CN115650926A - Azole selenone functional reagent and application thereof - Google Patents

Azole selenone functional reagent and application thereof Download PDF

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CN115650926A
CN115650926A CN202211434442.8A CN202211434442A CN115650926A CN 115650926 A CN115650926 A CN 115650926A CN 202211434442 A CN202211434442 A CN 202211434442A CN 115650926 A CN115650926 A CN 115650926A
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substituted
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halo
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汤日元
简锦桐
董丽
黄子豪
郭雪莹
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South China Agricultural University
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Abstract

The invention provides a azol selenone functional reagent and application thereof, which can regulate and control the growth of crops and strengthen the nutritive value of the crops. The azol selenone functional reagent can promote the growth of crops and improve the content of soluble protein, soluble sugar, total phenol, flavonoid, glucosinolate, chlorophyll, carotenoid, anthocyanin, free amino acid, mineral substances and functional organic selenium in the crops.

Description

Azole selenone functional reagent and application thereof
Technical Field
The invention belongs to the technical field of agriculture, and particularly relates to a oxazoleleno-selenone functional reagent for regulating and controlling plant growth and enhancing nutrition and application thereof.
Background
With the improvement of living standard, people pay more and more attention to the quality and the function of agricultural products. The demand for agricultural products has evolved from being full to good to healthy. How to strengthen the nutrition of crops and improve the added value of the crops becomes a technical problem to be solved by modern agriculture. Selenium-rich agricultural products are important functional agricultural products, selenium is a trace element indispensable to animals and human bodies, has a positive effect on human health, and people have increasingly growing demand for the selenium-rich agricultural products.
The proper amount of selenium can promote the growth and development of plants, improve the quality of the plants, improve the oxidation resistance and stress resistance, and can be converted into seleno-amino acid and selenoprotein to meet the dietary requirements of human bodies. In the past, selenate and selenite have been used as selenium sources and compounded into fertilizers to enhance the selenium content of crops. However, selenate and selenite have high toxicity and cause environmental pollution. Another problem is that many plants do not absorb selenate and selenite well or convert them efficiently into functional organic selenium. Seleno-amino acids, such as selenocysteine and selenomethionine, can directly and effectively enhance the selenium content of plants, but the seleno-amino acids are unstable, are easy to be oxidized and desalenized to lose efficacy in storage and scene application, and are expensive. In recent years, yeast selenium, an organic selenium source developed by using yeast, which is produced by enriching selenium in a cell protein structure of growing yeast, is safer, more stable and easier to absorb than inorganic selenium, has also been developed and applied to selenium fortification of crops. Although the selenium-enriched technical products for crops have made certain progress and application, the related technical products are relatively limited and are difficult to meet the requirements of crop growth regulation and nutrition enrichment.
Therefore, through a large number of experiments, the inventor develops the azoles selenone plant nutrition enhancer, can obviously regulate and control the growth condition of plants, and simultaneously improves the content of nutrients such as soluble protein, soluble sugar, amino acid, flavone, polyphenol, functional organic selenium, chlorophyll and the like of the plants. Therefore, the azol selenone functional reagent can be used for the growth regulation and the nutrition enhancement of plants and developing derivative functional products.
Disclosure of Invention
The primary object of the present invention is to provide a highly biocompatible oxazolelenosone derivative; the invention also aims to provide a azol selenone functional reagent which is used in the fields of plant growth regulation, nutrition enhancement, seed treatment and the like; still another object of the present invention is to provide a functional product for nutrition enrichment.
The purpose of the invention is realized by the following technical scheme:
a carfentrazone derivative for promoting seed germination and plant growth, improving plant quality and being capable of being converted into seleno-amino acids by plants, having the structure shown in formula (I):
Figure BDA0003946556240000021
in the general formula (I):
Y 1 is O, S, N-R 2 ；
Y 2 Is N, C-R 3 ；
Y 3 Is N, C-R 4 ；
R 1 ，R 2 Independently of one another, from hydrogen, C 1 -C 12 Alkyl, halo C 1 -C 12 Alkyl radical, C 3 -C 12 Cycloalkyl, halo C 3 -C 12 Cycloalkyl radical, C 2 -C 12 Alkenyl radical, C 2 -C 12 Alkynyl, C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl, halo C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylthio group C 1 -C 12 Alkyl, halo C 1 -C 12 Alkylthio group C 1 -C 12 Alkyl, sulfinyl-containing C 1 -C 12 Alkyl, halogen-and sulfinyl-containing C 1 -C 12 Alkyl radical, containing sulfonyl radical C 1 -C 12 Alkyl, containing halogen and sulphonyl C 1 -C 12 Alkyl, C substituted by amino 1 -C 12 Alkyl, halo C substituted by amino 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxycarbonyl group, CONH 2 ，C 1 -C 12 Alkylaminocarbonyl, di (C) 1 -C 12 Alkyl) aminocarbonyl, C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl radical, quilt C 1 -C 12 Alkylaminocarbonyl-substituted C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl, C substituted by halogen 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylaminocarbonyl radical C 1 -C 12 Alkyl, di (C) 1 -C 12 Alkyl) aminocarbonyl group C 1 -C 12 Alkyl radical, C 3 -C 12 cycloalkyl-C 1 -C 12 Alkyl, substituted or unsubstituted C 6 -C 20 aryl-C 1 -C 12 Alkyl, substituted or unsubstituted C 6 -C 20 Aryl, substituted or unsubstituted C 2 -C 20 A heteroaryl group;
R 3 ，R 4 independently of one another, from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, fluoroacetate, -CHO, C 1 -C 12 Alkyl, halo C 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxy, halo C 1 -C 12 Alkoxy radical, C 3 -C 12 Cycloalkyl radicals, halo radicals C 3 -C 12 Cycloalkyl radical, C 2 -C 12 Alkenyl radical, C 2 -C 12 Alkynyl, C 2 -C 12 Alkenyloxy, halogeno C 2 -C 12 Alkenyloxy radical, C 2 -C 12 Alkynyloxy, halo C 2 -C 12 Alkynyloxy, C 1 -C 12 Alkylthio, halo C 1 -C 12 Alkylthio radical, C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl, halo C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylthio C 1 -C 12 Alkyl, halo C 1 -C 12 Alkylthio group C 1 -C 12 Alkyl, sulfinyl-containing C 1 -C 12 Alkyl, halogen-and sulfinyl-containing C 1 -C 12 Alkyl radical, containing sulfonyl radical C 1 -C 12 Alkyl, halogen-containing and sulphonyl C 1 -C 12 Alkyl, C substituted by amino 1 -C 12 Alkyl, halo C substituted by amino 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxycarbonyl, CONH 2 ，C 1 -C 12 Alkylaminocarbonyl, di (C) 1 -C 12 Alkyl) aminocarbonyl, C substituted by cyano 1 -C 12 An alkoxy group,C 1 -C 12 alkoxycarbonyl radical C 1 -C 12 Alkyl radical, by C 1 -C 12 Alkylamino carbonyl-substituted C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl, C substituted by halogen 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylaminocarbonyl radical C 1 -C 12 Alkyl, di (C) 1 -C 12 Alkyl) aminocarbonyl group C 1 -C 12 Alkyl radical, C 3 -C 12 cycloalkyl-C 1 -C 12 Alkyl, substituted or unsubstituted C 6 -C 20 aryl-C 1 -C 12 Alkyl, substituted or unsubstituted C 2 -C 20 heteroaryl-C 1 -C 12 Alkyl, substituted or unsubstituted C 6 -C 20 Aryl, substituted or unsubstituted C 2 -C 20 A heteroaryl group;
and/or, R 2 And R 3 Are connected to each other and to R 2 And a nitrogen atom of (C) and a connection R 3 Together form a substituted or unsubstituted five to seven membered ring with or without N, O and/or S heteroatoms;
and/or, R 3 And R 4 Are connected to each other and to the connection R 3 And R 4 Together form a substituted or unsubstituted five to seven-membered ring with or without N, O and/or S heteroatoms.
In any of the sections herein, said C 1 -C 12 Alkyl and alkyl moieties having the corresponding number of carbon atoms (e.g., alkyl moieties in alkoxy, thio moieties in alkylthio, etc.), preferably C 1 -C 8 Alkyl, more preferably C 1 -C 4 An alkyl group. As an example of the aforementioned alkyl group, there may be specifically mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 2-hexyl, 3-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl and the like and isomers thereof.
In any of the sections herein, theC mentioned above 3 -C 12 Cycloalkyl groups and cycloalkyl moieties having the corresponding number of carbon atoms (e.g. C) 3 -C 12 cycloalkyl-C 1 -C 12 Alkyl), preferably C 3 -C 8 Cycloalkyl, more preferably C 3 -C 6 Cycloalkyl groups, exemplary cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and the like, monocyclic or polycyclic cycloalkyl groups.
In any of the sections herein, said C 6 -C 20 Aryl groups and aryl moieties having the corresponding number of carbon atoms (e.g. C) 6 -C 20 aryl-C 1 -C 12 Alkyl), preferably C 6 -C 14 Aryl, exemplary aryl groups include, but are not limited to, phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, pyrenyl, indenyl, and the like.
In any of the sections herein, said C 2 -C 20 Heteroaryl and heteroaryl moieties having the corresponding number of carbon atoms (e.g. C) 2 -C 20 heteroaryl-C 1 -C 12 Alkyl) is selected from N, O, S, se and/or B, preferably the heteroatom is selected from N, O and/or S. Said C is 2 -C 20 Heteroaryl and heteroaryl moieties having the corresponding number of carbon atoms (e.g. C) 2 -C 20 heteroaryl-C 1 -C 12 Alkyl) is preferably C 2 -C 12 Heteroaryl, more preferably C 2 -C 8 A heteroaryl group; exemplary heteroaryl groups include, but are not limited to, pyridyl, pyrimidinyl, pyrazinyl, piperazinyl, indolyl, furyl, pyranyl, thienyl, thiazolyl, acridinyl, quinolinyl, isoquinolinyl, phenanthrolinyl, phenothiazinyl, phenoxazinyl, and the like.
