CN107324985B - Preparation method of beta-diketone compound - Google Patents
Preparation method of beta-diketone compound Download PDFInfo
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- 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
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Abstract
The invention relates to the field of compound preparation, and discloses a preparation method of a beta-diketone compound, wherein the method comprises the following steps: the methyl carboxylate is reacted with a ketone in the presence of the solvent of the present invention and a potassium alkali metal alkoxide. The method for preparing the beta-diketone compound has high yield and safety, and is suitable for industrial application. Particularly, when the method is used for preparing the 3, 5-heptanedione, the yield of the 3, 5-heptanedione reaches over 60 percent, and is far higher than the yield of the 3, 5-heptanedione prepared by taking DMF as a solvent in the prior art.
Description
Technical Field
The invention relates to the field of compound preparation, in particular to a preparation method of a beta-diketone compound.
Background
The beta-diketone compound is a compound with a special structure and is widely applied to the fields of catalysts, heat stabilizers, luminescent materials and the like.
It is well known that the ester ketone condensation process is a common process for preparing β -diketone compounds. For example, journal articles J.org.chem (Vol.50.No26.1985.5598-5604) reported the preparation of 3, 5-heptanedione in 48.3% yield by reacting ethyl propionate with methyl ethyl ketone in the presence of sodium hydride in tetrahydrofuran as solvent.
In journal literature Zhumanal Obshcheni Khimii (1958, 28, 2845-2846), malonyl chloride is reacted with Grignard reagent EtMgBr to synthesize 3, 5-heptanedione with a yield of 51%. The reaction conditions are-70 ℃ and difficult to handle, so that the industrialization is difficult.
In view of the above, there is no method for producing a β -diketone compound safely and in high yield in the existing art.
Disclosure of Invention
The invention aims to overcome the defects of low yield and unsafe beta-diketone compound prepared by the prior art and provides a preparation method of the beta-diketone compound.
In order to achieve the above object, the present invention provides a method for preparing a β -diketone compound represented by formula (4), wherein the method comprises: reacting a methyl carboxylate represented by formula (1) with a ketone represented by formula (2) in the presence of a solvent represented by formula (3) and a potassium alkali metal alkoxide;
CH3O-CO-CR1R2R3formula (1);
CH3-CO-CR1R2R3formula (2);
R4O-(CH2(CH2)nO)m-R4formula (3);
R3R2R1C-CO-CH2-CO-CR1R2R3formula (4);
wherein R is1、R2And R3Each independently is hydrogen or C1-C4Alkyl groups of (a);
wherein n and m are the same or different, and n and m are each independently selected from 1, 2 or 3; r4Is methyl or ethyl.
The method for preparing the beta-diketone compound has high yield and safety, and is suitable for industrial application. Particularly, when the method is used for preparing the 3, 5-heptanedione, the yield of the 3, 5-heptanedione reaches over 60 percent, and is far higher than the yield of the 3, 5-heptanedione prepared by taking DMF as a solvent in the prior art.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides a method for producing a β -diketone compound represented by formula (4), wherein the method comprises: reacting a methyl carboxylate represented by formula (1) with a ketone represented by formula (2) in the presence of a solvent represented by formula (3) and a potassium alkali metal alkoxide;
CH3O-CO-CR1R2R3formula (1);
CH3-CO-CR1R2R3formula (2);
R4O-(CH2(CH2)nO)m-R4formula (3);
R3R2R1C-CO-CH2-CO-CR1R2R3formula (4);
wherein R is1、R2And R3Each independently is hydrogen or C1-C4Alkyl of (2), e.g. R1、R2And R3May each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, one of n-butyl, sec-butyl, isobutyl and tert-butyl; preferably, R1、R2And R3Each independently is hydrogen or C1-C2Alkyl groups of (a) may each independently be hydrogen, methyl or ethyl, for example; more preferably, the methyl carboxylate represented by formula (1) is methyl propionate, and the ketone represented by formula (2) is methyl ethyl ketone.
In formula (3), n and m are the same or different, and n and m are each independently selected from 1, 2 or 3; preferably, n and m are both 1; or n is 1 and m is 2 or 3; more preferably, n is 1 and m is 2.
In the formula (3), R4Is methyl or ethyl, preferably methyl.
Most preferably, the solvent represented by formula (3) is diethylene glycol dimethyl ether.
