CN112174952A - Beta-carboline-oxazoline novel multifunctional ligand beta3Carox, its preparation and application - Google Patents
Beta-carboline-oxazoline novel multifunctional ligand beta3Carox, its preparation and application Download PDFInfo
- Publication number
- CN112174952A CN112174952A CN201910597141.9A CN201910597141A CN112174952A CN 112174952 A CN112174952 A CN 112174952A CN 201910597141 A CN201910597141 A CN 201910597141A CN 112174952 A CN112174952 A CN 112174952A
- Authority
- CN
- China
- Prior art keywords
- beta
- carboline
- oxazoline
- carox
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention relates to a novel beta-carboline-oxazoline multifunctional ligand beta3CarOx and preparation and application thereof, wherein the chemical structural formula of the compound is shown as the following formula (I):
in the general formula (I), "' represents a chiral center, and the spatial configuration is R or S; r1，R2The substituents are shown in the specification. The patent relates to a beta-carboline-oxazoline multifunctional chiral ligand beta3CarOx can be used for asymmetric addition reaction catalyzed by transition metal, and has good inhibition effect on various important agricultural pathogenic bacteria.
Description
Technical Field
The invention relates to a novel multifunctional chiral ligand beta which is connected with the 3-position of beta-carboline and the 2-position of oxazoline3CarOx and preparation and application thereof, belonging to the field of applied organic chemistry.
Background
The 'Ligand' (Ligand) plays an important role in the fields of biology and chemical research, and the obtained 'multifunctional Ligand' with chemical Ligand and drug lead potential has a wide development space, and the subject group proposes the concept of the 'multifunctional Ligand' so as to discover small molecules with catalyst Ligand potential and drug activity at the same time and verify the concept by isoquinoline-oxazoline compounds (chem.Commun., 2019, 55, 5902-.
Beta-carbolines containing a substructure of a pyridine ring are widely distributed in natural products and medicines, show various biological activities, are mostly researched in the field of medicinal chemistry at present, and also show the potential of 'ligands' in chemical synthesis catalysts. On the other hand, heterocyclic compounds containing oxazoline are widely distributed in active natural products and drug molecules and play an important role in drug molecule design and candidate compound discovery (J.Agric.FoodChem.2016, 64, 8927-8934; J.Agric.FoodChem.2018, 66, 8957-8965). In view of the modifiability and chiral diversity of oxazoline, ligands containing pyridine-oxazoline structures have increasingly important positions in asymmetric synthesis, and show excellent catalytic performance in various reactions (chem.Rev., 2009, 109, 2505-containing 2550; Org.Lett., 2015, 17, 5939-containing 5941; chem.Soc.Rev., 2018, 47, 1783-containing 1810), and the preparation and functional research (biological activity and catalytic activity) of beta-carboline-oxazoline compounds is not reported at present.
In conclusion, the oxazoline-carboline hybrid has the potential of being used as a multifunctional ligand, and can realize novel catalytic synthesis and the discovery of drug candidate compounds. The invention designs and synthesizes a novel multifunctional chiral ligand beta with the 3-position of beta-carboline connected with the 2-position of oxazoline3CarOx is found to be used in asymmetric addition reaction, and ligand molecules show good bacteriostatic activity to various agricultural pathogenic bacteria. With the prevalence of pyridine-oxazoline chiral ligands in novel efficient asymmetric synthesis and the diversified biological activities shown by carboline and oxazoline, the beta-carboline-oxazoline multifunctional ligand beta provided by the invention3CarOx, will show great potential in drug synthesis development.
Disclosure of Invention
The invention provides a novel multifunctional chiral ligand beta with 3-position of beta-carboline connected with 2-position of oxazoline3Carox and its preparation and application. The beta-carboline-oxazoline chiral ligand beta is synthesized by condensing beta-carboline-3-carboxylic acid and chiral amino alcohol and then cyclizing3CarOx having the structure of the following general formula (I):
the invention relates to a beta-carboline-oxazoline chiral multifunctional ligand beta3CarOx can be used for asymmetric addition reaction of phenylboronic acid and nitroolefin, and higher catalytic activity and stereoselectivity are obtained; meanwhile, the ligand has good bacteriostatic activity on agricultural pathogenic bacteria.
