CN113087667B - Synthesis method of imidazolidinone derivative - Google Patents
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- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
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- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
The invention discloses a synthetic method of an imidazolinone derivative. The amidine compound and the polyalcohol compound are used as raw materials, the cobalt catalyst is used for catalyzing the high value of the polyalcohol to be converted into a series of imidazolone derivatives, a novel and green synthetic path which accords with the sustainable chemical principle is developed, the high value conversion of renewable resources is realized, and the synthetic requirement of the imidazolone derivatives is met. The synthesis method has the advantages of wide substrate applicability, good functional group compatibility, use of recyclable cheap metal catalyst and use of air as an oxidant, has the potential to prepare the imidazolone derivatives in one step on a large scale, and also provides an important way for converting biomass resources into high-value functional molecules.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthetic method of an imidazolidinone derivative.
Background
The imidazolone compounds are nitrogen-containing heterocyclic compounds with good biological activity and pharmacological activity, are widely present in natural active products, and play an important role in human health and industrial and agricultural production. Many imidazolinone fungicides, herbicides, natural drugs, and the like have been found.
The construction of imidazolinone derivatives has been an attractive topic for the scientific community due to their encouraging properties. The conventional methods in the related art for imidazolinone functional molecules involve the following reactions: (1) cyclization reaction of diamide compounds; (2) cyclizing condensation reaction of amino ester and cyanamide; (3) intermolecular condensation cyclization reaction of 1, 3-dicarbonyl compound and guanidine; (4) pd catalyzed multi-component reaction of isocyanoacetate with an amine. Although the synthesis method has the advantages of easily available raw materials and low price, the synthesis method needs to be carried out under the conditions of high temperature and high pressure, has higher requirements on equipment, and has the obvious defects of complicated steps, low yield, large amount of waste water and waste residue generated in the production process, serious environmental pollution and the like.
Therefore, it is necessary to develop a synthetic method of the imidazolidinone derivative; the method has high yield and is environment-friendly.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a method for synthesizing chiral beta-aryl substituted carboxylic acid derivatives, which has good selectivity and higher product yield.
In order to achieve the purpose, the invention adopts the technical scheme that: a synthetic method of an imidazolinone derivative comprises the following steps: : the method comprises the following steps: in a solvent, reacting a polyalcohol compound and an amidine compound in a cobalt catalyst and an alkaline substance to obtain the imidazolone derivative;
the structure of the polyalcohol compound is shown as a compound I in the following formula;
the structure of the ether compound is shown as a compound II in the following formula;
the structure of the imidazolone derivative is shown as a compound III in the following formula;
wherein R is1And R2Are all independently selected from alkyl and arylOne of a group and hydrogen;
R1and R2The same or different;
R1and R2Can form a ring;
R3one selected from the group consisting of alkyl, alkoxy, aryl, trifluoromethyl, amino, halogen and hydrogen.
According to some embodiments of the invention, the R is1Is selected from C1～C12Alkyl groups of (a); preferably, said R is1One selected from the group consisting of methyl, ethyl, propyl, n-butyl, and n-nonyl; preferably, said R is1Is selected from C6～C12Aryl of (2); more preferably, said R1One selected from phenyl and benzyl.
According to some embodiments of the invention, the R is2Is selected from C1～C12Alkyl groups of (a); preferably, said R is2One selected from the group consisting of methyl, ethyl, propyl, n-butyl, and n-nonyl; preferably, said R is2Is selected from C6～C12Aryl of (a); more preferably, said R2One selected from phenyl and benzyl.
According to some embodiments of the invention, the R is3Is selected from C1～C12One of alkyl, aryl and aryl derivatives of (a); preferably, said R is3One selected from the group consisting of pyridyl, phenyl and benzyl; preferably, said R is3Selected from methoxyphenyl; preferably, said R is3Selected from cyclopropane.
According to some embodiments of the invention, the R is3Selected from the group consisting of halophenyl; more preferably, the halogenated phenyl group includes one of a fluorinated phenyl group, a chlorinated phenyl group, a brominated phenyl group and an iodophenyl group.
According to some embodiments of the invention, the molar ratio of the polyol compound to the amidine compound is 1 to 10: 1.
the excessive polyol is beneficial to the reaction and improves the reaction yield.
