CN113200833A - Preparation method of arylmethylene cyclohexenone compound - Google Patents
Preparation method of arylmethylene cyclohexenone compound Download PDFInfo
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- CN113200833A CN113200833A CN202110372183.XA CN202110372183A CN113200833A CN 113200833 A CN113200833 A CN 113200833A CN 202110372183 A CN202110372183 A CN 202110372183A CN 113200833 A CN113200833 A CN 113200833A
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- ionic liquid
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- vanillin
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 arylmethylene cyclohexenone compound Chemical class 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002608 ionic liquid Substances 0.000 claims abstract description 17
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 16
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000012141 vanillin Nutrition 0.000 claims abstract description 16
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000000741 silica gel Substances 0.000 claims abstract description 11
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 239000003957 anion exchange resin Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
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Classifications
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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
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a preparation method of an arylmethylene cyclohexenone compound, which takes vanillin and 1, 3-cyclohexanedione as raw materials, takes silica gel supported ionic liquid as a catalyst, and reacts under the condition of heating and refluxing a solvent to obtain a target product. Compared with the prior art, the invention solves the technical problems of relatively complex preparation process, use of solvents which are bad for the environment, inconvenient operation, difficult catalyst recycling and the like in the existing compound preparation process.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and relates to a preparation method of an arylmethylene cyclohexenone compound.
Background
2, 2' - (4-hydroxy-3-methoxy) phenyl-methylenebis (3-hydroxy-2-cyclohexen-1-one) compound having the formula:
the above arylmethylene cyclohexenone compound is a known (synth. Commun, 35: 2339-. Wang et al reported that such compounds were synthesized using PEG-400 as a phase transfer catalyst, but two other by-products, xanthene compounds, were also produced (Chemical Journal on Internet,9(9), 2007); hu et al synthesized this compound using aromatic aldehyde and 1, 3-cyclohexanedione as raw materials in benzene and an enzyme as a catalyst, and the reaction required the use of benzene as a solvent (Chinese Chemical Letters,22 (7): 777-780, 2011). So far, no literature report on the synthesis of the compound exists.
Disclosure of Invention
The invention aims to provide a preparation method of an arylmethylene cyclohexenone compound, which solves the technical problems of relatively complex preparation process, use of a solvent which is bad for the environment, inconvenient operation, difficult catalyst recycling and the like in the existing compound preparation process.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of an arylmethylene cyclohexenone compound comprises the steps of taking vanillin and 1, 3-cyclohexanedione as raw materials, taking silica gel supported ionic liquid as a catalyst, and reacting under the condition of heating and refluxing a solvent to obtain a target product 2, 2' - (4-hydroxy-3-methoxyl) phenyl-methylene bis (3-hydroxy-2-cyclohexene-1-one).
Further, the preparation method comprises the following steps:
(1) weighing vanillin and 1, 3-cyclohexanedione, placing into a solvent, adding a catalyst silica gel immobilized ionic liquid, and heating and refluxing for reaction;
(2) after the reaction is finished, filtering the obtained reaction liquid to obtain filtrate, namely a crude product, and purifying to obtain the target product.
Furthermore, in the step (2), a recrystallization method is adopted in the purification process, and the solvent used for recrystallization is absolute ethyl alcohol.
Furthermore, in the step (2), the filter cake obtained by filtering is washed by an organic solvent, then washed by water and dried in vacuum, and the catalyst silica gel-supported ionic liquid is obtained by recycling. Preferably, the vacuum degree is 5-10mmHg and the temperature is 60 ℃ during vacuum drying.
Further, the molar ratio of vanillin to 1, 3-cyclohexanedione is 1:1.5-1: 2.5.
Furthermore, the adding amount of the catalyst silica gel supported ionic liquid is5 to 7 percent of the molar weight of vanillin.
Further, the temperature of the heating reflux reaction is 75 ℃, and the time is 3-5 h.
Further, the solvent is ethanol with the volume fraction of 95%.
Further, the silica gel supported ionic liquid is Si- [ SbSipim [ ]][PF6]The anion exchange resin is solid at normal temperature, the cation is sulfonic acid ionic liquid loaded by silica gel, and the anion is hexafluorophosphate radical.