In the general formula (I), "' represents a chiral center, and the spatial configuration is R or S;
wherein the substituent R1Represents: c1～C8A phenyl group, a substituted phenyl group (the substituent on the phenyl group is C)1～C6The number of the substituent is 1-5), benzyl, substituted benzyl (the substituent on the phenyl is C)1～C6The number of the substituents is 1 to 5), hydroxymethylene, carboxylic acid, and carboxylic acid alkyl ester (C)1～C6)，C1～C6Hydrocarbyl carbonyl, phenylcarbonyl, substituted phenylcarbonyl (substituent on phenyl is C)1～C6The number of the substituent is 1-5), and substituted hydroxymethyl (the ortho position of the hydroxyl is substituted by C)1～C6Hydrocarbyl, phenyl, and substituted phenyl substitution of (a);
substituent R2Respectively represent: methyl, ethyl, isopropyl, sec-butyl, isobutyl, hydroxymethylene, hydrocarbyl carboxylate (1-6 carbons), aryl and arylmethylene;
and
the invention relates to a compound beta-carboline-3-oxazoline beta3Carox can be chemically synthesized according to the following synthetic route:
mainly comprises the following four steps of reaction:
step 1, adding L-tryptophan methyl ester hydrochloride, 37% formaldehyde and trifluoroacetic acid into a reaction system, stirring for 3 hours in an ice bath, tracking and monitoring by TLC, adjusting the pH to 5-6 by using 10% potassium carbonate aqueous solution after the reaction is completed, extracting for 2-3 times by using ethyl acetate, drying by using anhydrous sodium sulfate, and evaporating under reduced pressure to obtain yellow solid beta-tetrahydrocarboline-3-carboxylic acid methyl ester.
And 2, dissolving beta-tetrahydro carboline-3-carboxylic acid methyl ester in N, N-Dimethylformamide (DMF), adding potassium permanganate (1.2 times of the amount of the beta-tetrahydro carboline-3-carboxylic acid methyl ester) under an ice bath condition, stirring at room temperature for 8-12 hours, tracking and monitoring by TLC (thin layer chromatography), filtering after complete reaction, washing filter residues by methanol, and concentrating the obtained filtrate under reduced pressure to obtain the beta-carboline-3-carboxylic acid methyl ester.
And 3, dissolving beta-carboline-3-carboxylic acid methyl ester in methanol, adding a sodium hydroxide aqueous solution (1M) under an ice bath condition, stirring for 5 hours at 50 ℃, tracking and monitoring by TLC (thin layer chromatography), adding ethyl acetate and water after complete reaction, adjusting the pH to 5-6 by using hydrochloric acid, extracting with ethyl acetate, drying by using anhydrous sodium sulfate, and concentrating the extract under reduced pressure to obtain beta-carboline-3-carboxylic acid.
And 4, dissolving beta-carboline-3-carboxylic acid (1 time of the amount of) and amino alcohol compounds (1 time of the amount of) in dichloromethane, adding 1-hydroxybenzotriazole (1.3 times of the amount of) under an ice bath condition, then adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (1.3 times of the amount of) into the dichloromethane, stirring the mixture at room temperature for reaction, tracking and monitoring by TLC (thin layer chromatography), washing the mixture by using water, a saturated sodium bicarbonate solution and a saturated sodium chloride solution respectively after the reaction is completed, drying the mixture by using anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and carrying out silica gel column chromatography to obtain the beta-carboline-3-amidoalcohol.
And 5, dissolving beta-carboline-3-amide in dichloromethane, slowly dropwise adding diethylamino sulfur trifluoride (2 times in amount) under the protection of nitrogen, stirring and reacting for 4-6 hours at-78 ℃, tracking and monitoring by TLC, washing for 2-3 times by using a saturated sodium bicarbonate solution after the reaction is completed, drying by using anhydrous sodium sulfate, performing reduced pressure evaporation, and performing silica gel column chromatography to obtain a chiral ligand with 3-position carboline ring connected with 2-position chiral oxazoline ring.
The beta-carboline-Oxazoline chiral ligands beta3The synthesis of CarOx has the characteristics of cheap and easily obtained raw materials, easy operation and the like.