According to some embodiments of the invention, the temperature of the reaction is between 25 ℃ and 130 ℃.
According to some embodiments of the invention, the reaction time is between 1h and 24 h.
According to some embodiments of the invention, the cobalt catalyst comprises a nanocobalt catalyst.
The cobalt catalyst has the advantage of being easily separated from the product and can be recycled for many times.
According to some embodiments of the invention, the nanocobalt catalyst comprises nanocobalt supported on an inorganic material.
According to some embodiments of the present invention, the inorganic material-supported nanocobalt includes at least one of alumina-supported nanocobalt, titania-supported nanocobalt, zinc oxide-supported nanocobalt, activated carbon-supported nanocobalt, and manganese oxide-supported nanocobalt.
According to some embodiments of the invention, the molar ratio of the polyol compound to the cobalt catalyst is 1: 0.02-0.08.
The catalyst in proper proportion can improve the reaction yield, and the yield is reduced due to over-high or over-low of the catalyst.
According to some embodiments of the invention, the alkaline substance comprises at least one of an organic alkaline substance and an inorganic alkaline substance.
According to some embodiments of the invention, the organic basic substance comprises at least one of a sodium alkoxide and an amine.
According to some embodiments of the invention, the sodium alkoxide comprises at least one of sodium methoxide, sodium tert-butoxide, and potassium tert-butoxide.
According to some embodiments of the invention, the amine comprises triethylamine.
According to some embodiments of the invention, the inorganic basic substance comprises at least one of an alkali metal hydroxide and a carbonate.
According to some embodiments of the invention, the alkali metal hydroxide comprises at least one of sodium hydroxide, cesium hydroxide and potassium hydroxide.
According to some embodiments of the invention, the carbonate salt comprises at least one of potassium carbonate, sodium carbonate and cesium carbonate.
According to some embodiments of the invention, the solvent comprises at least one of an organic solvent and an inorganic solvent.
According to some embodiments of the invention, the organic solvent comprises at least one of a nitrile solvent, an amide solvent, an ether solvent, a pyridine solvent, an alcohol solvent, and an aromatic hydrocarbon solvent.
According to some embodiments of the invention, the nitrile solvent comprises acetonitrile.
According to some embodiments of the invention, the amide-based solvent comprises at least one of N-methylformamide, formamide, N-ethylformamide, and N, N-dimethylformamide.
According to some embodiments of the invention, the ethereal solvent comprises tetrahydrofuran.
According to some embodiments of the invention, the pyridine-based solvent comprises pyridine.
According to some embodiments of the invention, the alcoholic solvent comprises at least one of tert-amyl alcohol, isopropyl alcohol, isobutyl alcohol and methanol.
According to some embodiments of the invention, the aromatic hydrocarbon solvent comprises at least one of toluene and para-xylene.
According to some embodiments of the invention, the inorganic solvent comprises water.
According to some embodiments of the invention, the volume ratio of the solvent to the polyol compound is 1 to 2: 1.
according to some embodiments of the invention, the synthesis method further comprises the steps of: and after the reaction is finished, removing the solvent and purifying to obtain the imidazolone derivative.
According to some embodiments of the invention, the method of purification is thin layer chromatography.
According to some embodiments of the present invention, the stationary phase used in the thin layer chromatography is silica gel, the eluent used in the thin layer chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is petroleum ether: the ethyl acetate is (0.5-50): 1.
