CN110386914B - Whole synthesis method and application of natural product cerbera manghas aldehyde - Google Patents
Whole synthesis method and application of natural product cerbera manghas aldehyde Download PDFInfo
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- CN110386914B CN110386914B CN201910728042.XA CN201910728042A CN110386914B CN 110386914 B CN110386914 B CN 110386914B CN 201910728042 A CN201910728042 A CN 201910728042A CN 110386914 B CN110386914 B CN 110386914B
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- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention relates to a total synthesis method of natural product cerbera mangiferin and application thereof in plant protection, belonging to the technical field of pesticides. The invention takes genipin as a raw material, wherein the genipin is oxidized by IBX to obtain a compound 1 in the first step, DDQ and acid are added, and the compound 1 is oxidized and dehydrated to obtain cerbera mangiferin. The invention does not adopt a protecting group strategy, firstly IBX only oxidizes primary hydroxyl and does not react with acetal hydroxyl to obtain an intermediate 1; and then the oxidative dehydrogenation and the dehydration elimination are completed synchronously, and only two steps are needed to synthesize the natural product cerbera mangiferin, so that the synthetic route is obviously shortened, and the method has good application prospect. The invention discovers that the natural product cerbera manghas the activities of resisting plant viruses, killing insects and sterilizing for the first time, and can be used as a novel plant source pesticide or used as a lead compound for development.
Description
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a synthesis method of natural cerbera manghas aldehyde and application thereof in plant protection.
Background
With the increasing population of the world and the changing dietary structure of people, the pressure of grain production is increasing. And diseases, insects and grasses bring great threat to the production of grains, and continuous and effective control is required. Meanwhile, the environmental, toxicological and management requirements of the application of the agrochemical products are continuously strict, and the requirements on pest control products are also continuously increased. And the sustained development of disease and pest control agent resistance further limits the application of the medicine. Therefore, there is a continuous need to discover and develop new, effective, economical pest control agents to increase crop yield and to supply an increasing number of humans.
Natural products are primary or secondary metabolites produced by living cells. Historically, natural products have been an important component of medicine and a major tool in agriculture for the control of weeds, pathogens and pests. Cerbera Manghas is a natural product with aromatic cyclopentopyran structure, fumiko was first isolated from bark of Cerbera Manghas in 1977, and also from Gardenia jasminoides Ellis in 1986. Cerbera Manghas has bactericidal activity on Helminthosporium, pyricularia, and Leptosporium of Cucurbitaceae. Cerbera Manghas aldehyde has 100% inhibitory activity on herba Avenae Fatuae, semen Tritici Aestivi, herba Alii Fistulosi and herba Trigonellae Purpureae in the concentration range of 0.75-4 μg/ml. Isoe S. subject group reports the total synthesis work of cerbera manghas aldehyde: genipin is used as a raw material, hydroxyl protection, hydroxyl functionalization of acetal, elimination reaction and oxidative aromatization are carried out to obtain cerbera aldehyde. The process requires functional group protection deprotection, and the 1,1' -thiocarbonyldiimidazole used in the process is expensive and is easy to deteriorate. Is not beneficial to the mass preparation of natural products and the subsequent research of biological activity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a total synthesis method of natural product cerbera manghas the advantages of only two steps, good controllability, high total yield, mild reaction conditions and good repeatability. The natural product cerbera mangiferin has good anti-plant virus activity and insecticidal activity and also has bactericidal activity.
The aim of the invention can be achieved by the following technical scheme:
the chemical structural formula of the natural product cerbera manghas is as follows:
the total synthesis method is to take genipin as a raw material, selectively oxidize primary hydroxyl, and then perform oxidative dehydrogenation and dehydration elimination in one pot, thus obtaining the natural product cerberal.
The synthetic route of the total synthetic method is as follows:
the first step: the raw material genipin is oxidized by IBX (2-iodoxybenzoic acid) to obtain a compound 1, wherein the molar ratio of the genipin to the IBX in the oxidation reaction is 1:1-1.5, and the solvent is dimethyl sulfoxide.
And a second step of: adding DDQ and acid, oxidizing and dehydrating the compound 1 to obtain cerberaldehyde, wherein the molar ratio of the compound 1 to DDQ (2, 3-dichloro-5, 6-dicyano-p-benzoquinone) is 1:1-1.5, and the use amount of the acid is related to the type of the acid adopted; the acid can be p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, scandium trifluoromethanesulfonic acid and the like.
