CN106866419B - Terpene ester compounds and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the technical field of chemical synthesis, and discloses a terpene ester compound with a structure of a formula (I), wherein n is 0 or 1; the substituent R is mono-substituted or poly-substitutedHydrogen, halogen, cyano, hydroxyl, nitro, C1-C5 saturated or unsaturated aliphatic hydrocarbon, C1-C5 alkoxy, phenyl, substituted phenyl, benzyl, substituted benzyl, pyridyl and substituted pyridyl. The synthetic route takes (+) -anethol, substituted benzoic acid and derivatives thereof as starting raw materials, and has the advantages of reasonable synthetic route, high yield, easy separation and the like. The terpene ester compound can be used for preventing and treating agricultural diseases and insect pests.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, relates to a terpene ester compound with a novel structure, and particularly relates to a preparation method and application of a Tschimganin analogue.
Background
Terpene ester compounds have been developed into drugs very early and more, and due to their special structures and activity characteristics, more and more researchers are continuously pursuing the modification of their structures to change their activities or to develop new beneficial activities. The increase or change of some functional groups in the terpene ester compound can greatly improve the drug effect of the compound, reduce the toxic and side effects on human bodies and change the action property of the compound.
With the enhancement of the awareness of environmental protection and social sustainable development of people, the side effect of the pesticide is reduced to the minimum, and the development of the biological reasonable pesticide becomes a consensus all over the world. The botanical pesticide has the advantages of low toxicity, low residue, no harm to non-target organisms, no pollution to the environment and the like, and the development and application of the botanical pesticide become a trend gradually. And with the increasing public demand for green food and pollution-free food, the demand for plant-derived pesticides in the market is increasing day by day. The development of botanical pesticides is a necessary trend in social and scientific development.
The search of lead compounds from natural products is one of the important ways for research and development of new pesticides. Tschimganin is terpene ester compound separated from traditional insecticidal plant asafetida, and has good insecticidal, antitumor and broad-spectrum antibacterial activity.
Plant fungal diseases are the largest group of plant diseases, and include sunflower sclerotium (sunflower rot), Rape sclerotium (Rape rot), cotton rhizoctonia (Rhizoctonia), watermelon anthracnose pathogen (Colletotrichum lagenarium (Pass) Ell.et Halst), pear black spot pathogen (Alternaria kikuchiana Tanaka), rice blast pathogen [ Phyrularia grisea (Cooke) Sacc. ] and tomato leaf mold pathogen [ Fulvia fulva. Cif. ] and the like, which greatly affect the yield and quality of crops. Insect pests are one of the biggest threats in agricultural production, and each type of insect pest causes huge loss every year. In recent years, the emergence of new insecticides, particularly new insecticides having multiple unique insecticidal mechanisms and high safety, has been pursued more and more.
Therefore, the search for the Tschigmanin analogue with a novel structure has important practical significance for expanding the application of the Tschigmanin analogue and has great market potential.
Disclosure of Invention
Through a large number of researches, the Tschimganin analogue with a common structure is obtained. Based on the Tschmganin analogue synthesis method, the invention researches the biological activity of various Tschmganin analogues.
The terpene ester compound, namely Tschimganin analogue, has a chemical structure shown in a formula (I):
in the formula (I), n is 0 or 1; the substituent R is mono-substituted or multi-substituted hydrogen, halogen, cyano, hydroxyl, nitro, C1-C5 saturated or unsaturated aliphatic hydrocarbon, C1-C5 alkoxy, phenyl, substituted phenyl, benzyl, substituted benzyl, pyridyl and substituted pyridyl.
The present invention explains the terms in the context for describing the structure of the terpene ester compound of formula (I) in detail, but the explanation does not represent a specific limitation to the scope of the present invention.
The term "halogen" shall denote fluorine, chlorine, bromine or iodine.
The term "cyano" shall denote the group-CN.
The term "hydroxy" shall denote a group of-OH.
The term "nitro" shall denote-NO2A group of (1).