The method for synthesizing the imidazolidinone derivative according to the embodiment of the invention has at least the following beneficial effects: the method takes amidine compounds and polyalcohol compounds as raw materials, obtains the imidazolone derivatives through the high-value conversion of the polyalcohol under the action of a cobalt catalyst, develops a novel and green synthetic path which accords with the sustainable chemical principle, realizes the high-value conversion of renewable resources, and meets the synthetic requirements of the imidazolone derivatives; has great application prospect in the industry of preparing the imidazolone derivative on a large scale.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a product obtained in the first embodiment of the present invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of a product obtained in the first embodiment of the present invention;
FIG. 3 is a NMR chart of a product obtained in example two of the present invention;
FIG. 4 is the NMR spectrum of the product obtained in example two of the present invention;
FIG. 5 is the NMR spectrum of the product obtained in example III of the present invention;
FIG. 6 is the NMR spectrum of the product obtained in example III of the present invention;
FIG. 7 is a NMR spectrum of a product obtained in example four of the present invention;
FIG. 8 is the NMR spectrum of the product obtained in example four of the present invention;
FIG. 9 is a NMR chart of the product obtained in example five of the present invention;
FIG. 10 is the NMR spectrum of the product obtained in example V of the present invention;
FIG. 11 is a NMR chart of the product obtained in example VI of the present invention;
FIG. 12 is a NMR spectrum of a product obtained in example six of the present invention;
FIG. 13 is a NMR chart of a product obtained in example VII of the present invention;
FIG. 14 is a NMR carbon spectrum of a product obtained in example VII of the present invention;
FIG. 15 is a NMR spectrum of a product obtained in example eight of the present invention;
FIG. 16 is the NMR spectrum of the product obtained in example eight of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts are within the protection scope of the present invention based on the embodiments of the present invention.
The preparation method of the cobalt nano catalyst comprises the following steps: first, 5.89g of KMnO4, 8.8g of MnSO4, 100mL of water, 3mL of concentrated nitric acid were added to a 250mL round bottom flask and refluxed at 100 ℃ for 24 hours. Filtering and washing to obtain black solid. A second step; to a 250mL round bottom flask, 50mg of cobalt chloride, 700mg of the black solid prepared in the previous stage, and 30mL of water were added and stirred for 1 hour. The pH of the mixture was adjusted to 13 by adding sodium hydroxide solution, followed by centrifugation and drying. Calcining the obtained mixture in a tubular furnace at 800 ℃ for 4h to obtain the carbon material-supported cobalt nano catalyst, wherein the preparation method of the cobalt catalyst supported by other materials is also the same.
The first embodiment of the invention is as follows: a synthetic method of an imidazolinone derivative comprises the following steps:
after 0.25 mmol of benzamidine hydrochloride, 0.375 mmol of 1, 2-cyclohexanediol, 0.6 mmol of cesium carbonate, 60mg of cobalt metal catalyst supported on activated carbon (mass fraction of activated carbon: 3%) and 1 ml of pyridine were added to a schlenk tube (schlenk tube), and the mixture was stirred at 130 ℃ under air for 12 hours, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure, followed by separation and purification by thin layer chromatography using silica gel as a stationary phase and a mixed solvent of petroleum ether and ethyl acetate as an eluent (petroleum ether: ethyl acetate: 5:1, v/v), to obtain the desired product in 89% yield.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the first embodiment of the invention are respectively shown in fig. 1 and fig. 2, and the structural characterization data are as follows:
1H NMR(500MHz,CDCl3):δ7.98(d,J＝7.0Hz,2H),7.59-7.46(m,3H),2.05(m,8H).
13C NMR(126MHz,CDCl3):δ190.88,157.94,131.77,128.94,128.63,127.00,78.76,37.66,26.26.
IR(KBr):3053,1674,1556,1471,1345,763,695cm-1.
MS(EI,m/z):214.10[M]+.
from the above data, it is concluded that the structure of the product of example one of the present invention is shown in the following formula:
the second embodiment of the invention is as follows: a synthetic method of an imidazolinone derivative comprises the following steps:
adding 0.25 mmol of 4-methoxybenzamidine hydrochloride, 0.45 mmol of 1,2 cyclohexanediol, 0.5 mmol of potassium hydroxide, 45 mg of aluminum oxide supported cobalt metal catalyst (the mass fraction of aluminum oxide is 3%) and 1 ml of tert-amyl alcohol into a schlenk tube, stirring and reacting for 12 hours at 110 ℃ under air conditions, stopping heating and stirring, cooling to room temperature, carrying out reduced pressure rotary evaporation to remove the solvent, and separating and purifying by thin-layer chromatography to obtain the target product, wherein the stationary phase of the thin-layer chromatography is silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 5:1, v/v), and the yield of the obtained product is 84%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the second embodiment of the invention are respectively shown in fig. 3 and 4, and the structural characterization data are as follows:
1H NMR(500MHz,DMSO):δ7.95(d,J＝8.7Hz,2H),7.07(d,J＝8.8Hz,2H),3.83(s,3H),3.44(s,1H),1.92–1.80(m,6H),1.75(m,2H).