Compared with the prior art, the invention has the following advantages:
(1) the invention uses Si- [ SbSipim][PF6]The ionic liquid is used as a catalyst, and the 2, 2' - (4-hydroxy-3-methoxy) phenyl-methylene bis (3-hydroxy-2-cyclohexene-1-one) compound is prepared through one-step reaction, so that the preparation process is simple, the post-treatment process is simple, and the yield is high;
(2) ethanol is used as an organic solvent in the preparation process, so that the preparation method is green and environment-friendly;
(3) the catalyst is simple to prepare, the raw materials are easy to obtain and cheap, the catalyst can be recycled, and the recycling method is simple.
Drawings
FIG. 1 is an IR spectrum of 2, 2' - (4-hydroxy-3-methoxy) phenyl-methylenebis (3-hydroxy-2-cyclohexen-1-one) obtained in example 1, with wavenumbers (cm) on the abscissa-1) And the ordinate is Transmittitation (%).
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the catalyst silica gel supports an ionic liquid Si- [ SbSipi m][PF6]The following references may be referenced for preparation: kang LQ, Cai YQ, et al, silicon-supported sulfonic acid-functionalized ionic coated with bmim][PF6]as a scavenger for the synthesis of amides.Molecular Diversity，15(1)：109-113，2011
The chemical reaction formula of the preparation method of 2, 2' - (4-hydroxy-3-methoxy) phenyl-methylene bis (3-hydroxy-2-cyclohexene-1-one) of the following examples is as follows:
example 1
In a 50mL round bottom flask was placed vanillin 0.760g (5.0mmol), 1, 3-cyclohexanedione 0.840g (7.5mmol), shaken well and the catalyst ionic liquid Si- [ SbSipi m ] added][PF6]0.25g of 95 percent ethanol 5mL, heating and refluxing, stirring for 3h, filtering while the reaction is finished, washing a filter cake by using 95 percent ethanol and water, and drying in vacuum to obtain Si- [ SbSipi m][PF6]The ionic liquid can be recycled. And cooling the filtrate to obtain a crude product of 2, 2' - (4-hydroxy-3-methoxyl) phenyl-methylene bis (3-hydroxy-2-cyclohexene-1-one), and recrystallizing with absolute ethyl alcohol to obtain a white solid product, wherein the yield is 84%, and the melting point is 198.3-198.7 ℃. The measured data using a Nicolet iS50 fourier transform infrared spectrometer are as follows: IR (cm)-1):3444, 3059, 2955, 2355,1584,1509,1372,845. Wherein 3444cm-1Is a stretching vibration absorption peak of an O-H bond, 3059cm-1Is a stretching vibration absorption peak of ═ C-H bond, 2955cm-1is-CH3The absorption peak of the C-H bond in the stretching vibration is 2355cm-1、1584cm-1And 1509cm-1Is a stretching vibration absorption peak of C ═ C bond, 1372cm-1is-CH3The plane swinging vibration absorption peak of the middle C-H bond is 845cm-1is-CH2Plane rocking vibration of middle C-H bondAbsorption peak. The product was confirmed to be 2, 2' - (4-hydroxy-3-methoxy) phenyl-methylenebis (3-hydroxy-2-cyclohexen-1-one).
Comparative example 1:
compared with the example 1, the catalyst is mostly the same except that the catalyst is changed into the conventional catalyst of p-toluenesulfonic acid, and the yield of the final product 2, 2' - (4-hydroxy-3-methoxy) phenyl-methylene bis (3-hydroxy-2-cyclohexene-1-one) is 69%.
Example 2:
compared with example 1, the molar ratio of vanillin to 1, 3-cyclohexanedione was largely the same, except that the molar ratio of vanillin to 1, 3-cyclohexanedione was changed to 1:2, and the yield of the final product, 2' - (4-hydroxy-3-methoxy) phenyl-methylenebis (3-hydroxy-2-cyclohexen-1-one), was 86%.
Example 3:
compared with example 1, the molar ratio of vanillin to 1, 3-cyclohexanedione was largely the same, except that the final product, 2' - (4-hydroxy-3-methoxy) phenyl-methylenebis (3-hydroxy-2-cyclohexen-1-one), was obtained in 83% yield.