In the present invention, the amount of the solvent to be used is not particularly limited as long as stirring of the reaction system can be achieved. However, in order to improve the reaction efficiency, it is preferable that the molar ratio of the amount of the solvent to the amount of the ketone is 0.9 to 5: 1, preferably 1 to 4: 1, more preferably 0.97 to 3: 1.
in the present invention, the alkali metal potassium alkoxide functions to increase the affinity for the alpha carbon of the ketone and facilitate the acylation reaction. In the present invention, the amount of the alkali metal potassium alkoxide used is not particularly limited as long as the reaction proceeds smoothly. However, if the amount of the alkali metal potassium alkoxide used is too small, the reaction effect is deteriorated; if the amount of the alkali metal potassium alkoxide is too large, side reactions may be caused to lower the yield. Therefore, preferably, the molar ratio of the amount of the alkali metal potassium alkoxide to the amount of the ketone is 1 to 1.25: 1, more preferably 1-1.2: 1, more preferably 1 to 1.1: 1.
in the present invention, the selection of the alkali metal potassium alkoxide is not particularly limited, and may be a selection conventionally used in the art, and for example, may be at least one of potassium methoxide, potassium ethoxide, potassium n-propoxide, potassium isopropoxide, potassium n-butoxide, potassium isobutoxide, potassium sec-butoxide, and potassium tert-butoxide; preferably, the alkali metal potassium alkoxide is at least one of potassium methoxide, potassium ethoxide, and potassium tert-butoxide.
In the present invention, the amount of the methyl carboxylate is not particularly limited and may be selected conventionally in the art. However, if the amount of the ketone is much larger than that of the methyl carboxylate, the yield of the target product is lowered due to the effect of self-condensation of the ketone; if the amount of methyl carboxylate is much greater than the amount of ketone, a large amount of unreacted methyl carboxylate must be recycled. Therefore, preferably, the molar ratio of the amount of the methyl carboxylate to the amount of the ketone is 3 to 10: 1, preferably 3 to 4.1: 1.
in the present invention, the reaction conditions are not particularly limited, and may be those conventional in the art. However, if the reaction temperature is too low, the reactivity becomes poor and the reaction time is prolonged, resulting in a decrease in productivity; if the reaction temperature is too high, waste of solvent and reactants occurs and more side reactions occur to decrease the product yield. Therefore, preferably, the reaction conditions include: the temperature is 0-100 ℃, preferably 60-75 ℃; the time is 2-6h, preferably 4-5 h.
In the present invention, the method of adding the reactants is not particularly limited, and may be a method conventionally used in the art. Preferably, the solvent and the potassium alkali metal alkoxide are first mixed to obtain a mixture, and then the mixture of the methyl carboxylate and the ketone is added dropwise to the mixture. Preferably, the dropping time is 10 to 60min, more preferably 20 to 40 min. In the present invention, "dropping" means dropping the mixed solution into the mixture at a substantially uniform speed for a predetermined time.
In the present invention, the method may further include: after the reaction is completed, the β -diketone compound represented by the formula (4) is separated from the reaction product. Specifically, adding water into the reaction product, adjusting the pH value to 6-7 by concentrated hydrochloric acid, cooling to room temperature, filtering to separate inorganic salt, separating an organic layer and a water layer, rectifying and purifying the organic layer, and separating unreacted raw materials, solvent and other impurities.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the β -diketone compound was quantitatively determined by gas chromatography external standard method;
method for calculating the yield in the following examples and comparative examples:
yield of β -diketone compound (molar amount of β -diketone compound produced/molar amount of reactant ketone) × 100%
Example 1
135g (1.2mol) of potassium tert-butoxide (obtained from Chemicals, Inc., national pharmacy Co., Ltd., abbreviated as "national pharmacy Co., the same applies hereinafter) and 104.5g (1.16mol) of ethylene glycol dimethyl ether (obtained from national pharmacy Co., Ltd.) were charged in a 1 liter four-neck flask, and heated under reflux to 20 ℃ with stirring by a mechanical stirrer. Then, a liquid mixture composed of 319g (3.6mol) of methyl propionate (from TCI, Japan) and 86.5g (1.2mol) of methyl ethyl ketone (from Chinese medicine) was added at a constant rate through a constant pressure dropping funnel, the dropping time was 20min, and then stirring was further carried out at 75 ℃ for 4.5 hours, the temperature was lowered to 40 ℃, 120g of ice water was added, and the pH was adjusted to 6 with concentrated hydrochloric acid. Then, the mixture was filtered through a suction flask to remove potassium chloride, and the filtrate was separated into an organic layer and an aqueous layer. As a result of gas chromatography analysis of the organic layer, 103g (0.80mol) of 3, 5-heptanedione was produced with a yield of 66.6% (based on butanone).
