CN114380664A - Alkali metal polyol salt and preparation method thereof - Google Patents
Alkali metal polyol salt and preparation method thereof Download PDFInfo
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- CN114380664A CN114380664A CN202210085687.8A CN202210085687A CN114380664A CN 114380664 A CN114380664 A CN 114380664A CN 202210085687 A CN202210085687 A CN 202210085687A CN 114380664 A CN114380664 A CN 114380664A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/28—Metal alcoholates
- C07C31/30—Alkali metal or alkaline earth metal alcoholates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
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- C—CHEMISTRY; METALLURGY
- 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
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An alkali metal polyol salt compound useful as a catalyst for aldol condensation reaction having the general formula: (MO) xR1(R2)(R3) (OH) n. Wherein M is an alkali metal, R1Is C2‑C20Alkyl radical, R2And R3Is straight-chain or branched C1‑C5Alkyl of R2And R3May be the same. The number of hydroxyl groups in the alkali metal polyol salt compound is less than the number of hydroxyl groups in the starting alcohol, x + n is the number of hydroxyl groups in the starting alcohol, x is not less than 1, and n is not less than 0. The invention also relates to a preparation method of the compound. Due to the fact thatThe alcohol generated by the hydrolysis of the catalyst has a boiling point higher than that of the aldol condensation reaction material, so that the recovery of the reaction material is easily realized.
Description
Technical Field
The invention relates to a preparation method of a catalyst applicable to aldol condensation, in particular to an alkali metal polyol salt compound and a preparation method thereof.
Background
The aldol condensation reaction to produce corresponding beta-aldol or beta-ketal is one of the important reactions in organic synthesis, and the reaction is dehydrated to form alpha and beta-unsaturated aldehyde or ketone, and further hydrogenated to obtain saturated higher aldehyde or ketone. Is an important intermediate and solvent for many medicines, perfumes, additives and the like. At present, basic catalysts are commonly used for aldol condensation reactions. The traditional alkaline catalyst is commonly sodium hydroxide, potassium, sodium carbonate, potassium, organic amine and the like. The catalyst has low cost, high catalytic activity and low reaction selectivity. And sodium alkoxide is an alkali metal organic alkoxide which has been studied and applied earlier, and is useful as an organic synthesis intermediate, a strongly basic catalyst, a water absorbing agent, and the like. In an organic reaction system, the high-purity metal alkoxide has the advantages of high activity, good selectivity, high yield and the like.
At present, the most synthesis and application research in metal alkoxides is monobasic alkoxide, which mainly comprises sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert-butoxide and the like. The alkoxide is hydrolyzed in water to produce hydroxide and corresponding alcohol. Since the boiling point of the corresponding alcohol produced as a by-product is close to the boiling point of the starting material in the aldol condensation reaction, azeotropy is likely to be formed. So that the raw material and the alcohol are not easy to separate and the raw material waste is easy to cause. The use of metal alkoxides in aldol condensation reactions is severely affected.
Disclosure of Invention
The invention aims to provide an alkali metal polyhydric alkoxide compound which can be used as a catalyst for aldol condensation reaction, wherein the corresponding alcohol generated by hydrolysis of the compound has a high boiling point, and the boiling point is 100-450 ℃, preferably 120-420 ℃, and preferably 150-400 ℃.
It is another object of the present invention to provide a process for producing the alkali metal polyol salt compound of the present invention.
The invention provides an alkali metal polyalcohol compound used as an aldol condensation reaction catalyst, which is characterized in that the structural general formula of the compound is as follows:
(MO)xR1(R2)(R3)(OH)n (1)
wherein M is an alkali metal, R1Is C2-C20Alkyl radical, R2And R3Is straight chainOr C with a branched chain1-C5Alkyl of R2And R3May be the same. The number of hydroxyl groups in the alkali metal polyol salt compound is less than the number of hydroxyl groups in the starting alcohol, x + n is the number of hydroxyl groups in the starting alcohol, x is not less than 1, and n is not less than 0.
In the alkali metal polyol salt compound of the present invention, M is preferably Li, Na, K.
It is another object of the present invention to provide a process for producing the alkali metal polyol salt compound of the present invention. The method is simple to operate, and the product can be applied to aldol condensation reaction without purification. The preparation scheme adopted comprises the following steps:
(1) carrying out reduced pressure rectification on the polyhydric alcohol to remove water, and then mixing the polyhydric alcohol after water removal with an organic solvent;
(2) heating and preheating, adding excessive alkali metal hydroxide under the stirring state, introducing inert gas for protection, heating and refluxing for reaction for 2-10 h, and simultaneously separating water generated by the reaction of the system. When the reaction is finished, reduced pressure distillation is started to obtain a crude alkali metal polyol salt compound.
(3) Vacuum filtering to obtain solid matter. And then vacuum drying for 2-4 h, removing the solvent to obtain powdery alkoxide particles, and sealing and storing for later use.