According to the invention, R is a compound of the general formula (I) 2 And R 3 The five-seven membered ring formed by connecting with each other comprises but is not limited to one of a pyridine ring, a piperidine ring, a piperazine ring, an isoquinoline ring, a pyrazine ring, a quinoline ring and a pyrimidine ring; preferably, a pyridine ring, a piperidine ring, a piperazine ring, an isoquinoline ring, or a pyrazine ring.
According to the invention, the compounds of the above general formula (I)Compound (I), R 3 And R 4 The five-to seven-membered ring formed by connecting with each other comprises but is not limited to one of a benzene ring, a pyridine ring, a furan ring, a thiophene ring, a pyrimidine ring and a pyrazine ring; preferably a benzene ring.
In any part herein, the substituents in said substituted or unsubstituted are independently selected from C 1 -C 4 Alkyl (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl) of (C), halogeno C 1 -C 4 Alkyl (the aforementioned C substituted by fluorine, chlorine, bromine or iodine) 1 -C 4 Alkyl group), C 1 -C 4 Alkoxy, halo C of 1 -C 4 Alkoxy group of (1), C 1 -C 4 Alkylthio of, C 1 -C 4 Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C 1 -C 4 Alkoxycarbonyl, C 1 -C 4 Acyloxy and the like; wherein C in the remaining radicals 1 -C 4 The alkyl moiety of (a) may be exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; the halogenated halogen atoms are selected from fluorine, chlorine, bromine and/or iodine.
According to the invention, the compound of formula (I) above, preferably Y 1 Is O or S.
According to the invention, the compound of formula (I) above, preferably Y 3 Is N.
According to the compounds of the present invention represented by the above general formula (I), preferably, R 1 ，R 2 Independently of one another, from the group consisting of hydrogen, monofluoromethyl, difluoromethyl, trifluoromethyl, benzyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, naphthylmethyl, cyclohexylmethyl, cyclopentylmethyl, picolyl, pyrimidylmethyl, 3-tolylmethyl, 3-methoxyphenylmethyl, 3-trifluoromethylbenzyl, 3, 5-ditrifluoromethylmethyl, 3-trifluoromethyl-5-fluorophenylmethyl, 3, 5-dimethoxyphenylmethyl, 4-cyanophenylmethyl, 2, 4-dichlorophenylmethyl, 2-chloropyridine-4-methyl, 2-chlorothiazole-5-methyl, n-pentyl, phenyl, methyl, isopropyl, ethoxycarbonylmethyl, pentafluorobenzyl;
R 3 ，R 4 independently of one another, from hydrogen, methyl,
Figure BDA0003946556240000041
Further preferably, Y 1 Is O or S; y is 2 Is C-R 3 ；Y 3 Is C-R 4 ；R 3 And R 4 Are connected to each other and to R 3 And R 4 Together the two C atoms of (a) form a substituted or unsubstituted phenyl ring.
The invention also provides a salt formed by the compound shown in the general formula (I) and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid or citric acid.
In the present invention, the term "acceptable salt" means a salt whose cation or anion is known and which can be used for forming uses in the art.
Suitable salts with bases are, for example: salts formed from compounds of formula (I) containing carboxyl groups include salts of alkali metals (e.g., sodium and potassium), alkaline earth metals (e.g., calcium and magnesium), ammonium and amines.
Suitable salts with acid addition, such as those formed from compounds of formula (I) containing amino groups, include salts with inorganic acids, for example, the hydrochloride, sulfate, sulfite, phosphate, hydrogen phosphate and nitrate salts, and salts with organic acids, such as acetic, malic, tartaric, citric, lactic, salicylic and oxalic acids, and the like.
The compounds of general formula (I) according to the invention are exemplified by the following specific compounds, but the invention is not limited to these compounds:
Figure BDA0003946556240000042
Figure BDA0003946556240000051
Figure BDA0003946556240000061
as another aspect of the invention, the invention provides the following compounds I-52-I-172 and agriculturally acceptable salts thereof, which are used as azoles selenone functional reagents and are applied to the fields of plant growth regulation, nutrition enhancement, seed treatment and the like.
Figure BDA0003946556240000062
Figure BDA0003946556240000071
Figure BDA0003946556240000081
Figure BDA0003946556240000091
Figure BDA0003946556240000101
The reaction route of the compound of the general formula (I) of the present invention is shown in the following (1): in the reaction formula R 1 As defined herein before, wherein "X" is Cl, br, I.
Figure BDA0003946556240000111
Y 1 ,Y 2 ,Y 3 Having the meanings as defined herein before.
In the reaction, the base includes, but is not limited to, at least one of potassium carbonate and potassium tert-butoxide.
Organic solvents include, but are not limited to, at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, 1, 4-dioxane, and acetone; more preferably acetonitrile.
The conditions for the heating reaction are preferably: stirring and reacting in an oil bath at 40-120 ℃; more preferably: stirring and reacting for 24 hours in an oil bath kettle at 100 ℃.
In the post-treatment process, the reagent for extraction is preferably ethyl acetate; the dried reagent is preferably anhydrous Na 2 SO 4 (ii) a Purification is preferably carried out by column chromatography; when column chromatography is used for purification, the eluent used is preferably petroleum ether and ethyl acetate.
Alternatively, the reaction route of the compound of the general formula (I) of the present invention is carried out by a stepwise method as shown in the following (2):
Figure BDA0003946556240000112
wherein Y is 1 ,Y 2 ,Y 3 Having the meanings as defined herein before. .
Step 1: heating a compound shown in a formula (A) and selenium powder in an organic solvent under the action of alkali to react to obtain an intermediate compound shown in a formula (B);
and 2, step: heating the intermediate compound shown in the formula (B) and sodium monochlorodifluoroacetate in an organic solvent in the presence of alkali to react to obtain the compound shown in the general formula (C).
The alkali in the reaction in the step 1 is any one or a mixture of more of potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium carbonate, lithium carbonate and sodium carbonate. Preferably any one of potassium tert-butoxide, sodium tert-butoxide and lithium tert-butoxide.
The heating temperature in the reaction of step 1 is 40 to 140 deg.C, preferably 80 deg.C.
The organic solvent used in the reaction in the step 1 is any one or a mixture of a plurality of acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and 1, 4-dioxane. Preferably, the organic solvent is selected from N, N-dimethylformamide.
The reaction of step 1 is carried out under an atmosphere of air, nitrogen, or argon. Preferably under an atmosphere of nitrogen or argon.
The alkali in the reaction in the step 2 is any one or a mixture of more of potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium carbonate, lithium carbonate and sodium carbonate. Preferably any one of potassium tert-butoxide, sodium tert-butoxide and lithium tert-butoxide.
The heating temperature in the reaction of step 2 is 40 to 140 ℃, preferably 80 ℃.
The organic solvent used in the reaction in the step 2 is any one or a mixture of a plurality of acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and 1, 4-dioxane. Preferably, the organic solvent is selected from N, N-dimethylformamide.
The reaction of step 2 is carried out under the atmosphere of air, nitrogen or argon. Preferably under an atmosphere of nitrogen or argon.
The compounds of the general formula (I) and the compounds of the formulae I-52 to I-172 show synergistic effects on the growth and development of plants, seed treatment and nutritional quality in the technical field of agriculture. In the present specification, the plant is a food crop, a vegetable and a fruit. The grain crops include, but are not limited to, wheat, rice, corn, sweet potato, soybean, broad bean, pea, mung bean, and the like. The vegetables include, but are not limited to, radish, turnip, cabbage, mustard, celery, tomato, eggplant, pepper, cucumber, pumpkin, etc. The fruits include, but are not limited to, apples, pears, hawthorns, oranges, grapefruits, peaches, longans, grapes, litchis, strawberries, pineapples, mangoes, apricots, plums, and the like. The replanting materials include, but are not limited to: the germination rate is improved, the emergence rate is improved, the germination time is prolonged, the emergence time is prolonged, the root length is increased, the hypocotyl length is increased, the weight is increased, the content of soluble sugar is increased, the content of soluble protein is increased, the content of flavonoid is increased, the content of total phenol is increased and the like.
The compounds of the general formula (I) and the compounds of the formulae I-52 to I-172 show synergistic effects on the growth and development of plants, seed treatment and nutritional quality in the technical field of agriculture. Therefore, the second technical scheme of the invention relates to the application of the compound with the general formula (I) and the compounds with the formulas I-52-I-172 as plant growth regulators and seed treatment agents, and provides a nutrition regulating composition which comprises an active component and an agriculturally acceptable carrier, wherein the weight percentage of the active component in the composition is 0.01-99.99%.
Process for the preparation of the composition as defined above: the compound of formula (I) and/or the compounds of formulae I-52 to I-172 are mixed with a carrier. The active ingredient in such compositions may comprise a single compound or a mixture of several compounds according to the invention.