13C NMR(126MHz,DMSO):δ190.66,162.62,130.09,129.54,121.35,114.57,76.03,55.90,37.60,25.95.
IR(KBr):2917，1712，1613，1435，1251，839，754cm-1.
MS(EI,m/z):244.10[M]+.
from the above data, it is concluded that the structure of the product obtained in example two of the present invention is shown in the following formula:
the third embodiment of the invention is as follows: a synthetic method of an imidazolinone derivative comprises the following steps:
0.25 mmol of 4-fluoro benzamidine hydrochloride, 0.5 mmol of 1,2 cyclohexanediol, 0.5 mmol of sodium methoxide, 60mg of titanium dioxide supported nano cobalt catalyst (the mass fraction of titanium dioxide is 3%) and 1 ml of methanol are added into a schlenk tube, after stirring and reacting for 10 hours under the condition of air at 120 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, the solvent is removed by reduced pressure rotary evaporation, and then the mixture is separated and purified by thin layer chromatography, the target product is obtained, the stationary phase of the thin layer chromatography is silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 7:1, v/v), and the yield of the product is 83%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the third embodiment of the invention are respectively shown in fig. 5 and 6, and the structural characterization data are as follows:
1H NMR(500MHz,DMSO):δ8.04(s,2H),7.37(t,J＝7.8Hz,2H),1.80(m,8H).
13C NMR(126MHz,DMSO):δ189.53,164.62(d,J＝250Hz),130.11(d,J＝7.6Hz),125.70,116.44,116.32(d,J＝22.0Hz),76.80,37.53,25.95.
IR(KBr):3746，2872，2357，1703，1441，1290，851，664cm-1.
HRMS(ESI):Calcd.for C13H13FN2O[M+39]+:271.0643；found:271.0643.
according to the above data, the structure of the product obtained in the third embodiment of the present invention is deduced to be shown as the following formula:
the fourth embodiment of the invention is as follows: a synthetic method of an imidazolinone derivative comprises the following steps:
after 0.25 mmol of 3-pyridinebenzamidine hydrochloride, 60mg of activated carbon-supported nanocobalt catalyst (the mass fraction of activated carbon is 3%), 0.375 mmol of 1,2 pentanediol, 0.3 mmol of triethylamine and 10 hours are added into a schlenk tube, heating and stirring are stopped, the mixture is cooled to room temperature, the solvent is removed by reduced pressure rotary evaporation, and then the mixture is separated and purified by thin-layer chromatography to obtain the target product, wherein the stationary phase of the thin-layer chromatography is silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate is 3:1, v/v), and the yield of the obtained product is 87%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the fourth embodiment of the invention are respectively shown in fig. 7 and 8, and the structural characterization data are as follows:
1H NMR(500MHz,CDCl3):δ9.22(s,1H),8.80(d,J＝4.2Hz,1H),8.35(d,J＝8.0Hz,1H),7.49(dd,J＝7.8,4.9Hz,1H),2.10(m,4H),2.04-1.93(m,4H).
13C NMR(126MHz,CDCl3):δ190.49,155.80,152.27,148.06,134.72,125.02,123.86,78.92,37.69,26.25.
IR(KBr):3441，2929，1709，1450，1089，706cm-1.
MS(EI,m/z):215.10[M]+.