Example 2
13.6g (0.12mol) of potassium tert-butoxide (purchased from Takara Shuzo Co., Ltd.) and 40mL (0.28mol) of diethylene glycol dimethyl ether were charged in a 250mL three-necked flask, and heated under reflux with stirring by a mechanical stirrer to 60 ℃. Then, a liquid mixture composed of 39mL (0.41mol) of methyl propionate (purchased from TCI, Japan) and 9mL (0.1mol) of methyl ethyl ketone (purchased from Chinese medicine) was added at a constant rate through a constant pressure dropping funnel for 40min, followed by stirring at 60 ℃ for 4.5 hours, cooling to 40 ℃, adding 20g of ice water, and adjusting the pH to 6 with concentrated hydrochloric acid. Then, the mixture was filtered through a suction flask to remove potassium chloride, and the filtrate was separated into an organic layer and an aqueous layer. The organic layer was analyzed by gas chromatography, whereby the yield of 3, 5-heptanedione was 64.3% (based on butanone).
Example 3
148g (1.32mol) of potassium tert-butoxide (Takara Shuzo Co., Ltd.) and 324.4g (3.6mol) of ethylene glycol dimethyl ether (Takara Shuzo Co., Ltd.) were placed in a 1 liter four-necked flask, and heated under reflux with stirring by a mechanical stirrer to 20 ℃. Then, a liquid mixture composed of 370g (4.2mol) of methyl propionate (available from TCI, Japan) and 86.5g (1.2mol) of methyl ethyl ketone (available from Chinese medicine) was added at a constant rate through a constant pressure dropping funnel, the dropping time was 30min, and then stirring was further carried out at 65 ℃ for 4.5 hours, the temperature was lowered to 40 ℃, 120g of ice water was added, and the pH was adjusted to 6 with concentrated hydrochloric acid. Then, the mixture was filtered through a suction flask to remove potassium chloride, and the filtrate was separated into an organic layer and an aqueous layer. The organic layer was analyzed by gas chromatography, whereby the yield of 3, 5-heptanedione was 62.2% (based on butanone).
Example 4
27.2g (0.24mol) of potassium tert-butoxide (from national pharmacy) and 43ml (0.24mol) of triethlyme-thylether (from Aladdin) are added in a 250ml three-necked flask, 69ml (0.72mol) of methyl propionate and 21.5ml (0.24mol) of butanone are added dropwise at a uniform rate at 60 ℃ for 40min, then stirred at 75 ℃ for 4.5 hours, cooled to 40 ℃, 24g of ice water is added, and the pH is adjusted to 6 with concentrated hydrochloric acid. Then, the mixture was filtered through a suction flask to remove potassium chloride, and the filtrate was separated into an organic layer and an aqueous layer. As a result of gas chromatography analysis of the organic layer, 19g (0.148mol) of 3, 5-heptanedione was produced with a yield of 61.7% based on butanone.
Example 5
27.2g (0.24mol) of potassium tert-butoxide (from Takara Shuzo Co., Ltd.) and 34ml (0.24mol) (Tianjin shin-Shenjing chemical research institute) of diethanol dimethyl ether were charged into a 250ml three-necked flask, 69ml (0.72mol) of methyl propionate (from TCI Co., Japan) and 21.5ml (0.24mol) of methyl ethyl ketone (from Takara Shuzo Co., Ltd.) were added dropwise at 60 ℃ over 40min, followed by stirring at 75 ℃ for 4.5 hours, cooling to 40 ℃, 24g of ice water was added, and the pH was adjusted to 6 with concentrated hydrochloric acid. Then, the mixture was filtered through a suction flask to remove potassium chloride, and the filtrate was separated into an organic layer and an aqueous layer. As a result of gas chromatography analysis of the organic layer, 18.8g (0.146mol) of 3, 5-heptanedione was produced with a yield of 60.8% (based on butanone).
Example 6
3, 5-heptanedione was prepared according to the method of example 1 except that "then stirred at 75 ℃ for 4.5 hours" of example 1 was changed to "then stirred at 60 ℃ for 4.5 hours". It was confirmed by gas chromatography that 92.7g (0.72mol) of 3, 5-heptanedione was produced in the solution in a yield of 60.3% (based on butanone).
Comparative example 1
3, 5-heptanedione was prepared by the method of example 1, except that 1.2mol of sodium hydride (50%) and 1.2mol of tetrahydrofuran were charged in a 1-liter four-necked flask. The organic layer was analyzed by gas chromatography, whereby the yield of 3, 5-heptanedione was 50% (based on butanone).
Comparative example 2
3, 5-heptanedione was prepared by the method of example 1, except that 1.2mol of potassium tert-butoxide and 1.2mol of DMF were added in a 1 liter four-necked flask and heated to 50 ℃ with stirring by a mechanical stirrer. The organic layer was analyzed by gas chromatography, whereby the yield of 3, 5-heptanedione was 45% (based on methyl ethyl ketone).