The term "aliphatic hydrocarbon group" means a chain-like hydrocarbon group having no benzene ring. And hydrocarbons having the basic properties of aliphatic compounds are called aliphatic hydrocarbons. The C1-C5 saturated aliphatic hydrocarbon group is the C1-C5 alkyl group. The term "alkyl" shall mean a monovalent group derived from an alkane by removing a hydrogen atom from any carbon atom of the alkane, the carbon atoms of which form a straight or branched chain backbone, and thus, can be divided into "straight chain alkyl" and "branched chain alkyl". The term includes the primary, secondary and tertiary alkyl subclasses, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl. In particular, the term "alkane" refers to a saturated hydrocarbon compound containing only carbon and hydrogen. The "C1-C5 unsaturated aliphatic hydrocarbon group" refers to a C1-C5 chain hydrocarbon group having an unsaturated bond.
The term "alkoxy" refers to a group in which one hydrogen on an alkane is replaced with an oxygen. "C1-C5 alkoxy" refers to a group in which one hydrogen of a C1-C5 alkane is replaced by oxygen.
The term "phenyl" shall denote a group in which a hydrogen on the phenyl ring (C6) is replaced. "substituted phenyl" means that the hydrogen of a carbon atom on the phenyl group is replaced with another group. "substituted phenyl" can be divided into mono-substituted phenyl and poly-substituted phenyl. The term "monosubstituted phenyl" is understood to mean phenyl in which a hydrogen of one carbon atom is replaced by another group. For example, this hydrogen may be substituted by halogen (fluorine, chlorine, bromine or iodine) to form o-, m-or p-halophenyl; or substituted by methyl to form o-methylphenyl, m-methylphenyl and p-methylphenyl; or substituted by methoxy to form o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl.
The term "polysubstituted phenyl" shall mean a phenyl group wherein the hydrogens of two or more carbon atoms are replaced by other groups. For example, two chlorine atoms, or two fluorine atoms, or one chlorine atom and one fluorine atom may be substituted for hydrogens on different carbon atoms; the hydrogen on the benzene ring is replaced by methyl and fluorine atoms to form 2-fluoro-p-methylphenyl; or the hydrogen on the benzene ring is replaced by methyl and chlorine, so that 3-chloro-2-methylphenyl can be formed; or the hydrogen on the benzene ring is substituted by two trifluoromethyl groups to form a 3, 5-trifluoromethylphenyl group.
The term "benzyl" is also known as benzyl, and has the structure phenyl-methylene-. The term "substituted benzyl" is understood to mean that the hydrogen of the benzyl group is replaced by another group, which may be on the phenyl group or on the methylene group.
The term "pyridyl" is understood to mean a group in which the hydrogen on the pyridine is replaced. And "substituted pyridyl" is understood to mean that the hydrogen of a carbon atom on the pyridyl is replaced by another group.
In addition, the invention also provides two preparation methods of the terpene ester compound. The first preparation method comprises the following steps: the terpene ester compound of formula (I) is obtained by using a compound of formula (II) as a raw material and carrying out catalytic esterification on 4-Dimethylaminopyridine (DMAP) and Dicyclohexylcarbodiimide (DCC) according to an esterification reaction in organic synthesis.
In the formula (II), n is 0 or 1; r is mono-substituted or multi-substituted hydrogen, halogen, cyano, hydroxyl, nitro, C1-C5 saturated or unsaturated aliphatic hydrocarbon, C1-C5 alkoxy, phenyl, substituted phenyl, benzyl, substituted benzyl, pyridyl and substituted pyridyl. The explanation of each term is described in the formula (I), and the description is omitted here.
Adding substituted aromatic acid, (+) -linalool and 4-dimethylaminopyridine into a reaction vessel, adding dichloromethane for dissolving and stirring, and cooling to 0 ℃ in an ice bath; slowly dripping a dichloromethane solution of dicyclohexylcarbodiimide into the solution in an ice bath, removing the ice bath after dripping, returning to room temperature and stirring to obtain the terpene ester compound shown in the formula (I). The specific synthetic route is as follows:
the second preparation method comprises the following steps: taking a compound with a structure shown in a formula (II) as a raw material, namely, firstly, carrying out acyl chlorination on the compound with the structure shown in the formula (II) by using thionyl chloride, and synthesizing the terpene ester compound shown in the formula (I) according to an esterification reaction in organic synthesis.