from the above data, it is concluded that the structure of the product obtained in example four of the present invention is shown in the following formula:
the fifth embodiment of the invention is as follows: a synthetic method of an imidazolinone derivative comprises the following steps:
0.25 mmol of benzamidine hydrochloride, 0.375 mmol of 2, 3-butanediol, 0.5 mmol of potassium tert-butoxide, 60mg of activated carbon-supported cobalt catalyst (the mass fraction of activated carbon is 3%) and 1 ml of pyridine are added into a schlenk tube, and after stirring and reacting for 10 hours at 130 ℃ under air conditions, heating and stirring are stopped, the mixture is cooled to room temperature, the solvent is removed by rotary evaporation under reduced pressure, and then the mixture is separated and purified by thin-layer chromatography, wherein the stationary phase of the thin-layer chromatography is silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 8:1, v/v), and the yield of the product is 65%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the fifth embodiment of the invention are respectively shown in fig. 9 and fig. 10, and the structural characterization data are as follows:
1H NMR(500MHz,CDCl3):δ7.99(d,J＝7.3Hz,2H),7.52(d,J＝7.6Hz,3H),1.50(s,6H)；
13C NMR(126MHz,CDCl3):δ190.69,158.39,132.02,128.98,128.38,127.07,69.07,24.02；
IR(KBr):3755，2923，2854，2369，1727，1459，1296，703；
MS(EI,m/z):188.10[M]+.
from the above data, it is concluded that the structure of the product obtained in example five of the present invention is shown in the following formula:
the sixth embodiment of the invention is as follows: a synthetic method of an imidazolinone derivative comprises the following steps:
0.25 mmol of benzamidine hydrochloride, 0.375 mmol of 1, 2-diphenyl-1, 2-diol, 0.25 mmol of potassium hydroxide, 60mg of cobalt catalyst and 1 ml of pyridine are added into a schlenk tube, after stirring and reacting for 12 hours under air conditions at 130 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, the solvent is removed by reduced pressure rotary evaporation, and then the mixture is separated and purified by thin layer chromatography, so that the target product is obtained, wherein the stationary phase of the thin layer chromatography is silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 6:1, v/v), and the yield of the target product is 85%.
The hydrogen spectrum and the carbon spectrum of the obtained product are respectively shown in fig. 11 and fig. 12, and the structural characterization data are as follows:
1H NMR(500MHz,CDCl3):δ8.06–8.03(m,2H),7.62–7.57(m,4H),7.55(ddd,J＝6.5,3.7,1.2Hz,1H),7.51-7.47(m,2H),7.35-7.30(m,4H),7.29-7.25(m,2H).
13C NMR(126MHz,CDCl3):δ186.17,140.15,132.27,128.98,128.52,128.15,128.05,127.89,127.39,127.29,79.59.
IR(KBr):3435,2923,1712,1619,1459,1251,766,694.
MS(EI,m/z):312.10[M]+.
the structure of the obtained product is deduced according to the data as shown in the following formula:
the seventh embodiment of the invention is: a synthetic method of an imidazolinone derivative comprises the following steps:
0.25 mmol of cyclopropyl amidine hydrochloride, 0.375 mmol of 2, 3-butanediol, 0.75 mmol of potassium carbonate, 60mg of manganese dioxide-supported cobalt catalyst (the mass fraction of manganese dioxide is 3%) and 1 ml of N, N-dimethylformamide are added into a schlenk tube, and after stirring and reacting for 12 hours under air conditions at 120 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, the solvent is removed by rotary evaporation under reduced pressure, and then the mixture is separated and purified by thin-layer chromatography, so that the target product is obtained, wherein the stationary phase of the thin-layer chromatography is silica gel, the eluent is a mixed solvent of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 6:1, v/v), and the yield of the product is 68%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the seventh embodiment of the invention are respectively shown in fig. 13 and 14, and the structural characterization data are as follows:
1H NMR(500MHz,CDCl3):δ1.82–1.73(m,1H),1.35(s,6H),1.20–1.12(m,2H),1.12–1.03(m,2H).
13C NMR(126MHz,CDCl3):δ191.16,157.62,66.39,23.88,10.66,8.61.
IR(KBr):3749，3152，2962，2357，1685，1492，1303，649.
MS(EI,m/z):152.10[M]+.
from the above data, it is concluded that the product obtained in example seven of the present invention has the following structure:
the eighth embodiment of the present invention is: a synthetic method of an imidazolinone derivative comprises the following steps:
after 0.25 mmol of 4-chlorobenzamidine hydrochloride, 0.5 mmol of pentane-2, 3-diol, 0.5 mmol of sodium hydroxide, 60mg of zinc oxide-supported cobalt catalyst (the mass fraction of zinc oxide is 3%) and 1.5 ml of pyridine were added to a schlenk tube, and the mixture was stirred at 120 ℃ under air for 12 hours, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure, followed by separation and purification by thin layer chromatography using silica gel as a stationary phase and a mixed solvent of petroleum ether and ethyl acetate as an eluent (petroleum ether: ethyl acetate: 4:1, v/v), to obtain a yield of the desired product of 72%.