The above compositions may be administered in the form of a formulation. The compounds of formula (I) and/or the compounds of formulae I-52 to I-172 are dissolved or dispersed as active ingredients in carriers or formulated so as to be more easily dispersed when used as a preparation; for example: the chemical preparation can be prepared into powder, wettable powder, missible oil, concentrated emulsion and microemulsion, suspension emulsion, granule, oil solution and ultra-low volume spray, smoke type, slow release agent and other pesticide dosage forms. In these compositions, at least one liquid or solid carrier is added, and when necessary, a suitable surfactant may be added. The carrier in the composition of the present invention is a substance satisfying the following conditions: it is formulated with active ingredients for convenient application to the locus to be treated, which may be a plant, seed or soil; or to facilitate storage, transport or handling. The carrier may be a solid or a liquid, including a substance which is normally a gas but which has been compressed to a liquid.
The compounds of the general formula (I) and/or the compounds of the formulae I-52 to I-172 show good conversion to additional values of plants in the agricultural technical field, such as seleno-substituted amino acids and the like. Thus, a third aspect of the present invention is directed to the use of a compound of formula (I) and/or compounds of formulae I-52 to I-172 as a botanical human selenium supplement to provide a nutritional supplement composition. For example: the method is characterized in that grain crops, vegetables and fruits subjected to selenium nutrition enrichment through the azol selenone derivative are used as raw materials, most of nutritional ingredients are reserved through a freeze drying technology and an ultrafine grinding technology, meanwhile, the food additive powder which is uniform and fine in drying is prepared, meanwhile, vegetables which are rich in nutrition, cheap and easy to obtain are used for matching, and a vegetable powder additive formula which is scientific in proportion and thick in vegetable flavor is obtained. The azol selenone derivatives or the plant powder with enhanced nutrition can also be used as feed additives of livestock and poultry such as chicken, duck, goose, cattle, sheep, pig, rabbit and the like, and can also be used as feed additives of aquatic animals such as fish, shrimp, turtle and the like.
The invention has the following advantages and beneficial effects:
(1) The preparation method of the oxazole selenone compound with the general formula (I) is simple, raw materials are easy to obtain, the cost is low, the growth and development of plants and the nutritional quality can be effectively improved, and the stress resistance capability, the oxidation resistance capability, the mineral element absorption capability and the like of the plants can be increased.
(2) The oxazole selenone compound with the general formula (I) can be converted into methylated selenocysteine and selenomethionine through plant metabolism, is suitable for the production of selenium-rich food, and meets the dietary requirements of human bodies.
(3) The azole selenone compound with the general formula (I) can be used as a seed treatment agent on plants, and the germination vigor of seeds can be improved and the nutrition of the seeds can be improved by soaking the plants.
(4) The azole selenone compound with the general formula (I) can be applied to plants by irrigation and spraying within the range of 0.1-100 mg/L, and has strong applicability.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The raw materials related to the invention can be directly purchased from the market. For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1: preparation of partial azole selenone compounds
Preparation of Compound I-1
Figure BDA0003946556240000131
1-benzyl triazole (0.20 mmol), selenium powder (0.40 mmol) and potassium carbonate (0.40 mmol) are added into a sealed tube and dissolved by 2mL of acetonitrile (MeCN), then bromofluoroacetate (0.50 mmol) is added, the reaction tube is sealed and placed in a 100 ℃ oil bath pot to be stirred for reaction for 24 hours. After TLC monitoring of the reaction, the reaction mixture was cooled to room temperature, extracted with ethyl acetate overnight, and the combined organic phases were dried over anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a yellow solid with a yield of 45.0%.
Preparation of Compound I-32
Figure BDA0003946556240000132
To a sealed tube was added 1- (methoxymethyl) imidazole (0.20 mmol), selenium powder (0.40 mmol), potassium carbonate (0.40 mmol) and dissolved with 2mL acetonitrile (MeCN), followed by methyl iodide (0.50 mmol), and the reaction tube was sealed and placed in a 100 ℃ oil bath and stirred for reaction for 24 hours. After TLC monitoring of the reaction, the reaction mixture was cooled to room temperature, extracted with ethyl acetate overnight, and the combined organic phases were dried over anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow liquid product with a yield of 50.0%.
Preparation of Compound I-35
Figure BDA0003946556240000141
To a sealed tube was added (S) -2- ((tert-butoxycarbonyl) amino) -3- (1H-imidazol-5-yl) propionic acid (0.20 mmol), selenium powder (0.40 mmol), potassium carbonate 0.40 mmol) and dissolved with 2mL acetonitrile (MeCN), followed by isopropyl bromide (0.50 mmol), the reaction tube was sealed and placed in a 100 ℃ oil bath and stirred for 24H. After the reaction was completed by TLC monitoring, the reaction mixture was cooled to room temperature, extracted with ethyl acetate overnight, and the organic phases were combined and washed with waterWater Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product with a yield of 70.0%.
Preparation of Compound I-36
Figure BDA0003946556240000142
Benzothiazole (0.20 mmol), selenium powder (0.40 mmol) and lithium tert-butoxide (0.40 mmol) are added into a sealed tube, dissolved in 2mLN and N Dimethylformamide (DMF) in a nitrogen atmosphere, and the reaction tube is sealed and placed in an oil bath kettle at 80 ℃ for stirring reaction for 12 hours. After TLC monitoring of the reaction, the reaction mixture was cooled to room temperature, extracted with ethyl acetate overnight, and the combined organic phases were dried over anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product with a yield of 60.0%.
Figure BDA0003946556240000143