In step (1) of the preparation method of the present invention, the organic solvent may be a hydrocarbon solvent, preferably an aromatic hydrocarbon solvent, such as benzene, toluene, ethylbenzene, etc.; the adding amount of the organic solvent is as follows: the ratio of the polyhydric alcohol/organic solvent is 0.5 to 30(mol/L), preferably 0.8 to 20, and most preferably 1 to 10.
In the step (2) of the preparation method of the present invention, the amount of the alkali metal hydroxide is: the molar ratio of M to polyol is 1:1 to 5:1, preferably 1.1:1 to 4:1, and most preferably 1.2:1 to 3: 1.
In the step (2) of the preparation method, the reaction temperature is usually in the range of 60-350 ℃, preferably 70-320 ℃, and most preferably 80-300 ℃.
In step (2) of the preparation method of the present invention, the reaction is preferably carried out under an inert gas atmosphere, for example, under the protection of argon or nitrogen.
The alkali metal polyhydric alkoxide compound can be used for various aldol condensation reactions and used as a catalyst to initiate condensation of ketone compounds and aldehyde compounds.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
The ethylene glycol solution is rectified under reduced pressure for 2 hours at the temperature of 80 ℃ to remove water. 11.6g of purified ethylene glycol was taken and put into a 250ml three-necked flask, and 187ml of toluene was added thereto. The temperature is increased to 80 ℃, and the mechanical stirring is carried out for 2 hours. Then 9g NaOH was added, nitrogen was introduced for three times for replacement, and an inert atmosphere was maintained. Heating to 125 ℃, mechanically stirring and refluxing for 6h, and separating water generated in the reaction process through a water separator. And when the reaction is finished, stopping heating, and starting reduced pressure distillation to obtain a crude product. The crude product was washed with organic ketone solvent by suction filtration under reduced pressure and finally dried under vacuum to give 6.1g of white powder. The final product is used as a catalyst for aldol condensation reaction, the dosage of the catalyst is 2 percent, the reaction temperature is 40 ℃, the reaction time is 5 hours, and the molar ratio of the raw materials of acetaldehyde, acetone and water is 1:5: 20. The acetaldehyde conversion was 72% and the selectivity was 80%.
Example 2
Rectifying the butanediol solution at 80 deg.C under reduced pressure for 2 hr to remove water. 10.3g of purified butanediol was charged into a 500ml three-necked flask, and 225ml of toluene was added thereto. The temperature is increased to 80 ℃, and the mechanical stirring is carried out for 3 hours. 13.7g of KOH were then added and replaced three times with argon, maintaining an inert atmosphere. Heating to 110 ℃, mechanically stirring and refluxing for 4h, and separating water generated in the reaction process through a water separator. And when the reaction is finished, stopping heating, and starting reduced pressure distillation to obtain a crude product. The crude product was washed with organic ketone solvent by suction filtration under reduced pressure and finally dried under vacuum to give 9.6g of white powder. The final product is used as a catalyst for aldol condensation reaction, the dosage of the catalyst is 2 percent, the reaction temperature is 40 ℃, the reaction time is 5 hours, and the molar ratio of the raw materials of acetaldehyde, acetone and water is 1:5: 20. The acetaldehyde conversion was 75% and the selectivity was 70%.
Example 3
Rectifying the glycerol solution at 80 deg.C under reduced pressure for 2 hr to remove water. 4.1g of the purified glycerol was taken and charged into a 500ml three-necked flask, and 222ml of toluene was added thereto. The temperature is increased to 80 ℃, and the mechanical stirring is carried out for 2 hours. Then 3.2g of LiOH was added and replaced three times with argon, maintaining an inert atmosphere. Heating to 130 ℃, mechanically stirring and refluxing for 5h, and separating water generated in the reaction process through a water separator. And when the reaction is finished, stopping heating, and starting reduced pressure distillation to obtain a crude product. The crude product was washed with organic ketone solvent by suction filtration under reduced pressure and finally dried under vacuum to give 5.4g of white powder. The final product is used as a catalyst for aldol condensation reaction, the dosage of the catalyst is 2 percent, the reaction temperature is 40 ℃, the reaction time is 5 hours, and the molar ratio of the raw materials of acetaldehyde, acetone and water is 1:5: 20. The acetaldehyde conversion was 74% and the selectivity was 82%.
Example 4
The neopentyl glycol solution was rectified under reduced pressure at 140 ℃ for 1h to remove water. 2.4g of the purified neopentyl glycol was charged into a 500ml three-necked flask, and 230ml of ethylbenzene was added thereto. The temperature is raised to 140 ℃, and the mechanical stirring is carried out for 4 hours. Then 2.76g NaOH was added and replaced three times with nitrogen, maintaining an inert atmosphere. Heating to 150 ℃, mechanically stirring and refluxing for 9h, and separating water generated in the reaction process through a water separator. And when the reaction is finished, stopping heating, and starting reduced pressure distillation to obtain a crude product. The crude product was washed with organic ketone solvent by suction filtration under reduced pressure and finally dried under vacuum to give 3.2g of white powder. The final product is used as a catalyst for aldol condensation reaction, the dosage of the catalyst is 2 percent, the reaction temperature is 40 ℃, the reaction time is 5 hours, and the molar ratio of the raw materials of acetaldehyde, acetone and water is 1:5: 20. The acetaldehyde conversion was 69% and the selectivity was 80%.