The hydrogen spectrogram and the carbon spectrogram of the product obtained in the example eight of the invention are respectively shown in fig. 15 and 16, and the structural characterization data are as follows:
1H NMR(500MHz,CDCl3):δ7.95(d,J＝8.5Hz,2H),7.52(d,J＝8.5Hz,2H),1.93(d,J＝7.4Hz,2H),1.47(s,3H),0.85(d,J＝7.4Hz,3H).
13C NMR(126MHz,CDCl3):δ189.86,162.81,138.38,129.36,128.42,126.63,72.97,30.91,22.87,8.23.
IR(KBr):3737，2917，2363，1712，1584，1438，1107，851，586.
HRMS(ESI):Calcd.for C12H13ClN2O[M+1]+:237.0789；found:237.0787.
according to the above data, the structure of the product obtained in the eighth embodiment of the present invention is deduced to be shown as the following formula:
in conclusion, the amidine compound and the polyalcohol compound are used as raw materials, the cobalt catalyst is used for catalyzing the high value of the polyalcohol to be converted into a series of imidazolone derivatives, a novel and green synthetic path which accords with the sustainable chemical principle is developed, the high value conversion of renewable resources is realized, and the synthetic requirement of the imidazolone derivatives is met. The synthesis method has the advantages of wide substrate applicability, good functional group compatibility, use of recyclable cheap metal catalyst and use of air as an oxidant, has the potential to prepare the imidazolone derivatives in one step on a large scale, and also provides an important way for converting biomass resources into high-value functional molecules.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
While the embodiments of the present invention have been described in detail with reference to the description and the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (7)
1. A synthetic method of an imidazolidinone derivative is characterized by comprising the following steps: the method comprises the following steps: in a solvent, reacting a polyalcohol compound and an amidine compound in a cobalt catalyst and an alkaline substance to obtain the imidazolone derivative;
the structure of the polyalcohol compound is shown as the following formula compound I;
the structure of the amidine compound is shown as a compound II in the following formula;
the structure of the imidazolone derivative is shown as a compound III in the following formula;
wherein R is1And R2Are all independently selected from C1~C12Alkyl of (C)6~C12One of aryl and hydrogen of (a);
R1and R2The same or different;
R1and R2Can form a ring;
R3is selected from C1~C12One of alkyl, alkoxy, pyridyl, phenyl, trifluoromethyl, amino, halogen and hydrogen of (a);
the cobalt catalyst is at least one of nano cobalt loaded by aluminum oxide, nano cobalt loaded by titanium dioxide, nano cobalt loaded by zinc oxide, nano cobalt loaded by active carbon and nano cobalt loaded by manganese oxide;
the alkaline substance is at least one of cesium carbonate, potassium hydroxide, sodium methoxide, triethylamine, potassium tert-butoxide, potassium carbonate and sodium hydroxide;
the solvent is at least one of pyridine, N-dimethylformamide, 1, 2-pentanediol, methanol and tertiary amyl alcohol.
2. The method of claim 1, wherein the imidazolinone derivative is synthesized by: the R is1One selected from the group consisting of methyl, ethyl, propyl, n-butyl, n-nonyl, and phenyl.
3. The imidazolinone derivative of claim 1A method of biosynthesis, characterized by: the R is2One selected from the group consisting of methyl, ethyl, propyl, n-butyl, n-nonyl, and phenyl.
4. The method of claim 1, wherein the imidazolinone derivative is synthesized by: the molar ratio of the polyalcohol compound to the amidine compound is 1-10: 1.
5. the method of claim 1, wherein the imidazolinone derivative is synthesized by: the reaction temperature is 25-130 ℃.
6. The method of claim 1, wherein the imidazolinone derivative is synthesized by: the reaction time is 1-24 h.
7. The method of claim 1, wherein the imidazolinone derivative is synthesized by: the molar ratio of the cobalt catalyst to the polyol compound is 0.02-0.08: 1.
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