The compound cerbera mangiferin has good plutella xylostella killing activity, and is equivalent to the activity of a commercial variety rotenone.
The compound cerbera mangiferin has plant virus resistance, can inhibit tobacco mosaic virus, capsicum virus, rice virus, tomato virus, sweet potato virus, melon virus, maize dwarf mosaic virus and the like, and can effectively prevent and treat virus diseases of various crops such as tobacco, capsicum, rice, tomatoes, melons, grains, vegetables, beans and the like.
The compound cerbera mangiferin of the invention shows bactericidal activity on the following 14 pathogenic bacteria, and the 14 pathogenic bacteria: cucumber wilt, peanut brown spot, apple ring spot, tomato early blight, wheat gibberella, potato late blight, rape sclerotium, cucumber gray mold, rice sheath blight, phytophthora capsici, rice bakanae, wheat sheath blight, corn small spot and watermelon anthrax.
The cerbera manghas aldehyde can be used as an active lead compound for developing green, efficient and safe pesticide varieties with plant virus resistance, insecticidal activity and bactericidal activity
The invention has the beneficial effects that: compared with the prior art, the method does not adopt a protecting group strategy, firstly IBX only oxidizes primary hydroxyl and does not react with acetal hydroxyl to obtain an intermediate 1; and then the oxidative dehydrogenation and the dehydration elimination are completed synchronously, only two steps are needed to synthesize the natural product cerbera manghas aldehyde, the synthetic route is obviously shortened, the total yield is obviously improved, the reaction condition is mild, the repeatability is good, the industrial amplified synthesis is easy to carry out, and the application prospect is good. The invention discovers that the natural product cerbera manghas the activities of resisting plant viruses, killing insects and sterilizing for the first time, and can be used as a novel plant source pesticide or used as a lead compound for development.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Example 1
The cerbera manghas aldehyde total synthesis route:
the preparation method comprises the following specific steps:
into a 500mL round bottom flask was charged 8.00g (35.4 mmol) of genipin, 10.89g (38.9 mmol) of 2-iodoxybenzoic acid (IBX) and 200mL of dimethyl sulfoxide. Under the protection of argon, after electromagnetic stirring for 3 hours at room temperature, 300mL of water is added. Filtering, extracting the filtrate with ethyl acetate four times, mixing the organic phases, washing with water, saturated saline washing, drying with anhydrous magnesium sulfate, filtering, desolventizing to obtain a crude product of the compound 1, and performing column chromatography to obtain a pure product of the compound 1, which is a light yellow solid.
A250 mL round bottom flask was charged with Compound 1 (1.00 g,4.46 mmol), DDQ (1.01 g,4.46 mmol), CF 3 SO 3 H (0.67 g,4.46 mmol), 100mL dichloromethane. Stirring at room temperature, after TLC tracking reaction is complete, cooling, adding sodium carbonate aqueous solution, separating liquid, washing aqueous phase with ethyl acetate twice, combining organic phases, washing once with water, washing once with saturated sodium chloride, drying with anhydrous magnesium sulfate, suction filtering, desolventizing, and column chromatography to obtain natural product cerbera mangiferin as bright yellow solid with a yield of 71%. 1 H NMR(400MHz,CDCl 3 )δ9.96(s,1H),9.17(s,1H),8.52(s,1H),7.95(d,J＝3.2Hz,1H),7.13(d,J＝3.2Hz,1H),4.00(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ185.20,164.84,149.87,148.32,148.12,130.45,125.27,124.60,115.23,113.64,52.54.
Example 2
The second step of the cerbera manghas aldehyde total synthesis route can also be carried out by adopting the following method:
a250 mL round bottom flask was charged with Compound 1 (1.00 g,4.46 mmol), DDQ (1.06 g,4.68 mmol), tsOH (0.77 g,4.46 mmol), 100mL toluene. Heating and stirring at 100 ℃, after TLC tracking reaction is completed, cooling, adding sodium carbonate aqueous solution, separating liquid, washing aqueous phase twice with ethyl acetate, combining organic phases, washing once with water, washing once with saturated sodium chloride, drying with anhydrous magnesium sulfate, filtering, desolventizing, and performing column chromatography to obtain natural product cerbera mangiferin which is a bright yellow solid with a yield of 76%.