Adding substituted benzoic acid into a reaction container, dissolving the substituted benzoic acid with toluene, adding thionyl chloride and N, N-dimethylformamide, heating, stirring and refluxing until the reaction is finished, distilling under normal pressure after the reaction is finished, removing the toluene and redundant thionyl chloride and the like to obtain substituted benzoyl chloride, and adding dichloromethane to dissolve the substituted benzoyl chloride for later use; and (3) adding (+) -camphol and triethylamine into another reaction bottle, dissolving with dichloromethane, dropwise adding dichloromethane solution of substituted benzoyl chloride under ice bath, removing the ice bath after dropwise adding, returning to room temperature and stirring to obtain the terpene ester compound shown in the formula (I). The specific synthetic route is as follows:
on the other hand, the invention also provides the application of the terpene ester compound with the structure of the formula (I) in the aspect of preventing and treating agricultural pests.
In another aspect, the invention also provides a pharmaceutical composition, the active ingredient of which contains the terpene ester compound with the structure of formula (I).
Compared with the prior art, the terpene ester compound and the synthesis method thereof have the following beneficial effects or advantages:
(1) the terpene ester compound with the structure of formula (I) has novel synthetic route, high yield and easy separation of products, and can be said to be the optimal route for preparing the compound. By adopting the synthetic route of the invention and selecting the compound with the structure of formula (II) as the raw material, different Tschimganin analogues can be obtained.
(2) The Tschimganin analogue has a novel compound structure and a large modification scope. Biological tests show that the compound has excellent acaricidal, insecticidal and bactericidal activities, can be used as a pesticide activity lead compound for deep research, can be used as an agricultural bactericide for application, and has potential production and application values.
The invention is further described in the following examples, which are not intended to limit the scope of the invention in any way as indicated by the claims.
Detailed Description
Example 1 Synthesis of Tschigmkanin analogs
In this example, commercial reagent (+) -camphol and substituted benzoic acid are used as starting materials, and the target product is obtained by catalytic esterification of 4-Dimethylaminopyridine (DMAP) and Dicyclohexylcarbodiimide (DCC). The synthesis route of the target product is as follows.
The specific operation process comprises the following steps: accurately weighing 0.01mol of substituted benzoic acid, 0.011mol of (+) -camphanol and 0.002mol of 4-Dimethylaminopyridine (DMAP) into a 50mL single-neck round-bottom flask, adding 25mL of Dichloromethane (DCM) for dissolving and stirring, and cooling to 0 ℃ in ice bath; accurately weighing 0.008mol of Dicyclohexylcarbodiimide (DCC), dissolving in 5mL of dichloromethane, slowly dropwise adding the solution in an ice bath, removing the ice bath after dropwise adding is finished, returning to room temperature, stirring for 10h, detecting reaction by Thin Layer Chromatography (TLC), and stopping reaction after the raw materials completely disappear. At the moment, the system is a suspension with solids, a decompression suction filter funnel is adopted to remove the solid substances, the liquid part is collected, and a rotary evaporator is used for removing the solvent to obtain a crude product. And (3) carrying out column chromatography on the crude product, eluting by using a developing agent, sequentially collecting eluates by using test tubes, and mixing to obtain a pure target product.
Example 2 Synthesis of Tschigmkanin analogs
This example starts with commercial reagent (+) -camphol and substituted benzoic acid.
The specific operation process comprises the following steps: accurately weighing 0.01mol of substituted benzoic acid, adding 10mL of toluene, 5mL of thionyl chloride and 5 drops of N, N-dimethylformamide, heating, stirring and refluxing for 2 hours; after the reaction is finished, carrying out normal pressure distillation, removing toluene, redundant thionyl chloride and the like to obtain substituted benzoyl chloride, and adding dichloromethane for dissolving for later use; and (3) accurately weighing 0.011mol of (+) -camphanol, 10mL of dichloromethane and 0.03mol of triethylamine in another reaction bottle, dropwise adding a dichloromethane solution of substituted benzoyl chloride under ice bath, removing the ice bath after dropwise adding, returning to room temperature and stirring to obtain the crude terpene ester of the formula (I). And (3) carrying out column chromatography on the crude product, eluting by using a developing agent, sequentially collecting eluates by using test tubes, and mixing to obtain a pure target product.
