CN114315539A - Process for preparing 1, 3-cyclohexanedione - Google Patents
Process for preparing 1, 3-cyclohexanedione Download PDFInfo
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- CN114315539A CN114315539A CN202011064973.3A CN202011064973A CN114315539A CN 114315539 A CN114315539 A CN 114315539A CN 202011064973 A CN202011064973 A CN 202011064973A CN 114315539 A CN114315539 A CN 114315539A
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- acid
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- cyclohexanedione
- hydrogenation reduction
- hydrochloric acid
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- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002253 acid Substances 0.000 claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 45
- 230000009467 reduction Effects 0.000 claims abstract description 42
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000020477 pH reduction Effects 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 74
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000005578 Mesotrione Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 239000005618 Sulcotrione Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 material monomers Chemical class 0.000 description 1
- KPUREKXXPHOJQT-UHFFFAOYSA-N mesotrione Chemical compound [O-][N+](=O)C1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O KPUREKXXPHOJQT-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- PQTBTIFWAXVEPB-UHFFFAOYSA-N sulcotrione Chemical compound ClC1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O PQTBTIFWAXVEPB-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of organic synthesis, and discloses a preparation method of 1, 3-cyclohexanedione. The method comprises the following steps: the method comprises the steps of using resorcinol as a raw material, and carrying out hydrogenation reduction and acidification crystallization, wherein the acidification crystallization comprises the following steps: a) contacting the hydrogenation reduction product with a first acid to ensure that the pH of the contacted product is 4-7, adding seed crystals, and keeping the temperature at 0-25 ℃ for 1-3 h; b) adjusting the pH of the product obtained in step a) to 1-3 by means of a second acid and maintaining the pH at 5-15 ℃ for 0.1-2 h. The 1, 3-cyclohexanedione prepared by the method provided by the invention has high purity, high yield and stable crystal form.
Description
Technical Field
The invention relates to the field of organic synthesis, and particularly relates to a preparation method of 1, 3-cyclohexanedione.
Background
The 1, 3-cyclohexanedione is used as an intermediate for organic synthesis, can be used for synthesizing various organic compounds such as material monomers, curing agents, solvents and the like, and is an intermediate of herbicide sulcotrione and mesotrione.
In the existing preparation method of 1, 3-cyclohexanedione, resorcinol is generally used as a starting material, and a 1, 3-cyclohexanedione product is obtained through hydrogenation reduction, acidification and recrystallization, and the preparation route is as follows.
No reports on 1, 3-cyclohexanedione in a stable crystal form exist in the prior art, such as CN200510489576.X, CN201110419160.6, JP0413644 and JP20013421632001, all of which are selected through catalysts, and have large influence on product selectivity and yield.
Therefore, it is urgently needed to provide a preparation method of 1, 3-cyclohexanedione with high purity, high yield and stable crystal form.
Disclosure of Invention
The invention aims to solve the problems of small particle size, low purity, unstable crystal form and the like of 1, 3-cyclohexanedione in the preparation process of a 1, 3-cyclohexanedione reaction liquid in the prior art, and provides a preparation method of 1, 3-cyclohexanedione, which has the advantages of high purity, high yield, stable crystal form, high storage stability and the like of the prepared 1, 3-cyclohexanedione.
In order to achieve the above object, the present invention provides a method for preparing 1, 3-cyclohexanedione, comprising: the method comprises the steps of using resorcinol as a raw material, and carrying out hydrogenation reduction and acidification crystallization, wherein the acidification crystallization comprises the following steps:
a) contacting the hydrogenation reduction product with a first acid to ensure that the pH of the contacted product is 4-7, adding seed crystals, and keeping the temperature at 0-25 ℃ for 1-3 h;
b) adjusting the pH of the product obtained in step a) to 1-3 by means of a second acid and maintaining the pH at 5-15 ℃ for 0.1-2 h.
Preferably, in step a), after contacting the hydrogenation reduction product with the first acid and making the pH of the product after contacting 4-6, seed crystals are added and kept at 5-15 ℃ for 1.5-2.5 h.
Preferably, in step b), the pH of the product obtained in step a) is adjusted by the second acid to 1.5-2.5 and maintained at 5-10 ℃ for 0.5-1.5 h.
Preferably, the first acid is one or more of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the first acid is hydrochloric acid and/or sulfuric acid.
Preferably, the concentration of the first acid is 0.5 to 50 wt%.
Preferably, the second acid is one or more of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the second acid is hydrochloric acid and/or sulfuric acid.
Preferably, the concentration of the second acid is 0.5 to 50 wt%.
Preferably, the first acid is the same as the second acid.
Preferably, the method further comprises the steps of carrying out solid-liquid separation and drying on the acidified crystallization product.