2 (3H) -benzothiazolylenone (0.20 mmol), sodium chlorodifluoroacetate (0.40 mmol) and sodium tert-butoxide (0.40 mmol) were added to a sealed tube, dissolved in 2mLN and N-Dimethylformamide (DMF) under nitrogen, the tube was sealed and placed in an oil bath at 80 ℃ to stir for 12 hours. After the reaction was completed by TLC monitoring, the reaction mixture was cooled to room temperature, extracted with ethyl acetate overnight, and the combined organic phases were dried over anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product with a yield of 50.0%.
The synthesis of other compounds not listed is shown in a series of oxazole selenone derivatives creatively developed in our earlier stage and preparation methods thereof (patent application No. 202210330025.2,202011222204.1, 202010743473.6).
Nuclear magnetic data for some compounds (other compounds except where noted: 1 HNMR,500MHz； 13 CNMR,125MHz, internal standard TMS, solvent: CDCl 3 ) The following:
compound I-1: yellow solid. Delta H 8.13(s,1H),7.58(t,J＝59.57Hz,1H),7.49(m,2H),7.40–7.33(m,3H),5.48 (s,2H)；δ C 160.99(t,J C-F ＝2.77Hz,1C),136.63,133.79,128.88(2C),128.77(2C),128.66,109.63(t,J C-F ＝ 254.57Hz,1C),53.47.。
Compound I-2: white solid. Delta H 7.83(t,J＝57.9Hz,1H),7.56-7.45(m,2H),7.44–7.33(m,3H),5.44(s,2H), 2.54(s,3H)；δ C 162.12(t,J C-F ＝3.32Hz,),148.36,134.10,128.88(2C),128.76(2C),128.58,111.14(t,J C-F ＝ 253.37Hz1C),53.43,11.61(t,J C-F ＝2.63Hz,).。
Compound I-3: delta. For the preparation of a coating H 8.14(s,1H),7.74-7.48(m,3H),7.39-7.30(m,3H),6.39(q,J＝7.04Hz,1H),1.86(d,J＝ 7.09Hz,3H)；δ C 160.18(t,J C-F ＝2.71Hz),138.49,136.53,128.70(2C),128.53,127.40(2C),109.47(t,J C-F ＝ 254.41Hz),58.23,19.20.。
Compound I-4: delta H 8.14(s,1H),7.58(t,J＝59.00Hz,1H),7.33(d,J＝7.5Hz,1H),7.31(s,1H),7.28(s,2H), 7.25(s,1H),4.55-4.50(m,2H),3.23-3.18(m,2H)；δ C 160.48(t,J C-F ＝2.67Hz),136.79,136.28,128.82 (2C),128.71(2C),126.98,109.53(t,J C-F ＝254.32Hz),51.46,33.82.。
Compound I-5: a brown liquid. Delta H 8.13(s,1H),7.58(t,J＝59.01Hz,1H),7.30(t,J＝7.50Hz,2H),7.22(d,J＝ 7.09Hz,2H),7.20(d,J＝7.23Hz,1H),4.33(t,J＝7.22Hz,2H),2.73(t,J＝7.65Hz,2H),2.32–2.18(m, 2H)；δ C 160.36(t,J C-F ＝2.78Hz),140.33,136.27,128.41(2C),128.29(2C),126.14,109.48(t,J C-F ＝254.37 Hz),49.87,32.55,29.11.。
Compound I-6: brown solid. Delta H 8.27(d,J＝8.36Hz,1H),8.08(s,1H),7.89(d,J＝7.64Hz,2H),7.74–7.48(m, 5H),5.88(s,2H)；δ C 160.91(t,J C-F ＝2.71Hz),136.57,133.70,131.24,129.66,129.33,128.86,128.76,126.88, 126.07,125.14,123.64,109.52(t,J C-F ＝254.7Hz),51.44.。
Compound I-7: a white solid. Delta H 8.16(s,1H),7.60(t,J＝59.04Hz,1H),4.14(d,J＝7.32Hz,2H),2.13-2.01 (m,1H),1.79-1.62(m,5H),1.30-1.19(m,3H),1.14-1.04(m,2H)；δ C 160.78(t,J C-F ＝2.56Hz),136.19, 109.63(t,J C-F ＝254.36Hz),56.04,36.86,30.37(2C),26.08,25.46(2C).。
Compound I-8: a yellow liquid. Delta H 8.16(s,1H),7.59(t,J＝59.04Hz,1H),4.21(d,J＝7.67Hz,2H),2.66-2.50(m, 1H),1.77-1.65(m,4H),1.61-1.52(m,2H),1.40-1.30(m,2H)；δ C 160.43(t,J C-F ＝2.68Hz),136.25,109.62 (t,J C-F ＝254.27Hz),54.71,38.67,30.04(2C),24.95(2C).。
Compound I-9: brown solid. Delta H 8.60(d,J＝4.53Hz,1H),8.21(s,1H),7.73-7.45(m,2H),7.36(d,J＝7.79Hz, 1H),7.24(d,J＝7.2Hz,1H),5.62(s,2H)；δ C 161.80(t,J C-F ＝2.80Hz),153.24,149.83,136.91,136.76, 123.27,122.87,109.65(t,J C-F ＝254.70Hz),54.99.。
Compound I-10: yellow solid. Delta H 8.71(d,J＝4.90Hz,2H),8.24(s,1H),7.60(t,J＝58.99Hz,1H),7.25(t,J＝ 4.90Hz,1H),5.77(s,2H)；δ C 163.18,162.72(t,J C-F ＝2.73Hz),157.51(2C),136.66,120.06,109.74(t,J C-F ＝ 254.60Hz),55.04.。
Compound I-11: a yellow liquid. Delta H 8.14(s,1H),7.59(t,J＝59.00Hz,1H),7.30-7.27(m,2H),7.25(d,J＝8.15 Hz,1H),7.16(d,J＝7.23Hz,1H),5.45(s,2H),2.36(s,3H)；δ C 160.86(t,J C-F ＝2.65Hz),138.55,136.62, 133.66,129.48,129.42,128.64,125.92,109.62(t,J C-F ＝254.55Hz),53.44,21.31.。
Compound I-12: brown solid. Delta. For the preparation of a coating H 8.14(s,1H),7.58(t,J＝58.99Hz,1H),7.27(d,J＝7.90Hz,1H),7.06(d,J＝ 7.12Hz,2H),6.89(d,J＝8.34Hz,1H),5.45(s,2H),3.81(s,3H)；δ C 161.07(t,J C-F ＝2.66Hz),159.81,136.65, 135.20,129.84,121.07,114.42,114.26,109.66(t,J C-F ＝254.60Hz),55.25,53.45.。
Compound I-13: yellow solid. Delta. For the preparation of a coating H 8.17(s,1H),7.76(s,1H),7.71(d,J＝7.71Hz,1H),7.68-7.45(m,3H),5.53 (s,2H)；δ C 161.47(t,J C-F ＝2.80Hz),136.91,134.64,132.42(d,J C-F ＝0.79Hz),131.24(q,J C-F ＝32.59Hz), 129.42,127.03-120.53(m,3C),109.65(t,J C-F ＝254.92Hz),52.93.。
Compound I-14: a white solid. Delta H 8.19(s,1H),7.99(s,2H),7.88(s,1H),7.55(t,J＝58.88Hz,1H),5.59(s,2H)；δ C 161.99(t,J C-F ＝2.90Hz),137.09(2C),135.97,132.28(q,J C-F ＝33.72Hz,2C),129.34,129.32,126.21- 119.70(m,2C),109.59(t,J C-F ＝255.26Hz),52.37.。
Compound I-15: brown solid. Delta. For the preparation of a coating H 8.19(s,1H),7.69–7.40(m,3H),7.32(d,J＝8.25Hz,1H),5.52(s,2H)；δ C 163.47-161.47(m,2C),137.16(d,J C-F ＝7.57Hz),137.00,133.10(dd,J C-F ＝33.56,8.01Hz),122.92(dd,J C-F ＝272.65,2.96Hz),121.56(p,J C-F ＝3.57Hz),119.55(d,J C-F ＝22.24Hz),113.33(dq,J C-F ＝24.46,3.83Hz), 109.62(t,J C-F ＝255.12Hz),52.39(d,J C-F ＝1.27Hz).。
Compound I-16: white solid. Delta H 8.15(s,1H),7.57(t,J＝58.99Hz,1H),6.65(d,J＝2.21Hz,2H),6.42(t,J＝2.21Hz,1H),5.39(s,2H),3.78(s,6H)；δ C 161.09(t,J C-F ＝2.77Hz),160.96(2C),136.64,135.83,109.64(t, J C-F ＝254.58Hz),106.80(2C),100.52,55.35(2C),53.54.。
Compound I-17: a white solid. Delta H 8.18(s,1H),7.67-7.43(m,5H),5.52(s,2H)；δ C 161.73(t,J C-F ＝2.68Hz), 138.66,136.96,132.58(2C),129.48(2C),118.22,112.70,109.58(t,J C-F ＝255.09Hz),52.82.。
Compound I-18: yellow solid. Delta H 8.18(s,1H),7.59(t,J＝58.93Hz,1H),7.46(d,J＝1.94Hz,1H),7.29–7.24 (m,2H),5.57(s,2H)；δ C 161.94(t,J C-F ＝2.64Hz),136.81,135.24,134.54,131.15,130.04,129.71,127.47, 109.59(t,J C-F ＝254.9Hz),50.45.。
Compound I-19: yellow solid. Delta H 8.54(d,J＝2.26Hz,1H),8.18(s,1H),7.86(dd,J＝8.22Hz,2.44Hz,1H), 7.53(t,J＝58.90Hz,1H),7.32(d,J＝8.2Hz,1H),5.46(s,2H)；δ C 161.43(t,J C-F ＝2.84Hz),151.94,150.08, 139.46,136.94,128.44,124.40,109.50(t,J C-F ＝255.10Hz),50.13.。
Compound I-20: a brown liquid. Delta. For the preparation of a coating H 8.17(s,1H),7.70(s,1H),7.51(t,J＝58.86Hz,1H),5.58(s,2H)；δ C 161.23(t, J C-F ＝2.81Hz),153.63,142.27,136.94,131.74,109.47(t,J C-F ＝255.21Hz),45.74.。
Compound I-21: yellow solid. Delta H 8.17(s,1H),8.03(d,J＝8.09Hz,2H),7.68-7.45(m,3H),5.52(s,2H),3.91 (s,3H)；δ C 161.47(t,J C-F ＝2.68Hz),161.43,138.48,136.83,130.42,130.06(2C),128.73(2C),109.61(t,J C-F ＝254.87Hz),53.03,52.19。
Compound I-22: brown solid. Delta. For the preparation of a coating H 8.22(s,1H),8.20(d,J＝3.00Hz,2H),7.67-7.43(m,3H),5.57(s,2H)；δ C 161.78(t,J C-F ＝2.81Hz),148.01,140.52,137.02,129.70(2C),123.99(2C),109.57(t,J C-F ＝255.09Hz), 52.52。
Compound I-23: yellow solid. Delta. For the preparation of a coating H 8.22(s,1H),8.16(d,J＝8.46Hz,1H),8.09(d,J＝8.50Hz,1H),7.81(d,J＝ 8.08Hz,1H),7.74–7.50(m,3H),7.44(d,J＝8.45Hz,1H),5.82(s,2H)；δ C 162.15(t,J C-F ＝2.86Hz),153.64, 147.74,137.29,136.86,129.94,129.38,127.57,126.95,119.91,109.73(t,J C-F ＝254.74Hz),55.66。
Compound I-24: yellow solid. Delta H 8.15(s,1H),7.56(t,J＝58.96Hz,1H),7.00–6.97(m,2H),6.76(d,J＝7.87 Hz,1H),5.93(s,2H),5.35(s,2H)；δ C 160.55(t,J C-F ＝2.74Hz),147.79,147.72,136.59,127.32,122.75, 111.53-107.48(m,3C),101.14,53.16。