Example 4:
compared with the example 1, the method is mostly the same, except that the molar ratio of the vanillin to the 1, 3-cyclohexanedione is changed to 1:2, the stirring time is changed to 4h, and the yield of the product 2, 2' - (4-hydroxy-3-methoxy) phenyl-methylenebis (3-hydroxy-2-cyclohexene-1-one) is 86%.
Example 5:
compared with the example 1, the method is mostly the same, except that the molar ratio of vanillin to 1, 3-cyclohexanedione is changed to 1:2, the stirring time is changed to 4h, the amount of the catalyst is changed to 0.30g, and the yield of the product 2, 2' - (4-hydroxy-3-methoxy) phenyl-methylenebis (3-hydroxy-2-cyclohexene-1-one) is 89%.
Example 6:
compared with the example 1, the method is mostly the same, except that the molar ratio of the vanillin to the 1, 3-cyclohexanedione is changed to 1:2, the stirring time is changed to 5h, and the yield of the product 2, 2' - (4-hydroxy-3-methoxy) phenyl-methylenebis (3-hydroxy-2-cyclohexene-1-one) is 87%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of an arylmethylene cyclohexenone compound is characterized in that vanillin and 1, 3-cyclohexanedione are used as raw materials, silica gel supported ionic liquid is used as a catalyst, and the reaction is carried out under the condition of heating and refluxing a solvent to obtain a target product 2, 2' - (4-hydroxy-3-methoxyl) phenyl-methylene bis (3-hydroxy-2-cyclohexene-1-one).
2. The method of claim 1, comprising the steps of:
(1) weighing vanillin and 1, 3-cyclohexanedione, placing into a solvent, adding a catalyst silica gel immobilized ionic liquid, and heating and refluxing for reaction;
(2) after the reaction is finished, filtering the obtained reaction liquid to obtain filtrate, namely a crude product, and purifying to obtain the target product.
3. The method of claim 1 or 2, wherein the molar ratio of vanillin to 1, 3-cyclohexanedione is 1:1.5 to 1: 2.5.
4. The method for preparing an arylmethylenecyclohexenone compound according to claim 1 or 2, wherein the amount of the catalyst silica gel-supported ionic liquid added is 5% to 7% of the molar amount of vanillin.
5. The process according to claim 1 or 2, wherein the temperature of the heating reflux reaction is 75 ℃ and the time is 3-5 hours.
6. The method according to claim 1 or 2, wherein the solvent is 95% by volume ethanol.
7. The method of claim 1 or 2, wherein the silica gel supported ionic liquid is Si- [ SbSipi m ™][PF6]The anion exchange resin is solid at normal temperature, the cation is sulfonic acid ionic liquid loaded by silica gel, and the anion is hexafluorophosphate radical.
8. The method according to claim 2, wherein the purification process in step (2) is performed by recrystallization, and the solvent used for recrystallization is absolute ethanol.
9. The method for preparing an arylmethylenecyclohexenone compound according to claim 2, wherein in the step (2), the filter cake obtained by filtration is washed with an organic solvent, then washed with water, and vacuum-dried, and the catalyst silica gel-supported ionic liquid is recovered.
10. The method of claim 9, wherein the degree of vacuum is 5-10mmHg and the temperature is 60 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580446A (en) * | 2009-06-25 | 2009-11-18 | 上海应用技术学院 | Method for preparing aryl methylene double (3-hydroxide radical-5, 5-dimethyl-2-cyclohexene-1-ketone) terpenoids |
| CN108715874A (en) * | 2018-05-28 | 2018-10-30 | 南京工业大学 | The method of Enzyme catalyzed synthesis xanthone compound and its derivative |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580446A (en) * | 2009-06-25 | 2009-11-18 | 上海应用技术学院 | Method for preparing aryl methylene double (3-hydroxide radical-5, 5-dimethyl-2-cyclohexene-1-ketone) terpenoids |
| CN108715874A (en) * | 2018-05-28 | 2018-10-30 | 南京工业大学 | The method of Enzyme catalyzed synthesis xanthone compound and its derivative |
Non-Patent Citations (1)
| Title |
|---|
| 汪多仁: "《绿色增塑剂》", 31 October 2011, 科学技术文献出版社 * |
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