CN111732561B - Method for dearomatization and peroxy alkylation of phenol - Google Patents
Method for dearomatization and peroxy alkylation of phenol Download PDFInfo
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- CN111732561B CN111732561B CN202010483693.XA CN202010483693A CN111732561B CN 111732561 B CN111732561 B CN 111732561B CN 202010483693 A CN202010483693 A CN 202010483693A CN 111732561 B CN111732561 B CN 111732561B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
Abstract
The invention relates to a method for dearomatization and peroxy alkylation of phenol, which comprises the steps of adding 2, 6-di-tert-butyl-p-cresol, cobalt acetate tetrahydrate, silver carbonate, isobutanol and tetrahydrofuran into a reactor, stirring in an oil bath kettle at the temperature of 40-80 ℃, heating and refluxing for 8-16 hours; after the reaction is stopped, standing and cooling, adsorbing and filtering impurities by using diatomite, washing the impurities for three times by using ethyl acetate, collecting filtrate, and carrying out reduced pressure distillation to obtain a crude product; adopting ethyl acetate: petroleum ether is 1:10, and performing column separation on the obtained crude product to obtain a yellow solid pure product of the 2, 6-di-tert-butyl-4-methyl- [4- (tetrahydrofuran peroxide) ] -2, 5-diene-1-cyclohexanone. The synthetic method has the advantages that the cobalt which is cheap and easy to obtain and rich in content is used for catalysis, the inorganic silver carbonate is used as an oxidant, the reaction condition is mild, the process is simple, and the product is stable, safe and unprecedented.
Description
Technical Field
The invention relates to a method for dearomatization and peroxy alkylation of phenol, in particular to a method for preparing 2, 6-di-tert-butyl-4-methyl- [4- (tetrahydrofuran peroxide) ] -2, 5-diene-1-cyclohexanone.
Background
In the past, cobalt has been widely used in the alloy industry, and in recent years, researchers have attracted more and more attention due to the specific catalytic effects exhibited by cobalt catalysts. Currently, many researchers have found that in some reactions, cobalt catalysts can replace some other noble metals. Cobalt catalysts are used later in organic synthesis compared to other transition metals. However, in the subsequent organic synthesis field, cobalt will be more and more widely used as a new-generation catalyst.
Peroxidation is generally considered to be a reaction in which some substances react with ozone, and some very active substances react with hydrogen peroxide to generate peroxides. In some peroxidation reactions, the peroxidation products are generally not stable enough to be explosive, and therefore strict control of the reaction conditions is required in the peroxidation reaction.
Aromatic compounds and heterocyclic compounds can be synthesized into a plurality of biological drug molecules through dearomatization reaction, and at present, according to literature reports, dearomatization reaction is mostly completed through some noble metal catalysts.
Based on the above, the patent utilizes cheap and easily available cobalt catalyst to catalyze and complete the peroxidation dearomatization reaction of 2, 6-di-tert-butyl-p-cresol and tetrahydrofuran to generate 2, 6-di-tert-butyl-4-methyl- [4- (peroxytetrahydrofuran) ] -2, 5-diene-1-cyclohexanone. The reaction conditions of the reaction are green and environment-friendly, and the reaction product is stable, safe and novel.
Disclosure of Invention
The invention aims to provide a method for producing a stable and novel product 2, 6-di-tert-butyl-4-methyl- [4- (tetrahydrofuran peroxide) ] -2, 5-diene-1-cyclohexanone by catalyzing 2, 6-di-tert-butyl-p-cresol and tetrahydrofuran with cobalt.
The scheme adopted by the invention for solving the technical problems is as follows:
a process for the dearomatization of a peroxyalkylation reaction of phenol comprising the steps of:
(1) adding 2, 6-di-tert-butyl-p-cresol, cobalt acetate tetrahydrate, silver carbonate, isobutanol and tetrahydrofuran into a reactor, and stirring, heating and refluxing the mixture in an oil bath kettle at the temperature of 40-80 ℃ for 8-16 hours;
(2) after the reaction is stopped, standing and cooling, adsorbing and filtering impurities by using diatomite, washing the impurities for three times by using ethyl acetate, collecting filtrate, and carrying out reduced pressure distillation to obtain a crude product;
(3) adopting ethyl acetate: the crude product was subjected to column chromatography with a flow of 1:10 petroleum ether to give 2, 6-di-tert-butyl-4-methyl- [4- (tetrahydrofuran peroxide) ] -2, 5-diene-1-cyclohexanone as a yellow solid pure product.
Preferably, in the step (1), the using ratio of the 2, 6-di-tert-butyl-p-cresol, the cobalt acetate tetrahydrate, the silver carbonate, the isobutanol and the tetrahydrofuran is as follows: mole: mole: mole: and ml is 0.0004: 0.00004: 0.0008: 0.002: 5.
preferably, the tetrahydrofuran is previously re-distilled with sodium heavy metal to remove water and impurities.
Preferably, the spherical vessel at the bottom end of the reactor is immersed in an oil bath of silicone oil, the level of which is higher than the level of the liquid in the reactor.
Preferably, the purity of 2, 6-di-tert-butyl-p-cresol is 99%, the purity of cobalt acetate tetrahydrate is 98%, the purity of silver carbonate is 99.5%, the purity of isobutanol is 99.5%, the purity of tetrahydrofuran is 99.9%, and the purity of ethyl acetate and petroleum ether is chemically pure.