Compound I-25: a white solid. Delta H 8.15(s,1H),7.55(t,J＝58.98Hz,1H),3.89(s,3H)；δ C 160.88(t,J C-F ＝3.96 Hz),136.24,109.67(t,J C-F ＝254.37Hz),37.67。
Compound I-26: a yellow liquid. Delta H 8.16(s,1H),7.59(t,J＝59.03Hz,1H),4.31–4.25(m,2H),1.92–1.84(m, 2H),1.41–1.28(m,7H),0.89(t,J＝6.93Hz,2H)；δ C 160.13(t,J C-F ＝2.81Hz),136.28,109.56(t,J C-F ＝ 254.27Hz),50.38,31.19,27.77,26.01,22.41,13.94。
Compound I-27: brown solid. Delta H 8.32(s,1H),7.95(m,2H),7.72(t,J＝59.00,1H),7.57–7.45(m,3H)；δ C ＝ 160.68(t,J C-F ＝2.58Hz),137.25,136.93,129.32,129.01(2C),124.80(2C),109.69(t,J C-F ＝254.94Hz)。
Compound I-30 as a yellow solid. Delta H 7.83(td,J＝59.60,1.6Hz,1H),7.39–7.32(m,5H),7.11(d,J＝2.58Hz,1H), 6.77(t,J＝2.52Hz,1H),5.33(s,1H)；δ C 158.80(t,J C-F ＝3.14Hz),134.34,129.06(2C),128.66,128.49(2C), 120.20,114.34,110.50(t,J C-F ＝252.30Hz),52.37。
Compound I-31 as a yellow solid. Delta. For the preparation of a coating H 8.23(t,J＝58.4Hz,1H),7.62(d,J＝7.9Hz,1H),7.39–7.23(m,7H),7.19– 7.13(m,1H),5.67(s,2H)；δ C 167.8,134.2,133.0,129.3,128.9,128.2,127.5,124.9,124.4,112.7(t,J C-F ＝ 251.0Hz),111.7(t,J C-F ＝2.7Hz),110.6,50.0。
Compound I-32 as a brown oil. 1 HNMR(600MHz,CDCl 3 ):δ H 6.93(d,J＝2.3Hz,1H),6.88(d,J＝2.3Hz,1H), 4.96(s,2H),4.23(q,J＝7.1Hz,2H),3.69(s,3H),1.28(t,J＝7.1Hz,3H). 13 CNMR(151MHz,CDCl3):δ C 167.09,157.95,119.85,119.36,77.21,77.00,76.79,61.90,50.52,37.27,14.03。
Compound I-33, yellow liquid. 1 HNMR(500MHz,CDCl 3 ):δ H 6.86(d,J＝2.31Hz,1H),6.82(s,1H),5.41(s, 2H),3.69(s,3H)； 13 CNMR(126MHz,CDCl 3 ):δ C 157.65,145.4(dm,J C-F ＝251.5Hz,146.70–146.48, 144.70–144.48,2C),141.6(dm,J C-F ＝258.4Hz,142.84–142.59,140.80–140.51,1C),137.6(dm,J C-F ＝254.2Hz,138.82–138.47,136.81–136.45,2C),120.22,118.18,41.47,37.29。
Compound I-34, brown liquid. 1 HNMR(600MHz,CDCl 3 ):δ H 8.02(s,1H),4.95(s,2H),4.27(q,J＝7.1Hz, 2H),3.90(s,3H),1.31(t,J＝7.1Hz,4H). 13 CNMR(151MHz,CDCl 3 ):δ C 167.09,157.95,119.85,119.36, 77.21,77.00,76.79,61.90,50.52,37.27,14.03。
Compound I-35, brown liquid. 1 HNMR(600MHz,CDCl 3 ):δ H 6.83(s,1H),5.87(s,1H),5.27(m,1H),5.14(d,J ＝7.4Hz,1H),5.04(m,1H),4.58(s,1H),3.23(s,1H),3.00(m,1H),1.44(s,9H),1.38-1.18(m,18H)；MS (ESI)m/z:462.1。
Compound I-36 as a yellow solid. Delta. For the preparation of a coating H 8.33(t,J＝57.7Hz,1H),7.78(d,J＝8.1Hz,1H),7.54-7.39(m,3H).δ C 188.2 (t,J＝3.2Hz),138.6,128.9,127.6,126.1,121.1,113.8(t,J＝4.5Hz),111.71(t,J＝256.1Hz)。
Compound I-37 as a yellow solid. Delta. For the preparation of a coating H 8.28(t,J＝57.6Hz,1H),7.77(s,1H),7.41(m,2H).δ C 188.6(t,J＝3.0Hz), 139.3,134.2,127.2,126.5,121.6,114.0(t,J＝4.9Hz),111.5(t,J＝256.8Hz)。
Compound I-38 as a yellow solid. Delta. For the preparation of a coating H 8.30(t,J＝57.9Hz,1H),7.55(s,1H),7.27(s,1H),2.37(s,3H),2.32(s,3H). δ C 187.6(t,J＝3.8Hz),137.1,137.0,135.5,126.1,121.2,114.4(t,J＝4.4Hz),111.7(t,J＝255.8Hz),20.3, 19.8。
Compound I-39, a yellow solid liquid. Delta H 8.26(t,J＝57.7Hz,1H),7.66(d,J＝1.8Hz,1H),7.63–7.52(m,2H).δ C 187.9(t,J＝3.0Hz),137.61,130.7,123.6,119.9,114.6(t,J＝4.7Hz),111.53(t,J＝256.4Hz)。
Compound I-40 as a yellow solid. Delta H 8.29(t,J＝57.7Hz,1H),7.49(m,2H),7.18(m,1H).δ C 189.2(t,J＝2.7Hz), 162.2(d,J＝248.2),139.3(d,J＝12.6Hz),124.1(d,J＝2.7Hz),121.9(d,J＝9.6Hz),114.1(d,J＝25.2Hz), 111.6(t,J＝257.0Hz),101.9(dt,J＝29.0,4.8Hz)。
Compound I-41 as a yellow solid. Delta H 8.28(t,J＝57.7Hz,1H),7.77(d,J＝8.9Hz,1H),7.41(s,1H),7.32(d,J＝8.8 Hz,1H).δ C 188.4(t,J＝3.0Hz),147.3,137.1,130.4,120.3(q,J＝259.6Hz),120.8,114.4(t,J＝4.7Hz), 113.9,111.6(t,J＝257.0Hz)。
Compound I-42, a yellow solid. Delta. For the preparation of a coating H 8.27(t,J＝57.9Hz,1H),7.66(d,J＝9.8Hz,1H),7.01(m,2H),3.85(s,3H). δ C 186.9(t,J＝3.2Hz),158.3,132.6,130.4,115.1,114.4(t,J＝4.6Hz),111.6(t,J＝255.8Hz),104.9,55.9。
Compound I-43 as a yellow solid. Delta H 8.27(t,J＝57.7Hz,1H),7.67(s,1H),7.62(d,J＝8.8Hz,1H),7.55(d,J＝8.7 Hz,1H).δ C 187.9(t,J＝2.8Hz),137.7,130.8,130.7,123.7,119.9,114.6(t,J＝4.7Hz),111.6(t,J＝256.6 Hz)。
Compound I-44, a white solid. Delta. For the preparation of a coating H 7.87(t,J＝58.2Hz,1H),7.54–7.37(m,4H).δ C 180.4(t,J＝3.7Hz),148.8, 127.5,126.0,111.9(t,J＝253.8Hz),111.5(t,J＝2.6Hz),110.94。
Compound I-45 as a white solid. Delta H 7.86(t,J＝58.2Hz,1H),7.32(d,J＝8.7Hz,2H),7.17(d,J＝9.1Hz,1H), 2.47(s,3H).δ C 180.4(t,J＝3.7Hz),147.1,136.5,127.5,126.7,111.9(t,J＝253.3Hz),111.7(t,J＝2.5Hz), 110.4,21.4。
Compound I-46, a white solid. Delta. For the preparation of a coating H 7.84(t,J＝58.3Hz,1H),7.39(d,J＝8.2Hz,1H),7.26(s,1H),7.18(d,J＝8.2 Hz,1H),2.46(s,3H).δ C 180.2(t,J＝3.7Hz),149.1,136.9,126.7,125.3,111.9(t,J＝253.9Hz),111.2,110.9 (t,J＝2.5Hz)。
Compound I-47 is a white solid. Delta. For the preparation of a coating H 7.82(t,J＝58.1Hz,1H),7.53(s,1H),7.41–7.34(m,2H).δ C 180.7(t,J＝3.4 Hz),147.4,132.1,128.4,126.2,111.8(t,J＝2.5Hz),111.7(t,J＝254.5Hz),111.6。
Compound I-48, a white solid. Delta H 7.82(t,J＝58.1Hz,1H),7.67(s,1H),7.51(dd,J＝8.7,1.7Hz,1H),7.33(d,J ＝8.7,1H).δ C 180.6(t,J＝3.5Hz),147.9,129.0,128.8,119.1,114.5(t,J＝2.9Hz),112.0,111.7(t,J＝255.2 Hz)。
Compound I-49, a white solid. Delta. For the preparation of a coating H 7.82(t,J＝58.1Hz,1H),7.62(d,J＝1.6Hz,1H),7.51(dd,J＝8.5,1.66Hz, 1H),7.39(d,J＝8.5Hz,1H).δ C 180.4(t,J＝3.5Hz),149.2,129.2,126.9,119.2,114.4,112.2(t,J＝2.7Hz), 111.8(t,J＝254.5Hz)。
Compound I-50 as a white solid. Delta. For the preparation of a coating H 8.27(t,J＝57.9Hz,1H),7.66(d,J＝9.8Hz,1H),7.01(m,2H),3.85(s,3H). δ C 186.9(t,J＝3.2Hz),158.3,132.6,130.4,115.1,114.4(t,J＝4.6Hz),111.6(t,J＝255.8Hz),104.9,56.2。
Compound I-51, a white solid. Delta. For the preparation of a coating H 7.82(t,J＝58.1Hz,1H),7.46(dd,J＝13.6,5.1Hz,2H),7.37(dd,J＝8.6,1.75 Hz,1H).δ C 180.52(t,J＝3.6Hz),149.1,132.2,126.4,126.3,111.8(t,J＝2.5Hz),111.7(t,J＝253.9Hz)。
Example 2: evaluation of azol selenone on growth and development of Chinese cabbage heart
Soaking the seeds of Chinese flowering cabbage in 5% sodium hypochlorite water solution for 10min, washing with deionized water, and soaking at 20 deg.C for 6h. Then, the seeds were uniformly sown on float trays (32.5X 22.4X 4 cm) filled with wet gauze, kept in the dark for 36 hours, and sprayed with deionized water twice a day. In the early cotyledon stage (typically 3.5-4 days), each tray was filled with 1/4 Hoagland nutrient solution containing different concentrations of compound (0 mg/L, 1mg/L, 5mg/L, 10mg/L, 15 mg/L). The processing method of selenite is completely the same as the above processing method. All trays were placed in a growth chamber with a photoperiod of 12 -2 s -1 Temperature 24. + -.2 ℃ Relative humidity 80 + -5%. Harvested after the seventh day of culture, and the fresh weight and hypocotyl length of the plant were measured for growth characteristics using electronic day and ImageJ software. The results are shown in Table 1.