Preferably, the conditions of the hydrogenation reduction include: the pressure is 0.5-10MPa, and the temperature is 50-150 ℃.
Through the technical scheme, the purity of the 1, 3-cyclohexanedione prepared by the technical scheme is more than 98.5%, the yield is more than 90%, and the product is crystalline and stable in the storage and transportation processes.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of 1, 3-cyclohexanedione obtained in inventive example 1.
Detailed Description
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, one or more new ranges of values may be obtained from combinations of values between the endpoints of each range, the endpoints of each range and the individual values, and the individual values of the points, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of 1, 3-cyclohexanedione, which comprises the following steps: the method comprises the steps of using resorcinol as a raw material, and carrying out hydrogenation reduction and acidification crystallization, wherein the acidification crystallization comprises the following steps:
a) contacting the hydrogenation reduction product with a first acid to ensure that the pH of the contacted product is 4-7, adding seed crystals, and keeping the temperature at 0-25 ℃ for 1-3 h;
b) adjusting the pH of the product obtained in step a) to 1-3 by means of a second acid and maintaining the pH at 5-15 ℃ for 0.1-2 h.
In the invention, the preparation yield is greatly improved by controlling the acidification crystallization process, and the recovered product is crystalline, large in particle and high in purity.
The method for preparing the 1, 3-cyclohexanedione by using the resorcinol as the raw material through hydrogenation reduction, acidification and crystallization has the following reaction route:
as a specific method for the above-mentioned hydrogenation reduction, any conventional method which can hydrogenate resorcinol can be used, and resorcinol and an inorganic strong base may be neutralized to form a salt and then subjected to hydrogenation reduction in the presence of a catalyst. For example, resorcinol and sodium hydroxide in a mass ratio of 1: 1 to 1.5 may be neutralized and then hydrogenated at 0.5 to 10MPa and 50 to 150 ℃ in the presence of a hydrogenation catalyst.
The hydrogenation catalyst may be various catalysts generally used in the art for hydrogenation reduction, and may be, for example, palladium on carbon or raney nickel catalyst.
According to the invention, after the hydrogenation reduction, the product of the hydrogenation reduction is subjected to the particular acidification crystallization step according to the invention, which consists in:
a) contacting the hydrogenation reduction product with a first acid to ensure that the pH of the contacted product is 4-7, adding seed crystals, and keeping the temperature at 0-25 ℃ for 1-3 h;
b) adjusting the pH of the product obtained in step a) to 1-3 by means of a second acid and maintaining the pH at 5-15 ℃ for 0.1-2 h.
In order to further promote the improvement of the yield of the preparation and the purity of the prepared product, in the invention, preferably, in the step a), after the hydrogenation reduction product is contacted with the first acid and the pH of the contacted product is 4-6, seed crystals are added and kept for 1.5-2.5h at the temperature of 5-15 ℃; more preferably, in step a), after contacting the hydrogenation reduction product with the first acid and bringing the pH of the product after contact to 4.2-5.8, seed crystals are added and kept at 5-15 ℃ for 1.5-2.5 h.
In order to further facilitate the improvement of the yield of the preparation and the purity of the product obtained, in the present invention, it is preferred that in step b), the pH of the product obtained in step a) is adjusted to 1.5-2.5 by the second acid and maintained at 5-10 ℃ for 0.5-1.5 h.
There is no particular limitation on the acid used in the above-mentioned acidifying crystallization process, and in the present invention, it is preferable that the first acid is one or more of hydrochloric acid, sulfuric acid, and nitric acid; more preferably, the first acid is hydrochloric acid and/or sulfuric acid. In one embodiment of the invention, the first acid is hydrochloric acid.
The concentration of the first acid is not particularly limited, and in the present invention, it is preferable that the concentration of the first acid is 0.5 to 50 wt%; more preferably, the concentration of the first acid is 5 to 20 wt%. In one embodiment of the present invention, the first acid is hydrochloric acid having a concentration of 5 wt%; in another embodiment of the present invention, the first acid is hydrochloric acid having a concentration of 10 wt%; in another embodiment of the present invention, the first acid is hydrochloric acid having a concentration of 15 wt%.
The concentration of the above second acid is not particularly limited, and in the present invention, it is preferable that the concentration of the second acid is 0.5 to 50 wt%; more preferably, the concentration of the second acid is 5 to 20 wt%.
For further ease of handling, in the present invention, preferably the first acid is the same as the second acid. In one embodiment of the invention, the first acid is hydrochloric acid at a concentration of 5 wt% as the second acid; in another embodiment of the present invention, the first acid is hydrochloric acid at a concentration of 10 wt% as the second acid; in another embodiment of the present invention, the first acid is hydrochloric acid with a concentration of 15 wt% as the second acid.