Preferably, the magnetic stirring speed in the step (1) is 400-600 rpm.
The invention provides a method for synthesizing 2, 6-di-tert-butyl-4-methyl- [4- (peroxytetrahydrofuran) ] -2, 5-diene-1-cyclohexanone by using 2, 6-di-tert-butyl-p-cresol and tetrahydrofuran, which has a reaction general formula as follows:
the synthetic method has the advantages that the cobalt which is cheap and easy to obtain and rich in content is used for catalysis, the inorganic silver carbonate is used as an oxidant, the reaction condition is mild, the process is simple, and the product is stable, safe and unprecedented.
Drawings
FIG. 1 is a schematic structural diagram of 2, 6-di-tert-butyl-4-methyl- [4- (peroxytetrahydrofuran) ] -2, 5-diene-1-cyclohexanone obtained by the invention.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1
Adding 0.4mmol of 2, 6-di-tert-butyl-p-cresol, 10 mol% of cobalt acetate tetrahydrate, 2eq of silver carbonate, 5eq of isobutanol and 5mL of tetrahydrofuran into a round-bottom flask, heating and refluxing in an oil bath kettle at 40-80 ℃, adjusting the rotating speed of a magnetic stirrer to 400-600 r/s, stopping the reaction after 8-16 hours of reaction, standing and cooling, adsorbing impurities by using kieselguhr, filtering by using ethyl acetate for three times, collecting filtrate, and carrying out reduced pressure distillation to obtain a crude product. Finally, using ethyl acetate: the petroleum ether is subjected to column separation by a 1:15 system to obtain a yellow solid pure product of 2, 6-di-tert-butyl-4-methyl- [4- (peroxytetrahydrofuran) ] -2, 5-diene-1-cyclohexanone.
The product was structurally determined via nuclear magnetic resonance hydrogen and carbon spectra:1H NMR(400MHz,CDCl3)δ6.62-6.50(m,2H),5.55(dd,J1＝4Hz,J1＝4Hz,1H),3.93-3.85(m,2H),2.00-1.76(m,3H),1.64-1.60(m,1H),1.36-1.33(m,3H),1.23(s,18H).13C NMR(100MHz,CDCl3)δ186.5,147.6,147.2,141.2,140.5,107.2,78.0,67.5,34.7,29.4,29.2,24.1,23.9.
while the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (6)
1. A process for the dearomatization of a peroxyalkylation reaction of phenol comprising the steps of:
(1) adding 2, 6-di-tert-butyl-p-cresol, cobalt acetate tetrahydrate, silver carbonate, isobutanol and tetrahydrofuran into a reactor, and stirring, heating and refluxing the mixture in an oil bath kettle at the temperature of 40-80 ℃ for 8-16 hours;
(2) after the reaction is stopped, standing and cooling, adsorbing and filtering impurities by using diatomite, washing the impurities for three times by using ethyl acetate, collecting filtrate, and carrying out reduced pressure distillation to obtain a crude product;
(3) adopting ethyl acetate: the crude product was subjected to column chromatography with a flow of 1:10 petroleum ether to give 2, 6-di-tert-butyl-4-methyl- [4- (tetrahydrofuran peroxide) ] -2, 5-diene-1-cyclohexanone as a yellow solid pure product.
2. The method according to claim 1, wherein the 2, 6-di-tert-butyl-p-cresol in the step (1), the cobalt acetate tetrahydrate, the silver carbonate, the isobutanol and the tetrahydrofuran are used in a molar ratio of: mole: mole: mole: and ml is 0.0004: 0.00004: 0.0008: 0.002: 5.
3. the process according to claim 1, characterized in that the tetrahydrofuran is previously re-distilled with sodium heavy metal to remove water and impurities.
4. The process according to claim 1, wherein the spherical vessel at the bottom end of the reactor is immersed in an oil bath of silicone oil, the level of the silicone oil being higher than the level of the liquid in the reactor.
5. The method of claim 1, wherein the purity of 2, 6-di-tert-butyl-p-cresol is 99%, the purity of cobalt acetate tetrahydrate is 98%, the purity of silver carbonate is 99.5%, the purity of isobutanol is 99.5%, the purity of tetrahydrofuran is 99.9%, and the purity of ethyl acetate and petroleum ether are chemically pure.
6. The method as claimed in claim 1, wherein the magnetic stirring speed in step (1) is 400-600 rpm.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078622A (en) * | 2019-06-11 | 2019-08-02 | 安阳工学院 | A kind of synthetic method of 4- ethyoxyl -1,1,2,4,5,6- hexahydro cyclobutane and naphthalene -2- benzoic ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110078622A (en) * | 2019-06-11 | 2019-08-02 | 安阳工学院 | A kind of synthetic method of 4- ethyoxyl -1,1,2,4,5,6- hexahydro cyclobutane and naphthalene -2- benzoic ether |
Non-Patent Citations (2)
| Title |
|---|
| Novel coumarin and furan from the roots of Angelica pubescens f. biserrata;Xiu-Wei Yang等;《Journal of Asian Natural Products Research》;20090831;第11卷(第8期);第698-703页 * |
| Trapping free radicals formed in the reaction of ozone with simple olefins using 2,6-di-tert-butyl-4-cresol (BHT);Pryor, William A.等;《Journal of Organic Chemistry》;19851231;第50卷(第2期);第185-189页 * |
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