Table 1: test of influence of partial compounds of the invention on fresh weight of flowering cabbage and hypocotyl length
Figure BDA0003946556240000191
Figure BDA0003946556240000201
Example 3: evaluation of Azole selenone on soluble protein content of Chinese cabbage heart
Total soluble protein content was determined by Coomassie blue staining, fresh frozen plant tissue (0.5 g) hydroponically incubated with compound was mixed with 4.0mL distilled water and ground, and centrifuged at 3000rpm for 10min. The supernatant (0.2 mL) was diluted with 0.8mL of distilled water and mixed with 5.0mL of Coomassie Brilliant blue G-250 solution. After 5min, the absorbance of the mixture was measured at 595nm using an ultraviolet spectrophotometer. Bovine serum albumin was used as a reference substance for soluble protein content analysis, and the results were expressed in mg/gFW. Compared with CK, the soluble protein content of the flowering cabbage after 1mg/L treatment of I-1, I-6, I-12, I-15, I-21, I-24, I-34 and I-47 is respectively increased by 21.78%, 17.92%, 15.98%, 21.22%, 24.58%, 23.13%, 10.76% and 20.77%; the soluble protein content of the Chinese flowering cabbage after being treated by 5mg/L is respectively increased by 23.28%, 27.12%, 25.98%, 21.22%, 14.58%, 20.13%, 16.26% and 21.88%; the content of soluble protein in the Chinese flowering cabbage after being treated by 10mg/L is respectively increased by 19.21%, 12.82%, 25.58%, 11.32%, 26.18%, 22.33%, 21.76% and 10.77%; the content of soluble protein in the flowering cabbage after being treated by 15mg/L is respectively increased by 21.78%, 27.92%, 25.78%, 22.22%, 14.01%, 13.13%, 20.76% and 22.77%.
Example 4: evaluation of Azole selenone on content of soluble sugar in Chinese cabbage
Total soluble sugar content was determined by anthrone colorimetry, and fresh frozen plant tissue (1.0 g) hydroponically cultured using the compound was mixed with 10mL of distilled water, ground, and boiled in a water bath at 100 ℃ for 30min. Also, about 10mL of distilled water was added, boiled in a water bath at 100 ℃ for 30min, and then filtered. Then, 25mL of distilled water was added. The solution (0.2 mL), distilled water (0.8 mL), ethyl acetate reagent (0.5 mL) and concentrated sulfuric acid (5 mL) were added in this order, vortexed, and then placed in a boiling water bath for 10min. After cooling to 25 ℃, the absorbance of the solution was measured at 630nm using an ultraviolet spectrophotometer. Glucose was used as a reference substance for soluble sugar content analysis, and the result was expressed as mg/g FW. Compared with CK, the soluble sugar content of the heart of the cabbage treated by 1mg/L of I-1, I-6, I-12, I-15, I-21, I-24, I-34 and I-47 is respectively increased by 13.27%, 17.59%, 13.54%, 19.35%, 11.35%, 22.11%, 21.12% and 20.35%; the soluble sugar content of the Chinese flowering cabbage after being treated by 5mg/L is respectively improved by 14.49%, 12.88%, 15.77%, 21.84%, 17.17%, 18.07%, 20.14% and 21.88%; the soluble sugar content of the Chinese flowering cabbage after being treated by 10mg/L is respectively increased by 10.83%, 22.68%, 12.45%, 11.19%, 18.24%, 16.43%, 20.37% and 22.95%; the soluble sugar content of the Chinese flowering cabbage after being treated by 15mg/L is respectively increased by 21.96%, 16.08%, 24.41%, 18.73%, 17.76%, 24.66%, 15.93% and 16.69%.
Example 5: evaluation of Azole selenone on content of Chinese cabbage total phenols
And determining the content of the total phenolic compounds by adopting a folin phenol colorimetric method. Fresh frozen plant tissue (0.5 g) following hydroponics with compound was extracted with 8.0mL absolute ethanol. The sample extract (1.0 mL) was mixed with 0.5mL of the Folin phenol reagent (diluted twice with deionized water), 1.5mL of 26.7% (w/v) sodium carbonate, and 7.0mL of distilled water. Finally, the mixture was left in the dark for 2 hours. The absorbance at 760nm was measured by an ultraviolet spectrophotometer. The results are expressed in mg/gFW, using gallic acid as a reference substance. Compared with CK, the content of the total phenols of the Chinese flowering cabbage after the treatment of 1mg/L of I-1, I-6, I-12, I-15, I-21, I-24, I-34 and I-47 is respectively increased by 12.24%, 5.74%, 11.09%, 13.49%, 18.23%, 11.65%, 7.63% and 20.35%; the content of the total phenols of the Chinese flowering cabbage after being treated by 5mg/L is respectively increased by 11.06%, 20.92%, 24.98%, 14.05%, 20.00%, 16.99%, 9.4% and 16.96%; the content of the total phenols of the Chinese flowering cabbage after the treatment by 10mg/L is respectively increased by 5.66%, 16.42%, 7.00%, 8.89%, 7.25%, 15.32%, 6.66% and 19.06%; the content of total phenols in the Chinese flowering cabbage after being treated by 15mg/L is respectively increased by 5.17%, 1.08%, 4.41%, 11.73%, 10.76%, 4.46%, 5.93% and 6.61%.
Example 6: evaluation of Azole selenone on Chinese cabbage flavone content
And (3) determining the content of total flavonoids by adopting an aluminum nitrate method. Fresh frozen plant tissue (0.5 g) following hydroponics with the compound was extracted with absolute ethanol (8.0 mL). The tissue extract (1.0 mL) was mixed with sodium nitrite solution (5%, 0.7 mL) for 5min. Aluminum nitrate (10%, 0.7 mL) was then added for 6min. Sodium hydroxide solution (5%, 5.0 mL) was added. The absorbance at 510nm was measured with an ultraviolet spectrophotometer. Rutin is taken as a reference substance, and the result is expressed in mg/gFW. Compared with CK, the content of the flowering cabbage flavonoid in the I-1, I-6, I-12, I-15, I-21, I-24, I-34 and I-47 after treatment at 1mg/L is respectively increased by 5.64%, 5.05%, 12.09%, 12.87%, 14.24%, 14.32%, 7.39% and 6.68%; the content of the flowering cabbage flavonoids after being treated by 5mg/L is respectively improved by 7.20%, 7.08%, 12.98%, 6.8%, 6.00%, 11.09%, 13.78% and 6.52%; the content of the flowering cabbage flavonoid after the treatment of 10mg/L is respectively increased by 8.42%, 9.96%, 7.88%, 6.72%, 5.37%, 8.47%, 7.63% and 7.08%; the content of flavonoid in Chinese flowering cabbage after being treated by 15mg/L is respectively improved by 7.57%, 11.08%, 7.63%, 9.07%, 11.92%, 10.52%, 8.47% and 6.61%.
Example 7: evaluation of Azole selenone on Cauliflower glucosinolate content
And (4) detecting the content of the glucosinolate by adopting a hydrolysis method. 2.8mL of acidified methanol (12.10 mol/L methanol +0.08mol/L acetic acid) was added to fresh plant tissue after hydroponic culture of about 0.50g of the powdered use compound, then used as a sample blank. Since acidification of methanol inhibits hydrolysis of glucosinolates by endogenous sarcosinases. For complete hydrolysis of the thioglycoside in the sample, 0.50g of the sample was mixed with 2.8mL of deionized water and incubated at 37 ℃ for 10min. After 2.1mL of 30.26mol/L methanol and 2mg of activated carbon were added, the reaction was stopped. Complete hydrolysis of glucosinolates produces equal molecular weight glucose. All samples were centrifuged twice at 13000rpm for 10min at 4 ℃, the supernatants were collected and analyzed for glucose content using a glucose kit (solibao BC 2500). The total glucosinolate content is equal to the difference in glucose content between the fully hydrolyzed sample and the blank sample. The results are expressed in. Mu. Mol/g. Compared with CK, the content of the glucosinolate of the cabbage heart after the treatment of 1mg/L of I-1, I-6, I-12, I-15, I-21, I-24, I-34 and I-47 is respectively improved by 13.26 percent, 5.93 percent, 15.19 percent, 7.63 percent, 2.34 percent, 10.53 percent, 2.61 percent and 6.37 percent; the content of the cabbage sulfoside treated by 5mg/L is respectively improved by 13.99%, 17.78%, 17.12%, 14.51%, 18.4%, 19.01%, 13.78% and 16.82%; the content of the glucosinolate after the treatment of 10mg/L is respectively improved by 6.16%, 5.17%, 8.43%, 6.53%, 9.92%, 10.52%, 13.87% and 17.15%; the content of the glucosinolate after the treatment of 15mg/L is respectively improved by 9.19 percent, 6.53 percent, 11.98 percent, 10.97 percent, 12.66 percent, 11.14 percent, 14.03 percent and 11.98 percent.
Example 8: evaluation of content of cabbage pigment by Azole selenone
The total chlorophyll content is determined by a colorimetric method. 0.1g of fresh plant tissue cultured by using the compound water is consumed in each treatment, 2mL of 95% ethanol and a little of calcium carbonate are added into a mortar firstly, the grinding fluid is completely absorbed into a 10mL centrifuge tube, then a little of 95% ethanol is used for cleaning the mortar and adding the mortar into the centrifuge tube, finally the volume of the centrifuge tube grinding fluid is fixed to 10mL by 95% ethanol, the grinding fluid is shaken up and placed in the dark for 24h, and the chlorophyll is fully extracted. Centrifuging at 4000r/min for 10min, collecting supernatant, and detecting absorbance at 663nm, 646nm and 470nm with ultraviolet-visible spectrophotometer. The calculation formula of the chlorophyll and carotenoid contents is as follows:
chlorophyll a (mg. L) -1 )＝12.21OD 663 -2.81OD 646
Chlorophyll b (mg. L) -1 )＝20.13OD 646 -5.03OD 663
Chlorophyll a + b (mg. L) -1 )＝17.32OD 646 +7.18OD 663
Carotenoid (mg. L) -1 )＝(1000OD 470 -3.27C a -104C b )/229
Chlorophyll (a, b and carotenoids) (mg. G) -1 )＝C*V*n/W(V＝0.01L,n＝1,W＝0.01g)
Wherein: c: concentration; v: chlorophyll extraction solvent volume; n: dilution times of the solution to be detected; w: sample mass.