Example 3
The second step of the cerbera manghas aldehyde total synthesis route can also be carried out by adopting the following method:
into a 250mL round bottom flask was charged compound 1 (1.00 g,4.46 mmol), DDQ (1.32 g,5.80 mmol), trifluoroacetic acid (5.09 g,44.6 mmol), 100mL 1, 2-dichloroethane. Heating and stirring at 80 ℃, after TLC tracking reaction is completed, cooling, adding sodium carbonate aqueous solution, separating liquid, washing aqueous phase twice with ethyl acetate, combining organic phases, washing once with water, washing once with saturated sodium chloride, drying with anhydrous magnesium sulfate, filtering, desolventizing, and performing column chromatography to obtain natural product cerbera mangiferin which is a bright yellow solid with a yield of 83%.
Example 4:
the cerbera manghas aldehyde total synthesis operation process comprises the following steps:
into a 500mL round bottom flask was charged 8.00g (35.4 mmol) of genipin, 14.87g (53.1 mmol) of 2-iodoxybenzoic acid (IBX) and 200mL of dimethyl sulfoxide. Under the protection of argon, after electromagnetic stirring for 3 hours at room temperature, 300mL of water is added. Filtering, extracting the filtrate with ethyl acetate four times, mixing the organic phases, washing with water, saturated saline washing, drying with anhydrous magnesium sulfate, filtering, desolventizing to obtain a crude product of the compound 1, and performing column chromatography to obtain a pure product of the compound 1, which is a light yellow solid.
A250 mL round bottom flask was charged with Compound 1 (1.00 g,4.46 mmol), DDQ (1.52 g,6.69 mmol), CF 3 SO 3 H (0.67 g,4.46 mmol), 100mL dichloromethane. Stirring at room temperature, after TLC tracking reaction is complete, cooling, adding sodium carbonate aqueous solution, separating liquid, washing aqueous phase with ethyl acetate twice, combining organic phases, washing once with water, washing once with saturated sodium chloride, drying with anhydrous magnesium sulfate, suction filtering, desolventizing, and column chromatography to obtain natural product cerbera mangiferin as bright yellow solid with a yield of 69%.
Example 5
Testing the activity of plutella xylostella larvae:
leaf dipping proposed by the International Commission on resistance action (IRAC) was used. 2mg of the drug sample of example 1 was weighed on an analytical balance in a 10mL small beaker, 50. Mu.L of dimethylformamide (analytically pure) was added for dissolution, and 10mL of water was added to prepare 200mg/kg of a drug solution. The cabbage leaves are immersed in a straight ophthalmic tweezer for 2-3 seconds, and the residual liquid is thrown away. 1 tablet at a time, 3 tablets per sample. Sequentially placed on the treated paper in the order of sample marking. After the liquid medicine is dried, the liquid medicine is put into a straight pipe with a length of 10cm and a mark, 2-year-old plutella xylostella larvae are inoculated, and the pipe orifice is covered by gauze. The test treatment was placed in a standard treatment chamber and the results were checked after 96 hours. Each compound was repeated 3 times. The control was prepared by adding only the emulsifier and solvent to distilled water and stirring well.
TABLE 1 Plutella xylostella killing Activity of Cerbera Manghas Guttifera aldehyde
As can be seen from Table 1, the plutella xylostella killing activity of cerbera mangiferin is equivalent to that of the commercial variety rotenone.
The compound shown in the general formula (I) can be directly used as an insecticidal bactericide, can be used together with an agriculturally acceptable carrier, can also be used in combination with other insecticidal and acaricidal bactericides such as tebufenpyrad, chlorfenapyr, etoxazole, fenpyroximate and the like, and has the synergistic effect and the additive effect.
Example 6
Determination of fungicidal activity the procedure is as follows:
in vitro sterilization test, cell growth rate assay (plate method):
a certain amount of medicament is dissolved in a proper amount of acetone, then the mixture is diluted to a required concentration by using an aqueous solution containing 200 mu g/mL of emulsifier, then 1mL of liquid medicament is respectively absorbed and injected into a culture dish, 9mL of culture medium is respectively added, and a 50 mu g/mL medicament-containing plate is prepared after shaking uniformly, and a plate added with 1mL of sterilized water is used as a blank control. The trays were cut along the outer edge of the mycelium with a punch of 4mm diameter and transferred to a medicated plate. Each treatment was repeated three times. The dishes were placed in a constant temperature incubator at 24.+ -. 1 ℃. After 48 hours, the expanded diameter of each treatment bacterial disc is investigated, the average value is calculated, and the relative antibacterial rate is calculated compared with a blank control.
TABLE 2 results of test for the bactericidal Activity of Cerbera Manghas Aldol
As can be seen from table 2, cerbera manghas exhibited activity against all fourteen fungi tested.