Example 3 structural characterization of several Tschigmkanin analogs
This example compiles SDH designations for each compound for Tschimganin analogs for use in the present invention.
SDH-2: the chemical name is (1R, 2S, 4R) -1, 7, 7-trimethylbicyclo [2.2.1] hept-2-yl-2-hydroxy-3, 5-dinitrobenzoate, yellow powder.
1H NMR(400MHz，CDCl3)δ12.90(s，1H)，9.06(d，J＝2.8Hz，1H)，8.98(d，J＝2.9Hz，1H)，4.75(d，J＝1.9Hz，1H)，1.87(dd，J＝3.7，2.2Hz，2H)，1.65-1.55(m，2H)，1.39-1.33(m，2H)，1.23(s，3H)，1.17(s，3H)，0.89(s，3H).
13C NMR(101MHz，CDCl3)δ168.35，159.92，129.55，126.55，90.53，48.70，
48.23，41.40，40.09，29.59，26.81，25.78，20.32，19.45.
HRMS, calculated as C17H19N2O7 -(M-H)-363.11977, measured 363.11548.
SDH-4: the chemical name is (1R, 2S, 4R) -1, 7, 7-trimethylbicyclo [2.2.1] heptane-2-benzoic acid ester, and the product is colorless oil.
1H NMR(400MHz，CDCl3)δ8.14-8.04(m，2H)，7.64-7.54(m，1H)，7.51-7.43(m，2H)，4.65(d，J＝1.9Hz，1H)，2.02-1.92(m，1H)，1.85-1.77(m，2H)，1.72-1.67(m，1H)，1.59-1.49(m，1H)，1.28(dd，J＝10.3，1.5Hz，1H)，1.21(s，3H)，1.14(s，3H)，0.87(s，3H).
HRMS, calculated as C17H23O2 +(M+H)+259.16926, measured 259.16925.
SDH-7: the chemical name is (1R, 2S, 4R) -1, 7, 7-trimethylbicyclo [2.2.1] hept-2-yl-4-fluorobenzoate, and the product is colorless oil.
1H NMR(400MHz，CDCl3)δ8.14-8.05(m，2H)，7.18-7.11(m，2H)，4.63(d，J＝1.9Hz，1H)，1.98-1.88(m，1H)，1.80(tt，J＝9.1，3.0Hz，2H)，1.71-1.66(m，1H)，1.54(ddt，J＝12.6，5.7，4.0Hz，1H)，1.28(dd，J＝10.4，1.5Hz，1H)，1.20(s，3H)，1.13(s，3H)，0.86(s，3H).
13C NMR(101MHz，CDCl3)δ166.93，165.90，164.41，132.04，131.95，126.95，126.92，115.59，115.37，86.84，48.61，48.40，41.45，39.83，29.74，26.89，25.91，20.29，19.49.
HRMS, calculated as C17H22FO2 +(M+H)+277.15983, measured 277.15979.
SDH-14: the chemical name is (1R, 2S, 4R) -1, 7, 7-trimethylbicyclo [2.2.1] heptan-2-yl-2-chlorobenzoate, white solid.
1H NMR(400MHz，CDCl3)δ7.90-7.85(m，1H)，7.50-7.40(m，2H)，7.37-7.31(m，1H)，4.65(d，J＝2.0Hz，1H)，1.97-1.87(m，1H)，1.82-1.72(m，2H)，1.71-1.65(m，1H)，1.52(tdd，J＝12.5，5.8，4.1Hz，1H)，1.27(dd，J＝10.3，1.5Hz，1H)，1.23(s，3H)，1.16(s，3H)，0.90(s，3H).
13C NMR(101MHz，CDCl3)δ166.16，133.59，132.33，131.41，131.10，130.65，126.56，88.01，48.49，48.44，41.46，39.77，29.71，26.91，25.85，20.38，19.56.