The content of the 1, 3-cyclohexanedione in the above-mentioned hydrogenation-reduction product may be from 0.5 to 50% by weight, preferably from 20 to 40% by weight. By using the hydrogenation reduction product with the concentration content of the 1, 3-cyclohexanedione, the purity and the yield of the 1, 3-cyclohexanedione can be further improved. In one embodiment of the invention, a hydrogenation reduction product having a 1, 3-cyclohexanedione content of 30% by weight is used.
The amount of the seed crystal to be added may be, for example: the seed crystal is added in an amount of 0.1 to 5g, preferably 0.1 to 1g, more preferably 0.4 to 0.6g, relative to 100g of the hydrogenation-reduction product. In one embodiment of the invention, 0.5g of seed crystals are added to 100g of the product of the hydrogenation reduction.
In the invention, the method also comprises the steps of carrying out solid-liquid separation and drying on the acidified crystallized product.
The solid-liquid separation can be carried out by adopting a standing liquid separation mode, a filtration mode or a centrifugal separation mode, and the separation can be realized. In one embodiment of the present invention, the acidified crystalline product is filtered and dried to obtain the 1, 3-cyclohexanedione product.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
In the following examples, "yield" refers to the formula of the 1, 3-cyclohexanedione obtained relative to the product obtained by hydrogenation reduction
Molar yield of the compound shown.
Example 1
(1) Reducing the temperature of 400g (0.548mol) of hydrochloric acid with the concentration of 5 weight percent to 5 ℃;
(2) dropwise adding 200g of hydrochloric acid (the content of 1, 3-cyclohexanedione in the hydrogenation reduction product is 30 wt%, and 0.536mol) into the hydrogenation reduction product in the step (1), dropwise adding until the pH value is 4.5, stopping dropwise adding, adding 1g of seed crystal, controlling the temperature to keep at 5 ℃, stirring for 2 hours, continuously dropwise adding hydrochloric acid until the pH value of the hydrogenation reduction product is 2, keeping the temperature at 5 ℃ for 1 hour, filtering and drying the acidified crystallization product to obtain the product, wherein the content of 1, 3-cyclohexanedione is 99.3%, the yield is 90.2%, and the XRD spectrogram of the crystal form of the prepared 1, 3-cyclohexanedione is shown in figure 1.
Example 2
(1) 200g (0.548mol) of hydrochloric acid with the concentration of 10 wt% is cooled to 10 ℃;
(2) dropwise adding 200g of hydrochloric acid (the content of 1, 3-cyclohexanedione in the hydrogenation reduction product is 30 wt%, and 0.536mol) into the hydrogenation reduction product in the step (1), dropwise adding until the pH is 5, stopping dropwise adding, adding 1g of seed crystal, controlling the temperature to be kept at 10 ℃, stirring for 2 hours, continuously dropwise adding hydrochloric acid until the pH of the hydrogenation reduction product is 2, keeping the temperature at 10 ℃ for 1 hour, filtering and drying the acidification crystallization product to obtain the product, wherein the content of 1, 3-cyclohexanedione is 98.8%, and the yield is 90.57%.
Example 3
(1) Reducing the temperature of 133.3g (0.548mol) of hydrochloric acid with the concentration of 15 wt% to 15 ℃;
(2) dropwise adding 200g of hydrochloric acid (the content of 1, 3-cyclohexanedione in the hydrogenation reduction product is 30 wt%, and 0.536mol) into the hydrogenation reduction product in the step (1), dropwise adding until the pH is 5.5, stopping dropwise adding, adding 1g of seed crystal, controlling the temperature to keep at 15 ℃, stirring for 2 hours, continuously dropwise adding hydrochloric acid until the pH of the hydrogenation reduction product is 2, keeping the temperature at 15 ℃ for 1 hour, filtering and drying the acidified crystallization product to obtain the product, wherein the content of 1, 3-cyclohexanedione is 98.5%, and the yield is 90.62%.
Example 4
(1) Reducing the temperature of 400g (0.548mol) of hydrochloric acid with the concentration of 5 weight percent to 5 ℃;
(2) dropwise adding 200g of the hydrogenation reduction product (containing 30 wt% of 1, 3-cyclohexanedione and 0.536mol) by using the hydrochloric acid in the step (1), dropwise adding until the pH value is 4.2, stopping dropwise adding, adding 1g of seed crystal, controlling the temperature to be kept at 5 ℃, stirring for 2 hours, continuously dropwise adding the hydrochloric acid until the pH value of the hydrogenation reduction product is 2, keeping the temperature at 5 ℃ for 1 hour, filtering and drying the acidified crystallization product to obtain the product, wherein the content of the 1, 3-cyclohexanedione is 95.2%, and the yield is 90.1%.
