor stirrer with a total impeller diameter of 90 mm was used. Toluene was continuously introduced into the reaction mass (1 mL / min) using a capillary. The nitrogen flow was maintained at approximately 100 L / h of dry nitrogen throughout the distillation. tert-Butyl alcohol and toluene were distilled off over a reaction time of approximately 5.5 hours, during which a thicker suspension was obtained. The reaction was terminated by lowering the temperature to 20 °C, and the mass was diluted after 6 hours and uniformly discharged from the reaction vessel.

[0118] The cooling ramp is maintained at -0.1 to 1 K / min down to a minimum of 20° C. The cooling procedure must be adapted to the device under consideration.

[0119] The slurry was pressed onto a filter. The residue was transferred with 50 mL of toluene (anhydrous) and the filter cake was washed twice with 50 mL of toluene (anhydrous) each. The filter cake was then washed twice with 200 mL of dry MTBE each. The final product was dried under inert conditions and under vacuum. Yield: 90.1%. Purity titration: 99.1% by weight.

Claims

1. 1. A method for producing an alkali metal alkoxide, comprising the steps of: i) providing in a reaction vessel in an inert atmosphere an organic compound having at least one —OH group and a molecular weight of 75 to 750 g / mol; ii) C １～６ adding an alkali metal alcoholate to obtain a reaction mixture; iii) heating the reaction mixture of step ii) to 25-180°C under stirring to obtain a mixture of the alkali metal alkoxide and C １～６ Obtaining alcohol; and iv) The obtained C １～６ distilling off the alcohol, wherein at least one non-polar solvent having a boiling point higher than that of the obtained alcohol is added to the mixture continuously or batchwise while distilling. A method comprising:

2. 2. The method of claim 1, wherein the organic compound having at least one —OH group is selected from substituted or unsubstituted aliphatic or aromatic hydrocarbons, silyl ethers, polyols, ethers, and polyethers, or mixtures thereof.

3. Said C １～６ 3. The method according to claim 1, wherein the alkali metal alcoholate is selected from potassium methanolate, potassium ethanolate, potassium 2-methylpropan-2-olate, potassium propan-2-olate, potassium propan-1-olate, potassium butan-2-olate, and potassium tert-butoxide.

4. 4. The method according to claim 1, wherein the at least one solvent is a non-polar and aprotic solvent, such as an aromatic hydrocarbon, an aliphatic hydrocarbon, or an ether.

5. the reactor is equipped with a rotating element for agitation; preferably 5. The method according to claim 1, wherein the at least one non-polar solvent is added when the moment of force M of the rotating element increases by at least 1.5 times, and wherein after the addition of the at least one non-polar solvent, the moment of force M decreases by at least 1.5 times.

6. 6. The method according to any one of claims 1 to 5, wherein the at least one non-polar solvent is present in an amount of 1 ml / mmol to 20 ml / mmol relative to the organic compound having at least one -OH group and having a molecular weight of 75 to 750 g / mol.

7. 7. The method according to any one of claims 1 to 6, wherein the reaction time is at least 3 hours.

8. 8. The method of claim 1, wherein the at least one non-polar solvent is washed off after reaction with a volatile non-polar solvent.

9. The organic compound having at least one —OH group and a molecular weight of 75 to 750 g / mol and the C １～６ 9. The process according to any one of claims 1 to 8, wherein the alkali metal alcoholate is present in a molar ratio of from 2:1 to 1:1.

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