HRMS, calculated as C17H22ClO2 +(M+H)+293.13028, measured 293.13025.
SDH-18: the chemical name is (1R, 2S, 4R) -1, 7, 7-trimethylbicyclo [2.2.1] hept-2-yl-2-iodobenzoate and white solid.
1H NMR(400MHz，CDCl3)δ8.02(dd，J＝7.9，1.1Hz，1H)，7.83(dd，J＝7.8，1.7Hz，1H)，7.43(td，J＝7.6，1.2Hz，1H)，7.21-7.13(m，1H)，4.66(d，J＝1.9Hz，1H)，1.95-1.86(m，1H)，1.82-1.73(m，2H)，1.72-1.66(m，1H)，1.52(tdd，J＝12.5，5.8，4.1Hz，1H)，1.27(dd，J＝10.3，1.5Hz，1H)，1.24(s，3H)，1.18(s，3H)，0.91(s，3H).
HRMS, calculated as C17H22IO2 +(M+H)+385.06590, measured 385.06583.
SDH-20: the chemical name is (1R, 2S, 4R) -1, 7, 7-trimethylbicyclo [2.2.1] hept-2-yl-4-cyanobenzoate, white solid.
1H NMR(400MHz，CDCl3)δ8.19-8.15(m，2H)，7.80-7.75(m，2H)，4.66(d，J＝1.9Hz，1H)，1.95-1.86(m，1H)，1.84-1.75(m，2H)，1.72-1.66(m，1H)，1.55(tdd，J＝12.6，5.7，4.1Hz，1H)，1.29(dd，J＝10.5，1.6Hz，1H)，1.20(s，3H)，1.13(s，3H)，0.85(s，3H).
HRMS, calculated as C18H22NO2 +(M+H)+284.16451, measured 284.16534.
SDH-22: the chemical name is (1R, 2S, 4R) -1, 7, 7-trimethylbicyclo [2.2.1] hept-2-yl-2-nitrobenzoate, white solid.
1H NMR(400MHz，CDCl3)δ7.89-7.84(m，1H)，7.82-7.78(m，1H)，7.66(dqd，J＝15.0，7.5，1.6Hz，2H)，4.64(d，J＝2.0Hz，1H)，1.80-1.76(m，1H)，1.73-1.63(m，3H)，1.53-1.43(m，1H)，1.25(dd，J＝10.3，1.5Hz，1H)，1.21(s，3H)，1.15(s，3H)，0.87(s，3H).
HRMS, calculated as C17H22NO4 +(M+H)+304.15433, measurementThe value is 304.15475.
SDH-23: the chemical name is (1R, 2S, 4R) -1, 7, 7-trimethylbicyclo [2.2.1] heptane-2-yl-3-nitrobenzoate, white solid.
1H NMR(400MHz，CDCl3)δ8.88(dd，J＝2.8，1.1Hz，1H)，8.48-8.37(m，2H)，7.73-7.66(m，1H)，4.68(d，J＝1.9Hz，1H)，1.99-1.88(m，1H)，1.82(tq，J＝9.0，2.9Hz，2H)，1.70(ddd，J＝10.4，4.0，2.3Hz，1H)，1.64-1.51(m，1H)，1.33-1.28(m，1H)，1.21(s，3H)，1.14(s，3H)，0.87(s，3H).
HRMS, calculated as C17H22NO4 +(M+H)+304.15433, measured 304.15439.
SDH-24: the chemical name is (1R, 2S, 4R) -1, 7, 7-trimethylbicyclo [2.2.1] hept-2-yl-4-nitrobenzoate, and the product is light yellow solid.
1H NMR(400MHz，CDCl3)δ8.35-8.29(m，2H)，8.27-8.21(m，2H)，4.67(d，J＝1.9Hz，1H)，1.97-1.86(m，1H)，1.86-1.76(m，2H)，1.70(ddd，J＝10.4，4.0，2.3Hz，1H)，1.63-1.51(m，1H)，1.30(dd，J＝10.5，1.5Hz，1H)，1.21(s，3H)，1.14(s，3H)，0.86(s，3H).