The anthocyanin content is determined by a colorimetric method. Approximately 1.0g of fresh plant tissue after hydroponics with compound was consumed, ground and incubated in 10mL of 60% methanol (pH = 3.0) for 2 hours in a water bath at 60 ℃. Then, the solution was filtered and adjusted to 10ml with 60% methanol. The absorbance at 535nm was measured with an ultraviolet spectrophotometer. The results are expressed in mg/gFW.
The results are shown in tables 2-4.
Table 2: test of Effect of some Compounds of the present invention on cabbage chlorophyll
Figure BDA0003946556240000221
Figure BDA0003946556240000231
Table 3: test of Effect of partial Compounds of the present invention on Cauliflower carotenoids
Figure BDA0003946556240000232
Table 4: test of Effect of some Compounds of the present invention on cabbage Heart anthocyanin
Figure BDA0003946556240000233
Example 9: evaluation of Cauliflower amino acid composition by Azole selenone
The composition of the amino acid in the cabbage heart is analyzed by adopting a full-automatic amino acid determinator. Lyophilized plant tissue (0.3 g) after hydroponics with compound was weighed into a centrifuge tube and 15mL of 5% sulfosalicylic acid solution was added. The extract was sonicated at room temperature for 1 hour, then centrifuged again at 13000rpm for 30 minutes. The sediment is re-extracted. The supernatant was diluted and filtered through a 0.22 μm membrane, and measured using an amino acid analyzer (L-8900; hitaci, JPN). The results are shown in Table 5.
Table 5: test of the Effect of some of the Compounds of the invention on the composition of free amino acids
Figure BDA0003946556240000241
Example 10: evaluation of absorption of cabbage Heart elements by Azole selenone
Determination of the multimineral elements in fresh plant tissue after hydroponic cultivation with compounds was determined by inductively coupled plasma combined with mass spectrometry (ICP-MS) (7700 s; agilent usa). First, in a microwave digestion system (WX-8000, yirao, CHN), 10mL of 65% nitric acid was added to 0.1g of lyophilized tissue and the procedure was followed according to standard procedures. The digested solution was then fixed in 50mL volumetric flasks in ultrapure water and analyzed for macro-elements (P, K, ca, mg, na) and micro-elements (Fe, zn, mn, cu). The results are shown in tables 6-7.
Table 6: influence of partial compounds on absorption of major elements of flowering cabbage
Figure BDA0003946556240000251
Table 7: influence of partial compounds on absorption of microelements from flowering cabbage
Figure BDA0003946556240000252
Figure BDA0003946556240000261
Example 11: effect of Azole selenone compound on the accumulation of selenium form in cabbage heart
The selenium species of the tissues after hydroponic culture using the compounds were determined using liquid chromatography-hydride generation-atomic fluorescence spectroscopy (LC-HG-AFS) (AFS 851, aurora, CHN). 0.2g of vacuum freeze-dried plant tissue was accurately weighed in a 50mL centrifuge tube, extracted with 10mL Tris-HCl, and sonicated in a 37 ℃ sonication water bath for 30min. Subsequently, the enzyme protease XIV was added and the sample was shaken for 20 hours in a shaker (rotation speed: 300 r/min). After enzymolysis, centrifuging at 10000rpm/min for 30min at 4 deg.C, collectingThe supernatant was filtered through a 0.22 μm membrane and stored at-20 ℃ until analysis. Separation of the different selenium species was performed using a Hamilton PRP-X100 anion exchange column (10 μm, 250X 4.1 mm). And drawing a standard curve by adopting five standard substances. Adding 10% formic acid, adding 40mmol/L (NH) 4 ) 2 HPO 3 The pH value of (1) was adjusted to 6, and ultrasonic degassing was carried out in an ultrasonic water bath for 30min at a flow rate of 1mL/min. The eluate from the column was mixed with 0.5% sodium hydroxide, 1.5% KI and 2% KBH 4 Mixed and then passed through a UV unit. After uv ablation, 9% hydrochloric acid was further added to the mobile phase. Finally, the generated H — Se gas was transferred from the gas-liquid separator to an AFS detector using argon as a carrier through a dryer. For quantification, a calibration standard solution of selenium compounds (containing selenomethionine, selenocysteine, methylselenocysteine, selenite and selenate) was prepared from 20.0 to 500.0. Mu.g/L. The selenium species was determined by matching with standard solutions. Furthermore, the quantitative calculation is based on peak area. The results are shown in Table 8.
Table 8: part of compounds have influence on accumulation of selenium form in cabbage heart
Figure BDA0003946556240000262
Figure BDA0003946556240000271
Example 12: effect of Azole selenone as seed treatment agent on cabbage hearts
Selecting plump cabbage seeds with moderate particle size, sterilizing the seeds for 15min by using 1wt% of sodium hypochlorite, and naturally airing the seeds indoors for later use. Weighing azoles selenone compound according to a preset concentration of 0-100mg/L, placing the azoles selenone compound in a 50mL centrifuge tube, and adding H 2 And O, treating for 20min by using an ultrasonic vibrator. Weighing the same weight of each group of disinfected seeds (about 2g of 300 seeds), placing the seeds in a 50mL conical flask with uniform specification, soaking the seeds in a shade solution at room temperature for 10h, wherein the weight (g) of the seeds and the volume (mL) of the seed soaking solution are 1.Then the seeds after soaking are taken out and washed by distilled water for three times, and then the seeds are placed indoors to be dried.
Putting the aired seeds into a germination box which is filled with 10mL of distilled water and is paved with germination paper sterilized by a sterilization pot, and placing 100 seeds in each box in order by 10 x 10; then, the germination boxes were placed in an incubator for germination, with day/night illumination set at 13000/0lx and temperature set at 25 ℃/20 ℃ (16 h/8 h) at room temperature, with 3 repetitions per treatment. Adding 1mLH every day 2 O, keeping the germination box moist. Counting the germination and emergence number every day, taking the bud length more than 1mm as the germination standard, taking the stem upright, cotyledon flat, and the color of the leaf changed from light yellow to light green as the emergence standard, continuously investigating for 7d after sowing, and counting and calculating the germination rate, emergence rate, average germination time, average emergence time and the like. Control group (CK): and replacing the suspension of the oxazolselenone compound with clear water for seed soaking treatment, wherein other conditions are the same as those of the experimental group. The results are shown in Table 9.
Germination rate = the number of germinated seeds/total number of test seeds × 100%;
emergence rate = number of normal seedlings/total number of test seeds × 100%;
average germination time = ∑ (Gt × Dt)/∑ Gt, (Gt means number of seeds germinated on day t, dt means day after sowing);
average time of emergence = ∑ (St × Dt)/∑ St, (St means number of seeds emerging on day t, dt means day after sowing).
Table 9: effect of partial Compounds as seed treatment on flowering cabbage seed
Compound number Germination percentage (%) Percentage of emergence (%) Time to germination (d) Time of emergence (d)
CK 95±1 82.67±2.78 1.00±0.01 5.57±0.10
I-1 99±2 88.00±3.22 1.00±0.02 5.77±0.12
I-6 99±3 86.00±4.76 1.01±0.02 5.39±0.09
I-12 98±1 86.33±3.26 1.02±0.01 5.20±0.13
I-24 100±0 88.67±3.33 0.98±0.00 5.00±0.08
I-37 98±2 88.33±3.65 0.96±0.02 4.98±0.06
I-44 96±1 88.33±2.54 1.01±0.01 5.10±0.04
I-54 95±1 92.88±2.67 1.00±0.00 4.87±0.06
Example 13: effect of Azole selenone as Rice seed treatment agent on Germination
Selecting dormant rice seeds, mixing thoroughly (the seed quality is more than 2 grade), primarily selecting the seeds with distilled water, sterilizing with 0.1% saturated sodium hypochlorite solution for 30min, and washing with running water for use. Repeating the steps by using 50 to 100 granules. Dissolving azolesulfonone compound with dimethyl sulfoxide, and diluting with surfactant-containing aqueous solution. The experimental group and the control group are respectively provided with 5 to 7 series doses. The method is carried out by adopting a paper bed germination method. And (3) soaking the disinfected rice seeds at room temperature according to the designed dosage, setting corresponding blank control treatment without medicaments, and recording the seed soaking time. After seed soaking, the seeds are washed by distilled water for 3 to 5 times and then are sucked dry by filter paper for standby. Placing one or more layers of qualitative filter paper in a germination dish or a germination tray, wetting the filter paper with distilled water, and draining off excessive water. The paper-on-paper method or the paper-between method is adopted. Transferring the set culture apparatus into artificial climate box or sunlight greenhouse, and culturing according to GB/T3543.4, GB/T2930, and GB/T2772, wherein the treatment is repeated for at least 4 times. During germination, the temperature, moisture and aeration were checked, and distilled water was added dropwise as appropriate to keep the filter paper moist. And regularly investigating and recording the germination condition and the growth state of the seedlings after treatment. According to the different azole selenone compounds, after the effects of different concentrations of treatment are different, investigation is carried out to investigate the root length (or root fresh weight) or bud length (or bud fresh weight) of each treatment. The results are shown in Table 10.