The invention relates to a chiral ligand beta with 3-position of carboline ring connected with 2-position of chiral oxazoline ring3CarOx, preferably the following compounds:
the beta-carboline-oxazoline chiral ligand beta provided by the invention3Carox activity against plant pathogenic fungi, including Rhizoctonia solani (Rhizoctonia solani), Rhizoctonia cerealis (Rhizoctonia cerealis), Sclerotium sclerotiorum (Sclerotium sclerotiorum), Rhizoctonia graminis (Fusarium graminearum), Rhizoctonia cerealis (Gaeumannomyces graminis), Botrytis cinerea (Botrytis cinerea), Phytophthora solani (Phytophthora infestans), Phytophthora capsici (Phytophthora capsici), Phytophthora solani (Alternaria solani), Phytophthora oryzae (Fusarium fujikoi), Phytophthora solani (Fusarium sukururi), Phytophthora cucumeri (Colletotrichum lagenarium), Pyricularia oryzae (Pyricularia oryzae).
Detailed Description
The invention will be further illustrated and understood by the following examples and results of activity assays, which are not intended to be limiting.
The first embodiment is as follows:
synthesis of beta-carboline-3-carboxylic acid (intermediate 3):
l-tryptophan methyl ester hydrochloride (5.1g, 20mmol) was weighed into a round-bottom flask, to which was added 37% formaldehyde (40mL) and trifluoroacetic acid (3.26mL) in that order; stirring for 3 hours at room temperature, after TLC monitoring reaction is completed, adjusting the pH to 5-6 by 10% potassium carbonate aqueous solution, extracting by ethyl acetate for three times, drying by anhydrous sodium sulfate, and evaporating under reduced pressure to obtain 4.55g of beta-tetrahydrocarboline-3-carboxylic acid methyl ester (intermediate 1) as a light yellow solid with the yield of 91%.
Weighing an intermediate beta-tetrahydro carboline-3-carboxylic acid methyl ester (intermediate 1) (4.6g, 20mmol), dissolving the intermediate beta-tetrahydro carboline-3-carboxylic acid methyl ester (intermediate 1) (4.6g, 20mmol) in a round-bottom flask, adding potassium permanganate (3g, 20mmol) under the ice bath condition, stirring at room temperature for 12 hours, filtering, washing filter residues with methanol, and concentrating the filtrate under reduced pressure to obtain yellow solid beta-carboline-3-carboxylic acid methyl ester (intermediate 2) (2.8g, yield 62%).
Weighing an intermediate beta-carboline-3-carboxylic acid methyl ester (intermediate 2) (2.8g, 12mmol), dissolving the intermediate in a round-bottom flask by using 30mL of methanol, adding 12mL (1M) of sodium hydroxide aqueous solution under ice bath, stirring for 5 hours at 50 ℃, tracking and monitoring by TLC (thin layer chromatography), adding ethyl acetate and water after the reaction is completed, adjusting the pH to 6-7 by using hydrochloric acid, extracting by using ethyl acetate, drying by using anhydrous sodium sulfate, and concentrating the extract under reduced pressure to obtain 2.33g of beta-carboline-3-carboxylic acid (intermediate 3) with the yield of 92%.
Example two:
chiral ligand (R-Et) -beta with 3-position of carboline ring connected with 2-position of chiral oxazoline ring3Synthesis of CarOx:
weighing the intermediate beta-carboline-3-carboxylic acid (3) (212mg, 1mmol) and R-2-amino-1-butanol (89mg, 1mmol) prepared above into a clean and dry pear-shaped bottle, adding 20mL of dichloromethane to dissolve the intermediate, adding HOBt (175mg, 1.3mmol), EDCi (250mg, 1.3mmol) under ice bath condition, stirring overnight at room temperature, washing the reaction system with water (10mL × 2), saturated sodium bicarbonate solution (10mL × 2) and saturated sodium chloride solution (10mL × 2), drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and performing silica gel column chromatography (eluent: V)Petroleum ether/VEthyl acetate1: 1, 1% triethylamine) to give the amidol intermediate 4a as a yellow oil in 68% yield.
Weighing intermediate amide alcohol 4a (141mg, 0.5mmol) into a Schlenk reaction bottle, adding 2mL of dichloromethane under the protection of nitrogen, and slowly dropwise adding di-ethyl-methyl-ethyl-ketone at-78 DEG CEthylaminesulfurofluoride (160mg, 1mmol) was stirred and reacted for 4 hours, the reaction system was washed with water (3 mL. times.2) and a saturated sodium bicarbonate solution (3 mL. times.2), dried over anhydrous sodium sulfate, evaporated under reduced pressure to remove the solvent, and subjected to silica gel column chromatography (eluent: V)Petroleum ether/VEthyl acetate1: 3, 1% triethylamine) to give (R-Et) - β as a yellow solid3CarOx, yield 62%.