Example 7
Antiviral activity is exemplified by anti-tobacco mosaic virus (Tobacco mosaic virus, TMV) activity,
1. virus purification and concentration determination:
the virus purification and concentration measurement are carried out by compiling tobacco mosaic virus SOP standard according to a measuring room generated by elements of university of south China. After 2 times of polyethylene glycol centrifugation treatment, the concentration of the virus crude extract is measured, and the virus crude extract is refrigerated at 4 ℃ for standby.
2. Cerbera manghas aldehyde solution preparation:
after weighing, adding DMF to dissolve the raw materials to obtain 1×10 5 Mu g/mL mother liquor, and then diluting the mother liquor to the required concentration by using an aqueous solution containing 1 per mill of Tween 80; the ribavirin preparation is directly diluted with water.
3. In vivo passivation:
selecting 3-5 She Qishan Xie smoke with uniform growth vigor, mixing the medicament with an equal volume of virus juice, inactivating for 30min, performing friction inoculation, wherein the virus concentration is 20 mug/mL, washing with running water after inoculation, repeating for 3 times, and setting 1 milltween 80 water solution for comparison. And counting the number of lesions after 3d, and calculating a result.
Inhibition ratio (%) = [ (control number of dried spots-treated number of dried spots)/control number of dried spots ] ×100%
TABLE 3 results of in vivo tobacco mosaic virus resistance tests on cerbera manghas aldehyde
From table 3 it can be seen that cerbera mangiferin has tobacco mosaic virus resistance.
Claims (5)
1. The total synthesis method of the natural product cerbera manghas is characterized by comprising the following synthesis routes:
firstly, carrying out an oxidation reaction, wherein the molar ratio of genipin to IBX in the oxidation reaction is 1:1-1.5, and the raw material genipin is oxidized by IBX to obtain a compound 1;
and secondly, adding DDQ and acid, wherein the acid adopts any one of p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid and scandium trifluoromethanesulfonate, and the compound 1 is oxidized and dehydrated to obtain cerbera mangiferin, and the molar ratio of the compound 1 to the DDQ is 1:1-1.5.
2. The method for total synthesis of cerbera manghas, as claimed in claim 1, wherein 8.00g of genipin and 10.89g of IBX are added into a round bottom flask in the first step.
3. The method for synthesizing cerbera manghas aldehyde as claimed in claim 1, wherein 8.00g of genipin and 10.89g of IBX are added into a round bottom flask;
in a second step, 1.00g of Compound 1, 1.06g of DDQ, 0.77g of p-toluene sulfonic acid, 100mL of toluene were charged to a round bottom flask.
4. The method for synthesizing cerbera manghas aldehyde as claimed in claim 1, wherein 8.00g of genipin and 10.89g of IBX are added into a round bottom flask;
second step 1.00g of Compound 1, 1.32g of DDQ, 5.09g of trifluoroacetic acid, 100mL of 1, 2-dichloroethane were charged into a round bottom flask.
5. The method for synthesizing cerbera manghas aldehyde as claimed in claim 1, wherein 8.00g of genipin and 14.87g of IBX are added into a round bottom flask;
second step 1.00g of Compound 1, 1.52g of DDQ, 0.67g of trifluoromethanesulfonic acid, 100mL of dichloromethane were added to a round bottom flask.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6191107A (en) * | 1984-10-11 | 1986-05-09 | Sankyo Co Ltd | Fungicide for agriculture and horticulture |
| CN107522691A (en) * | 2017-08-28 | 2017-12-29 | 暨南大学 | A kind of CHR20/21 Tacrines heterozygote compound and its preparation method and application |
| CN110074124A (en) * | 2018-01-26 | 2019-08-02 | 南开大学 | Application of the phenanthridines class compound on pesticide |
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- 2019-08-08 CN CN201910728042.XA patent/CN110386914B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6191107A (en) * | 1984-10-11 | 1986-05-09 | Sankyo Co Ltd | Fungicide for agriculture and horticulture |
| CN107522691A (en) * | 2017-08-28 | 2017-12-29 | 暨南大学 | A kind of CHR20/21 Tacrines heterozygote compound and its preparation method and application |
| CN110074124A (en) * | 2018-01-26 | 2019-08-02 | 南开大学 | Application of the phenanthridines class compound on pesticide |
Non-Patent Citations (1)
| Title |
|---|
| An Efficient Synthesis of Cerbinal, a 10π Aromatic Iridoid;Yuting GE;《Chemistry letters》;19921231;第139-140页 * |
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