Emergence rate = number of normal seedlings/total number of test seeds × 100%;
vitality index:
Figure BDA0003946556240000281
in the formula: VI = vitality index; x 1 = number of treated germinating seeds; x 0 = number of seeds processed; s = mean individual plant root length (or root fresh weight) or shoot length (or shoot fresh weight) in centimeters (cm) or grams (g) of germinating seedlings
Table 10: effect of partial Compounds as seed treatment Agents on Rice seeds
Figure BDA0003946556240000291
Different azolselenone can adjust the concentration and the seed soaking time according to the actual situation to obtain the best effect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The oxazolselenone derivative is characterized by having a structure shown in a general formula (I):
Figure FDA0003946556230000011
in the general formula (I):
Y 1 is O, S, N-R 2 ；
Y 2 Is N, C-R 3 ；
Y 3 Is N, C-R 4 ；
R 1 ，R 2 Independently of one another, from hydrogen, C 1 -C 12 Alkyl, halo C 1 -C 12 Alkyl radical, C 3 -C 12 Cycloalkyl, halo C 3 -C 12 Cycloalkyl radical, C 2 -C 12 Alkenyl radical, C 2 -C 12 Alkynyl, C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl, halo C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylthio group C 1 -C 12 Alkyl, halo C 1 -C 12 Alkylthio group C 1 -C 12 Alkyl, C containing sulfinyl groups 1 -C 12 Alkyl, halogen-and sulfinyl-containing C 1 -C 12 Alkyl containing sulfonyl group C 1 -C 12 Alkyl, containing halogen and sulphonyl C 1 -C 12 Alkyl, C substituted by amino 1 -C 12 Alkyl, halo C substituted by amino 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxycarbonyl, CONH 2 ，C 1 -C 12 Alkylaminocarbonyl, di (C) 1 -C 12 Alkyl) aminocarbonyl, C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl radical, by C 1 -C 12 Alkylamino carbonyl-substituted C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl, C substituted by halogen 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylaminocarbonyl radical C 1 -C 12 Alkyl, di (C) 1 -C 12 Alkyl) aminocarbonyl group C 1 -C 12 Alkyl radical, C 3 -C 12 cycloalkyl-C 1 -C 12 Alkyl, substituted or unsubstituted C 6 -C 20 aryl-C 1 -C 12 Alkyl, substituted or unsubstituted C 6 -C 20 Aryl, substituted or unsubstituted C 2 -C 20 A heteroaryl group;
R 3 ，R 4 independently of one another, from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, carboxyl, amino, nitro, fluoroacetate, -CHO, C 1 -C 12 Alkyl, halo C 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxy, halo C 1 -C 12 Alkoxy radical, C 3 -C 12 Cycloalkyl radicals, halo radicals C 3 -C 12 Cycloalkyl radical, C 2 -C 12 Alkenyl radical, C 2 -C 12 Alkynyl, C 2 -C 12 Alkenyloxy, halogeno C 2 -C 12 Alkenyloxy radical, C 2 -C 12 Alkynyloxy, halo C 2 -C 12 Alkynyloxy, C 1 -C 12 Alkylthio, halo C 1 -C 12 Alkylthio radical, C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl, halo C 1 -C 12 Alkoxy radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylthio C 1 -C 12 Alkyl, halo C 1 -C 12 Alkylthio group C 1 -C 12 Alkyl, sulfinyl-containing C 1 -C 12 Alkyl, C containing halo and sulfinyl 1 -C 12 Alkyl radical, containing sulfonyl radical C 1 -C 12 Alkyl, halogen-containing and sulphonyl C 1 -C 12 Alkyl, C substituted by amino 1 -C 12 Alkyl, halo C substituted by amino 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxycarbonyl, CONH 2 ，C 1 -C 12 Alkylaminocarbonyl, di (C) 1 -C 12 Alkyl) aminocarbonyl, C substituted by cyano 1 -C 12 Alkoxy radical, C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl radical, quilt C 1 -C 12 Alkylamino carbonyl-substituted C 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl, C substituted by halogen 1 -C 12 Alkoxycarbonyl radical C 1 -C 12 Alkyl radical, C 1 -C 12 Alkylaminocarbonyl radical C 1 -C 12 Alkyl, di (C) 1 -C 12 Alkyl) aminocarbonyl group C 1 -C 12 Alkyl radical, C 3 -C 12 cycloalkyl-C 1 -C 12 Alkyl, substituted or unsubstituted C 6 -C 20 aryl-C 1 -C 12 Alkyl, substituted or unsubstituted C 2 -C 20 heteroaryl-C 1 -C 12 Alkyl, substituted or unsubstituted C 6 -C 20 Aryl, substituted or unsubstituted C 2 -C 20 A heteroaryl group;
and/or, R 2 And R 3 Are connected to each other and to the connection R 2 And the N atom to which R is attached 3 Together form a substituted or unsubstituted five to seven-membered ring with or without N, O and/or S heteroatoms;
and/or, R 3 And R 4 Are connected to each other and to the connection R 3 And R 4 Together form a substituted or unsubstituted five to seven membered ring with or without N, O and/or S heteroatoms;
wherein the substituents in the substituted or unsubstituted group are independently selected from C 1 -C 4 Alkyl, halo C of 1 -C 4 Alkyl of (C) 1 -C 4 Alkoxy, halo C of 1 -C 4 Alkoxy group of (1), C 1 -C 4 Alkylthio of, C 1 -C 4 Alkylamino, fluoro, chloro, bromo, iodo, hydroxy, cyano, carboxy, amino, nitro, C 1 -C 4 Alkoxycarbonyl group, C 1 -C 4 And (4) acyloxy.
2. The oxazolselenone derivative and agriculturally acceptable salts thereof of claim 1, wherein R is 1 ，R 2 Independently of one another, from hydrogen, monofluoromethyl, difluoromethyl, trifluoromethyl, benzyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, naphthylmethyl, cyclohexylmethyl, cyclopentylmethyl, pyridylmethyl, pyrimidylmethyl, 3-tolylmethyl, 3-methoxymethylmethylPhenylmethyl, 3-trifluoromethylphenylmethyl, 3, 5-bistrifluoromethylmethyl, 3-trifluoromethyl-5-fluorophenylmethyl, 3, 5-dimethoxyphenylmethyl, 4-cyanophenylmethyl, 2, 4-dichlorophenylmethyl, 2-chloropyridine-4-methyl, 2-chlorothiazole-5-methyl, n-pentyl, phenyl, methyl, isopropyl, ethoxycarbonylmethyl, pentafluorobenzyl;
R 3 ，R 4 independently of one another, from hydrogen, methyl,
Figure FDA0003946556230000021
3. The oxazolselenone derivative and agriculturally acceptable salts thereof of claim 1, wherein Y is 1 Is O or S; y is 2 Is C-R 3 ；Y 3 Is C-R 4 ；R 3 And R 4 Are connected to each other and to the connection R 3 And R 4 Together the two C atoms of (a) form a substituted or unsubstituted benzene ring.
4. The oxazolselenone derivative and agriculturally acceptable salts thereof as claimed in claim 1, characterized in that the oxazolselenone derivative is selected from the following compounds:
Figure FDA0003946556230000031
Figure FDA0003946556230000041
5. the oxazolselenone derivative and agriculturally acceptable salts thereof as claimed in claim 1, wherein the agriculturally acceptable salt of the oxazolselenone derivative is formed by reacting the oxazolselenone derivative with an acid comprising at least one of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid, and citric acid.
6. Use of the azolselenone derivatives and their agriculturally acceptable salts according to claims 1 to 5 for regulating plant growth, seed treatment and improving the nutritional quality of plants.
7. The use of claim 6, wherein the regulation of plant growth and seed treatment includes, but is not limited to, promotion of germination rate, rate of emergence, time to germination, time to emergence, fresh weight, root length, hypocotyl length; improving the nutritional quality of plants includes, but is not limited to, soluble sugars, soluble proteins, total phenols, flavonoids, glucosinolates, chlorophyll, carotenoids, anthocyanins, free amino acid composition, mineral content absorption, formation of selenium forms.
8. The use according to claim 6, wherein the azolselenone derivatives and their agriculturally acceptable salts are used in concentrations ranging from 0.1mg/L to 200mg/L for the control of plant growth, seed treatment and for the improvement of the nutritional quality of plants.
9. The application of the azolselenone derivative and the agriculturally acceptable salt thereof in regulating and controlling plant growth, treating seeds and improving plant nutritional quality is characterized in that the azolselenone derivative has a structure shown as the following formula I-52-I-172:
Figure FDA0003946556230000051
Figure FDA0003946556230000061
Figure FDA0003946556230000071
Figure FDA0003946556230000081
Figure FDA0003946556230000091
10. a nutrient adjustment composition for regulating plant growth, seed treatment and improving plant nutritional quality, which comprises an active ingredient and an agriculturally acceptable carrier, wherein the active ingredient is the azolselenone derivatives and agriculturally acceptable salts thereof according to claims 1 to 5, or the active ingredient is the structural azolselenone derivatives and agriculturally acceptable salts thereof represented by I-52 to I-172 according to claim 9.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109020897A (en) * 2018-06-22 2018-12-18 华南农业大学 A kind of azole sulphur (selenium) ketone derivatives and its preparation method and application
CN112300079A (en) * 2020-11-05 2021-02-02 华南农业大学 N-difluoromethyl azole selenourea derivative or agriculturally and pharmaceutically acceptable salt and application thereof
CN114685495A (en) * 2022-03-31 2022-07-01 华南农业大学 N-difluoromethyl dinitrogen heterocyclic selenourea compounds with insecticidal, antibacterial, herbicidal and anticancer effects, and preparation and application thereof

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CN112300079A (en) * 2020-11-05 2021-02-02 华南农业大学 N-difluoromethyl azole selenourea derivative or agriculturally and pharmaceutically acceptable salt and application thereof
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