Compound (R-Et) -beta3The structural identification data for CarOx are as follows:
ESI-HRMS Calcd for C16H16N3O[M+H]+266.1293，found 266.1297.
example three:
chiral ligand (S-iPr) -beta with 3-position of carboline ring connected with 2-position of chiral oxazoline ring3Synthesis of CarOx:
weighing the synthesized intermediate beta-carboline-3-carboxylic acid (intermediate 3) (212mg, 1mmol) and S-valinol (103mg, 1mmol) in a clean and dry pear-shaped bottle, adding 20mL of dichloromethane for dissolving, adding HOBt (175mg, 1.3mmol) and EDCi (250mg, 1.3mmol) under ice bath condition, stirring overnight at room temperature, washing the reaction system with water (10mL × 2), saturated sodium bicarbonate solution (10mL × 2) and saturated sodium chloride solution (10mL × 2), drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and performing silica gel column chromatography (eluent: V: silica gel column chromatography)Petroleum ether/VEthyl acetate1: 2, 1% triethylamine) to give the amidol intermediate 4b as a yellow solid in 68% yield.
Weighing intermediate amide alcohol 4b (141mg, 0.5mmol) in a Schlenk reaction bottle, adding dichloromethane 2mL under the protection of nitrogen, slowly dropwise adding diethylaminosulfur trifluoride (160mg, 1mmol) at-78 ℃, stirring for reacting for 4 hours, washing the reaction system with water (3mL multiplied by 2) and saturated sodium bicarbonate solution (3mL multiplied by 2), drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and performing silica gel column chromatography (eluent: V)Petroleum ether/VEthyl acetate1: 3, 1% triethylamine),obtaining yellow solid (S-iPr) -beta3CarOx, yield 58%.
Compound (S-iPr) -beta3The structural identification data for CarOx are as follows:
1H NMR(400MHz，CDCl3)9.28(s，1H)，8.97(s，1H)，8.78(s，1H)，8.15(d，J＝7.92Hz，1H)，7.53-7.60(m，2H)，7.32(m，1H)，4.56(dd，J1＝8.48Hz，J2＝6.56Hz，1H)，4.21-4.31(m，2H)，1.96(m，1H)，1.09(d，J＝6.72Hz，3H)，0.97(d，J＝6.72Hz，3H).
ESI-HRMS Calcd for C17H18N3O[M+H]+280.1450，found 280.1453.
example four:
chiral ligand (S-tBu) -beta with 3-position of carboline ring connected with 2-position of chiral oxazoline ring3Synthesis of CarOx:
weighing the synthesized intermediate beta-carboline-3-carboxylic acid (3) (212mg, 1mmol) and S-tert-leucinol (117mg, 1mmol) in a clean and dry pear-shaped bottle, adding 20mL of dichloromethane for dissolving, adding HOBt (175mg, 1.3mmol) and EDCi (250mg, 1.3mmol) under ice bath condition, stirring overnight at room temperature, washing the reaction system with water (10mL multiplied by 2), saturated sodium bicarbonate solution (10mL multiplied by 2) and saturated sodium chloride solution (10mL multiplied by 2), drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and performing silica gel column chromatography (eluent: V: 1mmol)Petroleum ether/VEthyl acetate1: 3, 1% triethylamine) to obtain the product, amide alcohol intermediate 4c, yellow oil, yield 63%.
Weighing amidol intermediate 4c (155mg, 0.5mmol) into a Schlenk reaction bottle, adding dichloromethane 2mL for dissolving under the protection of nitrogen, slowly dropwise adding diethylaminosulfur trifluoride (160mg, 1mmol) at-78 ℃, stirring for reacting for 5 hours, washing the reaction system with water (3mL multiplied by 2) and saturated sodium bicarbonate solution (3mL multiplied by 2), drying with anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and performing silica gel column chromatography (eluent: V)Petroleum ether/VEthyl acetate1: 3, 1% triethylamine) to give (S-tBu) - β as a yellow solid3CarOx, yield 72%.