Comparative example 3
3, 5-heptanedione was prepared by the method of example 1, except that 1.2mol of potassium tert-butoxide and 1.2mol of toluene were added in a 1 liter four-necked flask, and heated to 60 ℃ with stirring by a mechanical stirrer. The organic layer was analyzed by gas chromatography, whereby the yield of 3, 5-heptanedione was 46% (based on butanone).
Comparative example 4
3, 5-heptanedione was prepared by the method of example 1, except that the solvent ethylene glycol dimethyl ether (1.16mol) was changed to methyl propionate (1.15 mol). The organic layer was analyzed by gas chromatography, whereby the yield of 3, 5-heptanedione was 5% (based on methyl ethyl ketone).
Comparative example 5
281g (2.5mol) of potassium tert-butoxide (available from Kokai Co.) and 553g (6mol) of methyl propionate (available from Nippon TCI Co.) were charged in a 1 liter four-necked flask, heated to 70 ℃ with stirring, and then 72g (1mol) of methyl ethyl ketone (available from Kokai Co.) was charged over 5 hours with a dropping funnel, followed by continuing the reaction with stirring at 70 ℃ for 5 hours, then cooled to room temperature, added with 200g of water, adjusted to pH 7 with dilute hydrochloric acid, and the reaction solution was allowed to stand to layer, and an organic layer was separated. The organic layer was analyzed by gas chromatography, whereby the yield of 3, 5-heptanedione was 30% (based on methyl ethyl ketone).
As is clear from comparison of comparative examples 1-2 with examples 1-6, the method for producing a β -diketone compound (particularly 3, 5-heptanedione) according to the present invention, using the compound represented by formula (3) as a solvent, has a higher yield than the prior art using water-soluble aprotic solvents such as tetrahydrofuran and DMF.
As is clear from comparison of comparative example 3 with examples 1 to 6, the method for producing a β -diketone compound (particularly 3, 5-heptanedione) according to the present invention, using the compound represented by formula (3) as a solvent, has a higher yield than the prior art, which uses toluene, which is a water-insoluble solvent.
Comparative examples 4 to 5, which have a low yield of 3, 5-heptanedione using methyl propionate as a solvent as a reactant, were compared with examples 1 to 6.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (14)
1. A method for producing a β -diketone compound represented by the formula (4), comprising: reacting a methyl carboxylate represented by formula (1) with a ketone represented by formula (2) in the presence of a solvent represented by formula (3) and a potassium alkali metal alkoxide;
CH3O-CO-CR1R2R3formula (1);
CH3-CO-CR1R2R3formula (2);
R4O-(CH2(CH2)nO)m-R4formula (3);
R3R2R1C-CO-CH2-CO-CR1R2R3formula (4);
wherein the methyl carboxylate represented by the formula (1) is methyl propionate;
wherein, the ketone shown in the formula (2) is butanone;
in formula (3), n is 1, m is selected from 1, 2 and 3; r4Is methyl or ethyl;
the alkali metal potassium alkoxide is potassium tert-butoxide.
2. The method according to claim 1, wherein the solvent represented by formula (3) is ethylene glycol dimethyl ether.
3. The process according to any one of claims 1-2, wherein the molar ratio of the amount of solvent to the amount of ketone is from 0.9 to 5: 1.
4. the process according to any one of claims 1-2, wherein the molar ratio of the amount of solvent to the amount of ketone is 1-4: 1.
5. the process according to any one of claims 1-2, wherein the molar ratio of the amount of solvent to the amount of ketone is from 0.97 to 3: 1.
6. the process of any of claims 1-2, wherein the molar ratio of the amount of potassium alkali alkoxide to the amount of ketone is from 1 to 1.25: 1.
7. the process according to any one of claims 1-2, wherein the molar ratio of the amount of methyl carboxylate to the amount of ketone is from 3 to 10: 1.
8. the process according to any one of claims 1-2, wherein the molar ratio of the amount of methyl carboxylate to the amount of ketone is from 3 to 4.1: 1.
9. the method of any one of claims 1-2, wherein the reaction conditions comprise: the temperature is 0-100 ℃; the time is 2-6 h.
10. The method of any one of claims 1-2, wherein the reaction conditions comprise: the temperature is 60-75 ℃; the time is 4-5 h.
11. The method according to any one of claims 1-2, wherein the method further comprises: the solvent and the potassium alkali metal alkoxide are first mixed to obtain a mixture, and then the mixture of the methyl carboxylate and the ketone is added dropwise to the mixture.
12. The method of claim 11, wherein the dropping is for a period of 10-60 min.
13. The method of claim 11, wherein the dropping is for a period of 20-40 min.
14. The method according to any one of claims 1-2, wherein the method further comprises: after the reaction is completed, the β -diketone compound represented by the formula (4) is separated from the reaction product.
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