HRMS, calculated as C17H22NO4 +(M+H)+304.15433, measured 304.15427.
SDH-28: the chemical name is (1R, 2S, 4R) -1, 7-trimethylbicyclo [2.2.1] heptan-2-yl 4-tert-butyl-benzoate, white solid.
1H NMR(400MHz，CDCl3)δ8.06-8.02(m，2H)，7.52-7.48(m，2H)，4.64(d，J＝1.9Hz，1H)，2.02-1.93(m，1H)，1.85-1.77(m，2H)，1.69(dd，J＝10.3，1.7Hz，1H)，1.59-1.51(m，1H)，1.37(s，9H)，1.27(dd，J＝10.4，1.5Hz，1H)，1.21(s，3H)，1.13(s，3H)，0.87(s，3H).
HRMS, calculated as C21H31O2 +(M+H)+315.23186, measured 315.23184.
Example 4 acaricidal Activity of Tschmganin analogs
In this example, the acaricidal activity of Tschimganin analogues against spider mites was determined by the agar leaf method. The specific operation steps are as follows:
(1) preparing agar: accurately weighing 0.45g of agar, adding 100mL of distilled water, heating to completely dissolve the agar in the distilled water, pouring the agar solution into each hole of a 12-hole plate before the agar solution is not solidified, and pouring 2/3 accounting for the total volume of each hole until the agar is completely solidified for later use.
(2) Preparing a blade: selecting cowpea leaves with consistent leaf age, and shearing the cowpea leaves into circular leaves with the diameter consistent with that of the 12-hole plate; the cut leaves were immersed in 5mL of the test agent solution, taken out after 30s, dried and placed in a 12-well plate with the back side of the leaf facing upward.
(3) Inoculating mites: picking up 30 healthy and active female adult mites (Tetranychus truncatus) with age of 3-4 days by using a zero-number brush pen, moving the mites onto the leaves soaked with the agent without causing mechanical damage when using a brush pen brush, covering the leaves, and winding the leaves for one circle by using a sealing film. After 24h and 48h, carefully observing by using binocular dissecting mirrors, and lightly touching the feet of the mites by using the tip of a writing brush, wherein the immobile person is dead. Mortality and corrected mortality were calculated according to equations (1) and (2).
In the experiment, if the mortality of the control group is between 5 and 20 percent, the corrected mortality needs to be calculated; if the mortality rate of the control group is below 5%, the mortality rate is expressed; if the mortality rate of the control group is more than 20%, the experiment fails.
In the formula: p1Indicating mortality; k represents the number of dead insects; n represents the total number of treated worms.
In the formula: p2Indicating corrected mortality; ptIndicating treatment mortality; p0Indicating blank mortality.
The acaricidal activity of each Tschimganin analog is shown in table 1.
TABLE 1 results of the acaricidal Activity test of Tschimganin analogs
As can be seen from Table 1, various analogs of Tschimganin have significant acaricidal activity against Tetranychus truncatus. The compound SDH-23 has the acaricidal activity of 84.44% to the leaf-ampullate mite in 24 hours at 50 mu g/mL, which is equivalent to the control medicaments of bifenazate, pyridaben and hexythiazox.
Example 5 insecticidal Activity of Tschimganin analogs
In this example, the poisoning activity of Tschimganin analogues on cotton bollworms was determined by the insect-soaking method. The specific operation steps are as follows.
The toxicity of the tschimganin analogue to 3-year-old cotton bollworm larvae is determined by referring to 'pesticide indoor bioassay test standard insecticides' NY/T1154.6-2006. Soaking 3-year-old larva in the medicinal liquid with each concentration for 5s, sucking off the redundant medicinal liquid with filter paper, and inoculating into normal feed. Each treatment was repeated 3 times, with 10 replicates. The number of dead insects is checked after the treatment of the medicament for 24h, 48h and 72 h. The corrected mortality of larvae was calculated according to formula (3). The acaricidal activity of each Tschimganin analog is shown in table 2.