The compound (S-tBu) -beta3The structural identification data for CarOx are as follows:
1H NMR(400MHz，CDCl3)
9.75(s，1H)，8.94(s，1H)，8.78(s，1H)，8.14(d，J＝7.92Hz，1H)，7.53-7.56(m，2H)，7.31(m，1H)，4.49(dd，J1＝10.04Hz，J2＝8.56Hz，1H)，4.37(dd，J1＝8.08Hz，J2＝8.56Hz，1H)，4.19(dd，J1＝10.04Hz，J2＝8.08Hz，1H)，1.01(s，9H).
ESI-HRMS Calcd for C18H20N3O[M+H]+294.1606，found 294.1606.
example five:
novel beta-carboline-oxazoline multifunctional chiral ligand (R-Et) -beta3CarOx is used for Pd-catalyzed asymmetric addition reaction of 4-methoxyphenylboronic acid and 4-methylnitroolefin:
pd (TFA) was added to a 10mL reaction flask2(3.4mg，0.01mmol)、(R-Et)-β3CarOx (3.97mg, 0.015mmol), 2mL of anhydrous methanol, was stirred at 40 ℃ for half an hour. Subsequently p-methylnitrostyrene (41.5mg, 0.25mmol), p-methoxyphenylboronic acid (76mg, 0.5mmol) were added. TLC follow-up to monitor completion of the reaction, concentration under reduced pressure, column chromatography (V)Petroleum ether∶VEthyl acetate50: 1). The ee value of the addition product was 86%.
The structural identification data of the product are as follows:
1H NMR(400MHz，CDCl3)，7.09-7.17(m，6H)，6.82-6.87(m，2H)，4.92-4.94(m，2H)，4.82(dd，J1＝J2＝8.16Hz，1H)，3.77(s，3H)，2.31(s，3H).
EXAMPLE six: novel beta-carboline-oxazoline multifunctional chiral ligand (R-Bn) -beta3Determination of the bacteriostatic activity of CarOx and the results:
the in vitro antibacterial activity evaluation is carried out by adopting a plate hypha growth rate inhibition method, and test strains are selected to be activated on a PDA plate, wherein the test strains comprise Rhizoctonia solani (Rhizoctonia solani), Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), Fusarium graminearum (Fusarium graminearum), Botrytis cinerea (Botrytis cinerea), Phytophthora capsici (Phytophtora capsici) and Pyricularia oryzae (Phycularia cerealis). Preparing the compound into 50mg/L PDA drug-containing plates, preparing a bacterial cake with the diameter of 5mm from a test strain, placing the bacterial cake in the center of a drug-containing culture dish, culturing at the constant temperature of 25 ℃ until the test strain in a blank control dish grows to be close to the edge of the culture dish, measuring the colony diameter of each drug-containing plate by using a cross method, and calculating the inhibition rate of the compound on the growth of hyphae according to the following formula:
TABLE 1 novel beta-carboline-oxazoline multifunctional chiral ligands (R-Bn) -beta3Bacteriostatic activity of CarOx
NT：NOT TEST
In conclusion, the invention relates to a novel beta-carboline-oxazoline multifunctional chiral ligand beta3CarOx can be used for asymmetric addition reaction catalyzed by transition metal, has good inhibition effect on various important agricultural pathogenic bacteria, and has the potential of deep development as a multifunctional ligand.
The invention relates to a beta-carboline-oxazoline multifunctional chiral ligand beta3The preparation of CarOx, its catalytic asymmetric synthesis as a ligand for transition metals and its use as a potential agricultural fungicide has been described by way of specific example, and those skilled in the art can refer to the inventionIt will be apparent to those skilled in the art that other modifications, variations, and equivalents of the materials and process conditions which are appropriate to achieve the objects sought herein may be made without departing from the spirit and scope of the invention.