Example 5
(1) Reducing the temperature of 400g (0.548mol) of hydrochloric acid with the concentration of 5 weight percent to 5 ℃;
(2) dropwise adding 200g of hydrochloric acid (the content of 1, 3-cyclohexanedione in the hydrogenation reduction product is 30 wt%, and 0.536mol) into the hydrogenation reduction product in the step (1), dropwise adding until the pH value is 4.7, stopping dropwise adding, adding 1g of seed crystal, controlling the temperature to keep at 5 ℃, stirring for 2 hours, continuously dropwise adding hydrochloric acid until the pH value of the hydrogenation reduction product is 2, keeping the temperature at 5 ℃ for 1 hour, filtering and drying the acidified crystallization product to obtain the product, wherein the content of 1, 3-cyclohexanedione is 94.3%, and the yield is 90.5%.
Example 6
(1) 400g (0.548mol) of hydrochloric acid having a concentration of 5% by weight is prepared at room temperature (25 ℃);
(2) dropwise adding 200g of the hydrogenation reduction product (the content of 1, 3-cyclohexanedione in the hydrogenation reduction product is 30 wt%, and 0.536mol) by using the hydrochloric acid in the step (1), dropwise adding until the pH value is 4.5, stopping dropwise adding, adding 1g of seed crystal, controlling the temperature to be kept at 25 ℃, stirring for 2 hours, continuously dropwise adding the hydrochloric acid until the pH value of the hydrogenation reduction product is 2, keeping the temperature at 25 ℃ for 1 hour, filtering and drying the acidified crystallization product to obtain the product, wherein the content of the 1, 3-cyclohexanedione is 97.2%, and the yield is 85.2%.
Comparative example 1
(1) Reducing the temperature of 400g (0.548mol) of hydrochloric acid with the concentration of 5 weight percent to 5 ℃;
(2) dropwise adding 200g of hydrogenation reduction product (containing 30 wt% of 1, 3-cyclohexanedione and 0.536mol) by hydrochloric acid in the step (1), stopping dropwise adding when the pH value is 2, adding 1g of seed crystal, controlling the temperature to be kept at 5 ℃, stirring for 2 hours, continuing to keep the temperature for 1 hour, filtering and drying the acidification crystallization product to obtain the product, wherein the content of the 1, 3-cyclohexanedione is 92.1%, and the yield is 90.6%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A process for preparing 1, 3-cyclohexanedione, which comprises: the method is characterized in that resorcinol is taken as a raw material, and is subjected to hydrogenation reduction and acidification crystallization, wherein the acidification crystallization comprises the following steps:
a) contacting the hydrogenation reduction product with a first acid to ensure that the pH of the contacted product is 4-7, adding seed crystals, and keeping the temperature at 0-25 ℃ for 1-3 h;
b) adjusting the pH of the product obtained in step a) to 1-3 by means of a second acid and maintaining the pH at 5-15 ℃ for 0.1-2 h.
2. The method for preparing 1, 3-cyclohexanedione according to claim 1, wherein in step a), after the hydrogenation-reduction product is contacted with the first acid and the pH of the contacted product is 4 to 6, seed crystals are added and the reaction mixture is maintained at 5 to 15 ℃ for 1.5 to 2.5 hours.
3. The method for preparing 1, 3-cyclohexanedione according to claim 1 or 2, wherein in step b), the product obtained in step a) is adjusted to a pH of 1.5 to 2.5 by means of a second acid and is maintained at 5 to 10 ℃ for 0.5 to 1.5 h.
4. The method for producing 1, 3-cyclohexanedione according to any one of claims 1 to 3, wherein the first acid is one or more of hydrochloric acid, sulfuric acid and nitric acid;
preferably, the first acid is hydrochloric acid and/or sulfuric acid.
5. The method of producing 1, 3-cyclohexanedione according to claim 4, wherein the concentration of the first acid is from 0.5 to 50 wt%.
6. The method for producing 1, 3-cyclohexanedione according to any one of claims 1 to 4, wherein the second acid is one or more of hydrochloric acid, sulfuric acid and nitric acid;
preferably, the second acid is hydrochloric acid and/or sulfuric acid.
7. The method according to claim 6, wherein the concentration of the second acid is 0.5 to 50 wt%.
8. The method for producing 1, 3-cyclohexanedione according to any one of claims 1 to 4, wherein the first acid is the same as the second acid.
9. The process for producing 1, 3-cyclohexanedione according to any one of claims 1 to 4, wherein the process further comprises the step of subjecting the acidified crystalline product to solid-liquid separation and drying.
10. The method for producing 1, 3-cyclohexanedione according to any one of claims 1 to 4, wherein the conditions of the hydrogenation reduction comprise: the pressure is 0.5-10MPa, and the temperature is 50-150 ℃.
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Application publication date: 20220412 |