Corrected mortality ═ (treatment mortality-control mortality)/(100-control mortality) x 100% … … … … (3)
TABLE 2 results of the Tschimganin analogs for the killing activity of cotton bollworm
As can be seen from Table 2, the compounds SDH-25, SDH-26, SDH-27 and SDH-28 exhibit a certain insecticidal activity. The activity of SDH-28 is the best, and the insecticidal death rate of 48h can reach 60%. However, most compounds have great influence on the growth and development of cotton bollworms, and after the action of the pesticide, the test bollworms show symptoms of slow growth and dysplasia. The pesticide is shown to have certain insect growth regulation activity although the insecticidal activity is low, and needs to be studied in depth to be clear.
Example 6 bacteriostatic Activity of Tschimganin analogs
In the embodiment, the inhibition activity of the Tschimganin analogue on common phytopathogens is measured by adopting a growth rate method. The specific operation steps are as follows.
All tests were conducted in a clean bench and the materials used were sterilized using an autoclave. Under aseptic conditions, test strains are picked and placed in the center of a PDA culture medium plate containing different medicament concentrations, a blank PDA culture medium is used as a control, the test strains are placed in a constant temperature incubator at 25 ℃ for culture, and each gradient is tested in parallel for 3 times. And (4) investigating the growth condition of pathogenic bacteria hyphae according to the growth condition of the colonies in the blank control culture dish, and measuring the diameter of each treated colony by a cross method after the colonies in the blank control culture dish fully grow. The hyphal growth inhibition rate was calculated according to the formula (4). The bacteriostatic activity of each Tschimganin analog is shown in table 3.
TABLE 3 results of bacteriostatic activity test of Tschimganin analogues (% inhibition)
As can be seen from Table 3, most of the Tschimganin analogues show different degrees of bacteriostatic activity on sunflower sclerotium, rape sclerotium, cotton rhizoctone pathogenic bacteria and watermelon anthracnose pathogenic bacteria, wherein the bacteriostatic activity of SDH-2, SDH-7, SDH-11 and SDH-18 is over 50 percent, SDH-2 shows stronger inhibitory action on 4 pathogenic bacteria, has broad-spectrum bacteriostatic activity and has basically equivalent inhibitory activity to the control medicaments azoxystrobin and trifloxystrobin.
The present invention has been further described with reference to the examples, but the present invention is not limited to the above-described embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (7)
1. A terpene ester compound having the structure of formula (I):
wherein n is 1;
r is 2-Me, 4-Me, 2-Cl, 3-Cl, 4-Br, 4-I, 4-CN, 2-NO2、3-NO2、4-NO22-OMe, 3-OMe, 4-OMe or 4-t-Bu.
2. A process for preparing a terpene ester compound of claim 1, which is synthesized by esterification of a compound of formula (II):
wherein n is 1;
r is 2-Me, 4-Me, 2-Cl, 3-Cl, 4-Br, 4-I, 4-CN, 2-NO2、3-NO2、4-NO22-OMe, 3-OMe, 4-OMe or 4-t-Bu.
3. The preparation method according to claim 2, wherein the synthetic route is as follows:
4. the preparation method according to claim 2, wherein the synthetic route is as follows:
5. the preparation method of claim 3, which comprises adding substituted aromatic acid, (+) -linalool and 4-dimethylaminopyridine into a reaction vessel, adding dichloromethane to dissolve and stir, and cooling to 0 ℃ in ice bath; slowly dripping a dichloromethane solution of dicyclohexylcarbodiimide into the solution in an ice bath, removing the ice bath after dripping, returning to the room temperature and stirring.
6. The preparation method according to claim 4, which comprises adding substituted benzoic acid into a reaction vessel, dissolving with toluene, adding thionyl chloride and N, N-dimethylformamide, heating, stirring and refluxing until the reaction is finished; distilling at normal pressure, removing toluene and redundant thionyl chloride to obtain substituted benzoyl chloride, and adding dichloromethane to dissolve for later use; and (3) adding (+) -camphol and triethylamine into another reaction vessel, dissolving with dichloromethane, dropwise adding dichloromethane solution of substituted benzoyl chloride under ice bath, removing the ice bath after dropwise adding, returning to room temperature and stirring.
7. Use of a terpene ester compound according to claim 1 for controlling agricultural pests.
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