Claims (8)
1. Beta-carboline-oxazoline multifunctional ligand shown as the following general formula (I) and pharmaceutically acceptable salts thereof,
wherein "+" in the general formula (I) represents a chiral center, and the spatial configuration is R or S;
wherein the substituent R1Represents: c1～C8A phenyl group, a substituted phenyl group (the substituent on the phenyl group is C)1～C6The number of the substituent is 1-5), benzyl, substituted benzyl (the substituent on the phenyl is C)1～C6The number of the substituents is 1 to 5), hydroxymethylene, carboxylic acid, and carboxylic acid alkyl ester (C)1～C6)，C1～C6Hydrocarbyl carbonyl, phenylcarbonyl, substituted phenylcarbonyl (substituent on phenyl is C)1～C6The number of the substituent is 1-5), and substituted hydroxymethyl (the ortho position of the hydroxyl is substituted by C)1～C6Hydrocarbyl, phenyl, and substituted phenyl substitution of (a);
substituent R2Respectively represent: methyl, ethyl, isopropyl, sec-butyl, isobutyl, hydroxymethylene, hydrocarbyl carboxylate (1-6 carbons), aryl and arylmethylene;
and
2. compounds of the general formula (I) according to claim 1, characterized in that they are preferably selected from the following compounds:
3. the method for synthesizing the beta-carboline-oxazoline multifunctional ligand shown in the general formula (I) in the claim 1 is characterized in that the synthesis method is derived from tryptophan methyl ester hydrochloride and comprises the following five steps: (1) performing Pictet-Spengler reaction on tryptophan methyl ester hydrochloride to obtain beta-tetrahydro carboline-3-carboxylic acid methyl ester; (2) oxidizing the beta-tetrahydro carboline-3-carboxylic acid methyl ester by potassium permanganate to obtain beta-carboline-3-carboxylic acid methyl ester; (3) hydrolyzing the beta-carboline-3-carboxylic acid methyl ester to obtain beta-carboline-3-carboxylic acid; (4) condensing beta-carboline-3-carboxylic acid and chiral beta-amino alcohol to obtain chiral amidol; (5) chiral amidol is subjected to ring closure to obtain beta-carboline-3-oxazoline target substance beta3CarOx。
4. The beta-carboline-oxazoline chiral ligand beta of claim 13Application of CarOx in asymmetric catalytic reaction, including Michael addition reaction, Friedel-crafts reaction, imine and [2+3 ] of olefin]Cycloaddition reactions and asymmetric oxidation reactions.
5. The beta-carboline-oxazoline multifunctional ligand beta as set forth in claim 13Application of CarOx in preventing and treating agricultural plant diseases.
6. The use as claimed in claim 5, wherein the agricultural disease is sclerotinia sclerotiorum, rhizoctonia solani, botrytis cinerea, rhizoctonia cerealis, fusarium graminearum, botrytis cinerea, phytophthora infestans, phytophthora capsici, phytophthora infestans, rice bakanae disease, potato pythium solani, cucumber colletotrichum and pyricularia oryzae.
7. Use according to claims 5 and 6, of said beta-carboline-oxazoline multifunctional ligand beta3CarOx is processed into missible oil, aqueous emulsion, microemulsion, wettable powder, water dispersible granule and suspending agent.
8. The beta-carboline-oxazoline-containing multifunctional ligand beta as set forth in claims 1 and 23The application of CarOx in preventing and treating plant diseases is characterized in that the CarOx and one or more of commercial bactericides are combined to be used for preparing compound bactericides; the commercial fungicide is selected from mandipropamid, fluxapyroxad, fluopyram, azoxystrobin, pyraclostrobin, prothioconazole, trifloxystrobin, cyproconazole, mancozeb, epoxiconazole, tebuconazole, boscalid, metalaxyl, picoxystrobin, difenoconazole, propiconazole, chlorothalonil, tiadinil, thifluzamide, isotianil, ningnanmycin, probenazole, flumorphine, dimethomorph.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910597141.9A CN112174952B (en) | 2019-07-01 | 2019-07-01 | Beta-carboline-oxazoline novel multifunctional ligand beta3Carox, its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910597141.9A CN112174952B (en) | 2019-07-01 | 2019-07-01 | Beta-carboline-oxazoline novel multifunctional ligand beta3Carox, its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112174952A true CN112174952A (en) | 2021-01-05 |
| CN112174952B CN112174952B (en) | 2022-03-29 |
Family
ID=73914510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910597141.9A Active CN112174952B (en) | 2019-07-01 | 2019-07-01 | Beta-carboline-oxazoline novel multifunctional ligand beta3Carox, its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112174952B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073454A (en) * | 2022-08-09 | 2022-09-20 | 贵州大学 | Imidazopyridine-2-oxazoline compound and preparation method and application thereof |