Example 5
Rectifying hexanetriol solution at 80 deg.C under reduced pressure for 2 hr to remove water. 8.1g of refined hexanetriol was taken and put into a 500ml three-necked flask, and 300ml of toluene was added. The temperature is increased to 80 ℃, and the mechanical stirring is carried out for 3 hours. Then 3.62g NaOH was added and replaced by three times with aeration, maintaining an inert atmosphere. Heating to 115 ℃, mechanically stirring and refluxing for 10h, and separating water generated in the reaction process through a water separator. And when the reaction is finished, stopping heating, and starting reduced pressure distillation to obtain a crude product. The crude product was washed with organic ketone solvent by suction filtration under reduced pressure and finally dried under vacuum to give 9.2g of white powder. The final product is used as a catalyst for aldol condensation reaction, the dosage of the catalyst is 2 percent, the reaction temperature is 40 ℃, the reaction time is 5 hours, and the molar ratio of the raw materials of acetaldehyde, acetone and water is 1:5: 20. The acetaldehyde conversion was 70% and the selectivity was 79%.
Compared with the existing catalyst, the catalyst prepared by the invention has the following beneficial effects in aldol condensation reaction. The alcohol generated by the catalyst byproduct prepared by the method has a higher boiling point compared with the reaction material, so that the separation difficulty is reduced, and the material turnover separation and other operations are reduced. The material consumption is reduced, and the cost advantage is obviously improved. The comparison of the boiling point of the alcohol compound obtained by the alkali metal polyalcohol catalyst and the common alkali metal monoalcohol catalyst after the reaction hydrolysis and the boiling point of the common raw material for aldol condensation reaction in the embodiment of the invention is shown in table 1.
TABLE 1 comparison of boiling points of alcohol compounds formed by hydrolysis of alkoxide catalysts with aldol condensation reaction starting materials
The alkali metal polyol salt catalyst prepared by the invention has good catalytic performance in aldol condensation reaction. The alcohol generated by the hydrolysis of the catalyst has higher boiling point relative to the reaction materials, is easy to separate from the raw materials of the aldol condensation reaction, and can reduce the material consumption.
Claims (7)
1. An alkali metal polyalcohol compound used as a catalyst for aldol condensation reaction, which is characterized in that the compound has the following structural general formula:
(MO)x R1(R2)(R3)(OH)n (1)
wherein M is an alkali metal, R1Is C2-C20Alkyl radical, R2And R3Is straight-chain or branched C1-C5X + n is the number of hydroxyl groups in the starting alcohol, x is not less than 1,n≥0。
2. alkali metal polyalkoxide compound according to claim 1, characterized in that M is one of Li, Na, K.
3. A process for preparing the alkali metal polyol salt compound of claims 1-2, comprising the steps of:
(1) carrying out reduced pressure rectification on the polyhydric alcohol to remove water, and then mixing the polyhydric alcohol after water removal with an organic solvent;
(2) heating and preheating, adding excessive alkali metal hydroxide in a stirring state, heating and refluxing for 2-10 h, and separating water generated in the reaction of the system; when the reaction is finished, reduced pressure distillation is started to obtain a crude alkali metal polyol salt compound.
4. The method according to claim 3, wherein the organic solvent is a hydrocarbon solvent, and the amount of the organic solvent added is: the polyol/organic solvent ratio is 0.5 to 30 (mol/L).
5. The method according to claim 3, wherein the alkali metal hydroxide is used in an amount of: m/polyol is 1:1 to 5:1 (molar ratio).
6. The method according to claim 3, wherein the reaction temperature is 60 to 350 ℃.
7. The method of claim 3, wherein the reaction is carried out under an inert gas atmosphere.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010065020A (en) * | 2008-08-13 | 2010-03-25 | Ehime Univ | Method for producing aldol condensation compound |
| CN101948386A (en) * | 2010-09-15 | 2011-01-19 | 宜兴市恒兴精细化工有限公司 | Method for preparing 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate |
| CN105646570A (en) * | 2015-11-06 | 2016-06-08 | 河南开祥精细化工有限公司 | Novel organic titanate butanediol titanium, and synthesis method and application thereof |
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- 2022-01-25 CN CN202210085687.8A patent/CN114380664A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010065020A (en) * | 2008-08-13 | 2010-03-25 | Ehime Univ | Method for producing aldol condensation compound |
| CN101948386A (en) * | 2010-09-15 | 2011-01-19 | 宜兴市恒兴精细化工有限公司 | Method for preparing 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate |
| CN105646570A (en) * | 2015-11-06 | 2016-06-08 | 河南开祥精细化工有限公司 | Novel organic titanate butanediol titanium, and synthesis method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| "13005-19-1/rn，2144747-73-7 /rn", STN REGISTRY * |
| 谭露璐 等: "醇醛缩合反应催化剂", 化学工业与工程, vol. 23, no. 1, pages 70 - 74 * |
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