| CN115232115A (en) * | 2022-08-10 | 2022-10-25 | 贵州大学 | Quinclorazoline-quinazoline chiral ligand as well as preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837569A (en) * | 2016-04-29 | 2016-08-10 | 华南农业大学 | Harmaline oxazoline compound and preparation method and application thereof |
| CN105859713A (en) * | 2016-04-29 | 2016-08-17 | 华南农业大学 | Banisterine oxazoline derivate and preparation method and application thereof |
-
2019
- 2019-07-01 CN CN201910597141.9A patent/CN112174952B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837569A (en) * | 2016-04-29 | 2016-08-10 | 华南农业大学 | Harmaline oxazoline compound and preparation method and application thereof |
| CN105859713A (en) * | 2016-04-29 | 2016-08-17 | 华南农业大学 | Banisterine oxazoline derivate and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| TANMAY BANERJEE ET AL.: "Diphenylisobenzofuran Bound to Nanocrystalline Metal Oxides: Excimer Formation, Singlet Fission, Electron Injection, and Low Energy Sensitization", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073454A (en) * | 2022-08-09 | 2022-09-20 | 贵州大学 | Imidazopyridine-2-oxazoline compound and preparation method and application thereof |
| CN115073454B (en) * | 2022-08-09 | 2024-03-08 | 贵州大学 | Imidazo pyridine-2-oxazoline compound and preparation method and application thereof |
| CN115232115A (en) * | 2022-08-10 | 2022-10-25 | 贵州大学 | Quinclorazoline-quinazoline chiral ligand as well as preparation method and application thereof |
| CN115232115B (en) * | 2022-08-10 | 2024-04-16 | 贵州大学 | Quinclorac-oxazoline chiral ligand and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112174952B (en) | 2022-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112174952B (en) | Beta-carboline-oxazoline novel multifunctional ligand beta3Carox, its preparation and application | |
| CN102827077B (en) | Preparation method for phenanthridine derivative | |
| CN110372686A (en) | Adjacent (2- oxazoline group) aniline heterocyclic amides and the purposes as disinfectant use in agriculture | |
| CN112174953B (en) | Novel beta-carboline-oxazoline multifunctional ligand beta1Carox, its preparation and application | |
| CN109232363B (en) | Synthetic method of 3-selenocyanoindole compound | |
| CN115124463B (en) | Substituted quinoline compound and preparation method and application thereof | |
| CN110372622A (en) | Phenyl acetanides containing chiral oxazoline and the purposes as disinfectant use in agriculture | |
| CN102093355B (en) | C-3 acylated indolizine compound and preparation method thereof | |
| CN113563281B (en) | Benzophenone compound containing 1,3, 4-thiadiazole thioether structure and application thereof | |
| CN113072481B (en) | Indolo-cyclobutane skeleton compound, synthesis method and application | |
| CN107915628A (en) | A kind of green synthesis process of pyruvate | |
| CN114957116A (en) | 2, 3-dimethyl-8-fluoroquinoline-4-ester compound and preparation method and application thereof | |
| CN115232115B (en) | Quinclorac-oxazoline chiral ligand and preparation method and application thereof | |
| CN114276287A (en) | N- (substituted benzyloxy) amide compound and preparation method and application thereof | |
| CN112174954A (en) | Beta-carboline amide compound containing beta-arylamine and application of beta-carboline amide compound as agricultural bactericide | |
| CN107810961B (en) | Application of Topsentin alkaloid in resisting plant viruses and germs | |
| CN107814790B (en) | Topsentin derivative, preparation method thereof and application thereof in resisting plant viruses and germs | |
| CN101440068A (en) | Preparation of 4-(4-ethoxycarbonyl-1,2,3-triazole) phenylacetylene | |
| CN112174948A (en) | Novel thiazoline-tryptamine amide compound and application thereof as agricultural bactericide | |
| CN115611878A (en) | 3-arylamine (acylamino) pyridine oxazoline chiral ligand and preparation and application thereof | |
| CN114957215B (en) | Methylene bridged quinoline and 1,2, 3-triazole diheterocyclic compound and preparation method and application thereof | |
| CN108250152A (en) | It is a kind of with the 3,4- dihydroquinazoline derivatives and its synthetic method of antibacterial activity and application | |
| CN115925680B (en) | Trifluoromethyl-containing pyridine compound and preparation method and application thereof | |
| CN115433141B (en) | Alpha-oximino phenylacetamide compound, preparation method thereof and application thereof as agricultural bactericide | |
| CN111925370B (en) | Pyrazinopyrazoles naphthyridine compound and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |