CN112341334A - Terpene ester compound, preparation method thereof and application thereof in pest control of agricultural and forestry crops - Google Patents
Terpene ester compound, preparation method thereof and application thereof in pest control of agricultural and forestry crops Download PDFInfo
- Publication number
- CN112341334A CN112341334A CN202011244656.XA CN202011244656A CN112341334A CN 112341334 A CN112341334 A CN 112341334A CN 202011244656 A CN202011244656 A CN 202011244656A CN 112341334 A CN112341334 A CN 112341334A
- Authority
- CN
- China
- Prior art keywords
- substituted
- aliphatic hydrocarbyl
- formula
- ester compound
- terpene ester
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/34—Nitriles
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
- A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
-
- 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
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/04—Sulfonic acids; Derivatives thereof
- A01N41/06—Sulfonic acid amides
-
- 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
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/41—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by carboxyl groups, other than cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/22—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms
- C07C311/29—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/24—Sulfones; Sulfoxides having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/013—Esters of alcohols having the esterified hydroxy group bound to a carbon atom of a ring other than a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
- C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a terpene ester compound, a preparation method thereof and application thereof in the aspect of preventing and controlling pests of agricultural and forestry crops, belonging to the technical field of insect growth regulators. The terpene ester compound provided by the invention has a novel structure and a specific methyl substitution position, has excellent insect growth regulation activity, can be used for preventing and controlling pests in agriculture and forestry production, and has potential production application value. The invention provides a preparation method of terpene ester compounds, which takes (+) -fenchyl alcohol, substituted aromatic acid with a structure shown in a formula II or derivatives thereof as starting raw materials to obtain the terpene ester compounds with different structures through one-step esterification reaction or two-step reaction (substitution reaction and esterification reaction), and has the advantages of reasonable synthetic route, high yield, easy separation of products and the like.
Description
Technical Field
The invention relates to the technical field of insect growth regulators, in particular to a terpene ester compound, a preparation method thereof and application thereof in the aspect of pest control of agricultural and forestry crops.
Background
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, basically 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.
Due to the long history of chemical control, most pests have developed different degrees of resistance to traditional insecticides, and have a tendency to develop resistance to some agents developed in recent years, even to transgenic crops. Therefore, the development of the insect growth regulator with novel structure and unique action mechanism is the key for realizing the green prevention and control of the major pests.
Terpene ester compounds are increasingly being developed into drugs, and due to their specific structure and activity characteristics, more and more researchers are constantly pursuing the modification of their structures for the change of their activities or the emergence of 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. Therefore, the terpene ester compound with novel structure is searched, and has important practical significance for expanding the application of the terpene ester compound and great market potential.
Disclosure of Invention
The invention aims to provide a terpene ester compound, a preparation method thereof and application thereof in the aspect of controlling pests of agricultural and forestry crops.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a terpene ester compound which has a structure shown in a formula I:
in the formula I, X is positioned at any position on six carbons of a benzene ring; x is C, N or S;
n is 0 or 1; r1Is positioned at any position of six carbons on a benzene ring; m represents R1M is 1-5 and is an integer;
R1is hydrogen, halogen, cyano, hydroxyl, nitryl, carboxyl, C1-C10 saturated aliphatic alkyl, C1-C10 unsaturated aliphatic alkyl, C6-C20 aryl, C3-C20 heteroaryl, C1-C10 alkoxy, NR2R3、-CONR2R3、-COOR2or-SO2R4；
Wherein R is2、R3、R4Independently cyano, substituted cyano, hydroxyl, substituted hydroxyl, nitro, substituted nitro, amino, substituted amino, carboxyl, substituted carboxyl, C1-C10 saturated aliphatic hydrocarbyl, substituted C1-C10 saturated aliphatic hydrocarbyl, C1-C10 unsaturated aliphatic hydrocarbyl or substituted C1-C10 unsaturated aliphatic hydrocarbyl, wherein the substituent of the substituted cyano, substituted hydroxyl, substituted nitro, substituted amino, substituted carboxyl, substituted C1-C10 saturated aliphatic hydrocarbyl and substituted C1-C10 unsaturated aliphatic hydrocarbyl is independently C1-C10 saturated aliphatic hydrocarbyl, C1-C10 unsaturated aliphatic hydrocarbyl, C6-C20 aryl, C3-C20 heteroaryl or C1-C10 alkoxy.
Preferably, said R is1Is 3-CH3、2,4-(CH3)2、2,5-(CH3)2、3,5-(CH3)2、2,4,6-(CH3)3、4-t-Bu、2-C2H5、4-C2H5、2-OEt,4-OEt、3-NH2、4-NH2、2-OH、3-CN、3-(1-CH3CN)、2,3,4-F3、2,3,4,5-F4、4-Cl、2-Br、3-Br、2,5-Br2、2-I、3-I、2-CF3、3-CF3、4-CF3、4-CH2Cl、2-Cl-5-Br、4-SO2H、2-NO2-4-SO2H、2-OMe-5-SO2NH2、2-OH-4-SO2OH, 2-benzene, 2-naphthoic acid or naphthyridinic acid.
The invention provides a preparation method of the terpene ester compound in the technical scheme, which comprises the following steps:
mixing a compound with a structure shown in a formula II, (+) -fenchyl alcohol, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and a first organic solvent, and carrying out a first esterification reaction to obtain a terpene ester compound with a structure shown in a formula I;
or mixing the compound with the structure shown in the formula II, a second organic solvent, thionyl chloride and N, N-dimethylformamide for substitution reaction to obtain a substituted benzoyl chloride compound;
mixing the substituted benzoyl chloride compound, (+) -fenchyl alcohol, triethylamine and a third organic solvent, and carrying out a second esterification reaction to obtain a terpene ester compound with a structure shown in formula I;
in the formula II, X is positioned at any position on six carbons of a benzene ring; x is C, N or S;
n is 0 or 1; r1Is positioned at any position of six carbons on a benzene ring; m represents R1M is 1-5 and is an integer;
R1is hydrogen, halogen, cyano, hydroxyl, nitryl, carboxyl, C1-C10 saturated aliphatic alkyl, C1-C10 unsaturated aliphatic alkyl, C6-C20 aryl, C3-C20 heteroaryl, C1-C10 alkoxy, NR2R3、-CONR2R3、-COOR2or-SO2R4；
Wherein R is2、R3、R4Independently cyano, substituted cyano, hydroxyl, substituted hydroxyl, nitro, substituted nitro, amino, substituted amino, carboxyl, substituted carboxyl, C1-C10 saturated aliphatic hydrocarbon group, substituted C1-C10 saturated aliphatic hydrocarbon group, C1-C10 unsaturated aliphatic hydrocarbon group or substituted C1-C10 unsaturated aliphatic hydrocarbon group, wherein the substituted cyano, substituted hydroxyl, substituted nitro, substituted amino, substituted carboxyl, substituted C1-C10 saturated aliphatic hydrocarbon group and substituted C1-C10 unsaturated aliphatic hydrocarbon groupThe substituent in the unsaturated aliphatic hydrocarbon group of C1-C10 is independently saturated aliphatic hydrocarbon group of C1-C10, unsaturated aliphatic hydrocarbon group of C1-C10, aryl group of C6-C20, heteroaryl group of C3-C20 or alkoxy group of C1-C10.
Preferably, the molar ratio of the compound having the structure shown in formula II, (+) -fenchyl alcohol, 4-dimethylaminopyridine and dicyclohexylcarbodiimide is 1:1:0.2: 0.8.
Preferably, the temperature of the first esterification reaction is room temperature, and the time is 3-24 h.
The invention provides application of the terpene ester compound in the technical scheme in the aspect of preventing and controlling pests of agricultural and forestry crops.
Preferably, the agricultural and forestry crop pests include lepidoptera, coleoptera, orthoptera, hemiptera, thysanoptera, or pest mites.
The invention provides a terpene ester compound which has a structure shown in a formula I, has a novel structure and a specific methyl substitution position at a bicyclo [2.2.1] heptane position, has excellent insect growth regulation activity, can be used for preventing and controlling pests in agriculture and forestry production, and has potential production and application values.
The invention provides a preparation method of terpene ester compounds, which takes (+) -fenchyl alcohol, substituted aromatic acid with a structure shown in a formula II or derivatives thereof as starting raw materials to obtain the terpene ester compounds with different structures through one-step esterification reaction or two-step reaction (substitution reaction and esterification reaction), and has the advantages of reasonable synthetic route, high yield, easy separation of products and the like.
Drawings
FIG. 1 is a graph showing the effect of SDH-33 on the growth regulating activity of Helicoverpa armigera in application example 2.
Detailed Description
The invention provides a terpene ester compound which has a structure shown in a formula I:
in the formula I, X is positioned at any position on six carbons of a benzene ring; x is C, N or S;
n is 0 or 1; r1Is positioned at any position of six carbons on a benzene ring; m represents R1M is 1-5 and is an integer;
R1is hydrogen, halogen, cyano, hydroxyl, nitryl, carboxyl, C1-C10 saturated aliphatic alkyl, C1-C10 unsaturated aliphatic alkyl, C6-C20 aryl, C3-C20 heteroaryl, C1-C10 alkoxy, NR2R3、-CONR2R3、-COOR2or-SO2R4；
Wherein R is2、R3、R4Independently cyano, substituted cyano, hydroxyl, substituted hydroxyl, nitro, substituted nitro, amino, substituted amino, carboxyl, substituted carboxyl, C1-C10 saturated aliphatic hydrocarbyl, substituted C1-C10 saturated aliphatic hydrocarbyl, C1-C10 unsaturated aliphatic hydrocarbyl or substituted C1-C10 unsaturated aliphatic hydrocarbyl, wherein the substituent of the substituted cyano, substituted hydroxyl, substituted nitro, substituted amino, substituted carboxyl, substituted C1-C10 saturated aliphatic hydrocarbyl and substituted C1-C10 unsaturated aliphatic hydrocarbyl is independently C1-C10 saturated aliphatic hydrocarbyl, C1-C10 unsaturated aliphatic hydrocarbyl, C6-C20 aryl, C3-C20 heteroaryl or C1-C10 alkoxy.
In the present invention, m is preferably 2 to 4, and more preferably 3.
In the present invention, said R1Preferably 3-CH3、2,4-(CH3)2、2,5-(CH3)2、3,5-(CH3)2、2,4,6-(CH3)3、4-t-Bu、2-C2H5、4-C2H5、2-OEt,4-OEt、3-NH2、4-NH2、2-OH、3-CN、3-(1-CH3CN)、2,3,4-F3、2,3,4,5-F4、4-Cl、2-Br、3-Br、2,5-Br2、2-I、3-I、2-CF3、3-CF3、4-CF3、4-CH2Cl、2-Cl-5-Br、4-SO2H、2-NO2-4-SO2H、2-OMe-5-SO2NH2、2-OH-4-SO2OH, 2-benzene, 2-naphthoic acid or naphthyridinic acid.
In the present invention, the nalidixic acid preferably represents 4-dihydro-1-ethyl-7-methyl-1, 8-naphthalene-4-1-3-carboxylic acid or 1-ethyl-1, 4-dihydro-7-methyl-4-oxo-1, 8-naphthalene-3-carboxylic acid.
In the present invention, the terpene ester compound is preferably
The invention provides a preparation method of the terpene ester compound in the technical scheme, which comprises the following steps:
mixing a compound with a structure shown in a formula II, (+) -fenchyl alcohol, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and a first organic solvent, and carrying out a first esterification reaction to obtain a terpene ester compound with a structure shown in a formula I;
or mixing the compound with the structure shown in the formula II, a second organic solvent, thionyl chloride and N, N-dimethylformamide for substitution reaction to obtain a substituted benzoyl chloride compound;
mixing the substituted benzoyl chloride compound, (+) -fenchyl alcohol, triethylamine and a third organic solvent, and carrying out a second esterification reaction to obtain a terpene ester compound with a structure shown in formula I;
in the formula II, X is positioned at any position on six carbons of a benzene ring; x is C, N or S;
n is 0 or 1; r1Is positioned at any position of six carbons on a benzene ring; m represents R1M is 1-5 and is an integer;
R1is hydrogen, halogen, cyano, hydroxyl, nitryl, carboxyl, C1-C10 saturated aliphatic alkyl, C1-C10 unsaturated aliphatic alkyl, C6-C20 aryl, C3-C20 heteroaryl, C1-C10 alkoxy, NR2R3、-CONR2R3、-COOR2or-SO2R4；
Wherein R is2、R3、R4Independently of each otherThe substituted cyano group, the hydroxyl group, the substituted hydroxyl group, the nitro group, the substituted nitro group, the amino group, the substituted amino group, the carboxyl group, the substituted carboxyl group, the C1-C10 saturated aliphatic hydrocarbon group, the substituted C1-C10 saturated aliphatic hydrocarbon group, the C1-C10 unsaturated aliphatic hydrocarbon group or the substituted C1-C10 unsaturated aliphatic hydrocarbon group, wherein the substituent group in the substituted cyano group, the substituted hydroxyl group, the substituted nitro group, the substituted amino group, the substituted carboxyl group, the substituted C1-C10 saturated aliphatic hydrocarbon group and the substituted C1-C10 unsaturated aliphatic hydrocarbon group is independently the C1-C10 saturated aliphatic hydrocarbon group, the C1-C10 unsaturated aliphatic hydrocarbon group, the C6-C20 aryl group, the C3-C20 heteroaryl group or the C1-C10 alkoxy group.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
In one embodiment of the present invention, a compound having a structure represented by formula II, (+) -fenchyl alcohol, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and a first organic solvent are mixed and subjected to a first esterification reaction to obtain a terpene ester compound having a structure represented by formula I.
In the present invention, the compound having the structure represented by formula II is as follows:
in the formula II, X is positioned at any position on six carbons of a benzene ring; x is C, N or S;
n is 0 or 1; r1Is positioned at any position of six carbons on a benzene ring; m represents R1M is 1-5 and is an integer;
R1is hydrogen, halogen, cyano, hydroxyl, nitryl, carboxyl, C1-C10 saturated aliphatic alkyl, C1-C10 unsaturated aliphatic alkyl, C6-C20 aryl, C3-C20 heteroaryl, C1-C10 alkoxy, NR2R3、-CONR2R3、-COOR2or-SO2R4；
Wherein R is2、R3、R4Independently cyano, substituted cyano, hydroxy, substituted hydroxy, nitro, substituted nitro, ammoniaThe substituent group in the substituted cyano, the substituted hydroxyl, the substituted nitro, the substituted amino, the substituted carboxyl, the substituted C1-C10 saturated aliphatic hydrocarbon group and the substituted C1-C10 unsaturated aliphatic hydrocarbon group is independently C1-C10 saturated aliphatic hydrocarbon group, C1-C10 unsaturated aliphatic hydrocarbon group, C6-C20 aryl, C3-C20 heteroaryl or C1-C10 alkoxy.
In the compound of formula II, R is1Preferably 3-CH3、2,4-(CH3)2、2,5-(CH3)2、3,5-(CH3)2、2,4,6-(CH3)3、4-t-Bu、2-C2H5、4-C2H5、2-OEt,4-OEt、3-NH2、4-NH2、2-OH、3-CN、3-(1-CH3CN)、2,3,4-F3、2,3,4,5-F4、4-Cl、2-Br、3-Br、2,5-Br2、2-I、3-I、2-CF3、3-CF3、4-CF3、4-CH2Cl、2-Cl-5-Br、4-SO2H、2-NO2-4-SO2H、2-OMe-5-SO2NH2、2-OH-4-SO2OH, 2-benzene, 2-naphthoic acid or naphthyridinic acid.
In the present invention, the compound having the structure represented by formula II is preferably p-tert-butylbenzoic acid, o-ethoxybenzoic acid, 2,3, 4-trifluorobenzoic acid, p-trifluoromethylbenzoic acid, 4-methylsulfonylbenzoic acid or 2-naphthoic acid.
In the present invention, the molar ratio of the compound having the structure represented by formula II, (+) -fenchyl alcohol, 4-dimethylaminopyridine and dicyclohexylcarbodiimide is preferably 1:1:0.2: 0.8; the 4-dimethylaminopyridine and the dicyclohexylcarbodiimide act as catalysts for the esterification reaction.
In the present invention, the first organic solvent is preferably dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, hexane, acetonitrile, benzene, toluene or xylene; the amount of the first organic solvent is not particularly limited, and the first organic solvent can be used for fully dissolving materials.
In the invention, the compound of the structure shown in the formula II, (+) -fenchyl alcohol, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and the first organic solvent are preferably mixed by adding the organic solvent to a mixture of the compound of the structure shown in the formula II, (+) -fenchyl alcohol and 4-dimethylaminopyridine, stirring and mixing, and cooling to 0-10 ℃ in an ice bath to obtain a mixed solution; dissolving dicyclohexylcarbodiimide in the same organic solvent, and dropwise adding the obtained dicyclohexylcarbodiimide solution into the mixed solution under the ice bath condition. The concentration of the dicyclohexylcarbodiimide solution is not particularly limited, and the dicyclohexylcarbodiimide can be completely dissolved; the stirring and dropping process is not particularly limited in the present invention, and may be carried out according to a process well known in the art.
After the mixing is completed, the ice bath is preferably removed, and the reaction solution obtained by mixing is cooled to room temperature to perform the first esterification reaction. The process of cooling to room temperature is not specially limited, and the temperature is naturally cooled.
In the invention, the temperature of the first esterification reaction is preferably room temperature, and the time is preferably 3-24 h, and more preferably 6-18 h. The first esterification reaction is preferably carried out under the condition of stirring, and the stirring process is not particularly limited, so that the reaction can be smoothly carried out. The present invention preferably detects the reaction by Thin Layer Chromatography (TLC) and stops the reaction until the reaction raw materials are completely disappeared.
After the first esterification reaction is finished, preferably, the obtained reaction system is subjected to suction filtration, the obtained liquid part is collected, and a solvent is removed to obtain a crude product; the crude product is then subjected to column chromatography. In the invention, the suction filtration is preferably carried out by adopting a reduced pressure suction filtration funnel, and solid substances are removed by suction filtration; the desolventization is preferably carried out by a rotary evaporator; the developing solvent used for column chromatography separation is preferably a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is preferably (60-80): 1. After the column chromatography separation is completed, the elution liquid is preferably collected in sequence to obtain the terpene ester compound with the structure shown in the formula I. The process of suction filtration, collection and desolvation is not particularly limited in the present invention, and may be performed according to a process well known in the art. When the terpene ester compound having the structure shown in formula I is a solid, the present invention preferably further comprises drying the collected eluate, and the drying process is not particularly limited in the present invention, and can be performed according to the processes well known in the art.
In the present invention, the process of the first esterification reaction is as follows:
in the present invention, the terpene ester compound having the structure represented by formula I is preferably:
in another embodiment of the invention, the compound with the structure shown in formula II, the second organic solvent, thionyl chloride and N, N-dimethylformamide are mixed for substitution reaction to obtain the substituted benzoyl chloride compound.
The molar ratio of the compound with the structure shown in the formula II, thionyl chloride and N, N-dimethylformamide is not particularly limited and can be adjusted according to actual requirements; the N, N-dimethylformamide is used as a catalyst for the substitution reaction of the compound with the structure shown in the formula II and thionyl chloride.
In the present invention, the second organic solvent is preferably toluene; the amount of the second organic solvent is not particularly limited, and the second organic solvent can be used for completely dissolving materials.
In the invention, the process of mixing the compound with the structure shown in the formula II, the second organic solvent, the thionyl chloride and the N, N-dimethylformamide is preferably to dissolve the compound with the structure shown in the formula II in the second organic solvent, add the thionyl chloride and the N, N-dimethylformamide into the obtained solution, and stir and mix uniformly. The stirring process is not specially limited, and the materials can be uniformly mixed.
After the mixing is completed, the invention preferably carries out the substitution reaction under the conditions of stirring and refluxing; the temperature and time of the substitution reaction are not particularly limited in the present invention. The stirring and refluxing process is not particularly limited in the present invention, and may be carried out according to a process well known in the art.
After the substitution reaction is completed, the invention preferably carries out atmospheric distillation (solvent and redundant thionyl chloride are removed) on the obtained product system to obtain the substituted benzoyl chloride compound. The process of the atmospheric distillation is not particularly limited in the present invention, and may be carried out according to a process known in the art.
And (3) after obtaining the substituted benzoyl chloride compound, mixing the substituted benzoyl chloride compound, (+) -fenchyl alcohol, triethylamine and a third organic solvent, and carrying out a second esterification reaction to obtain the terpene ester compound with the structure shown in the formula I. In the present invention, the third organic solvent is preferably dichloromethane; the amount of the third organic solvent is not particularly limited, and the third organic solvent can be used for fully dissolving materials. In the present invention, the molar ratio of the substituted benzoyl chloride compound, (+) -fenchyl alcohol and triethylamine is not particularly limited, and may be adjusted according to the actual reaction requirements. In the invention, the triethylamine is used as an acid-binding agent for the esterification reaction of the substituted benzoyl chloride compound and (+) -fenchyl alcohol.
In the present invention, the substituted benzoyl chloride compound, (+) -fenchyl alcohol, triethylamine and the third organic solvent are preferably mixed by dissolving (+) -fenchyl alcohol and triethylamine in the third organic solvent to obtain a mixed solution; dissolving the substituted benzoyl chloride compound in the same kind of third organic solvent, and dropwise adding the obtained substituted benzoyl chloride compound solution into the mixed solution under the ice bath condition. The process of the dissolution and the dropping is not particularly limited in the present invention, and may be carried out according to a process well known in the art.
After the mixing is completed, the ice bath condition is preferably removed, and the second esterification reaction is preferably carried out under the stirring condition. The stirring process is not specially limited, and the smooth reaction can be ensured.
In the present invention, the process of the substitution reaction and the second esterification reaction is as follows:
the invention provides application of the terpene ester compound in the technical scheme in the aspect of preventing and controlling pests of agricultural and forestry crops. The method of the present invention is not particularly limited, and the method may be applied according to a method known in the art. In the present invention, the agricultural or forestry crop pests preferably include lepidoptera, coleoptera, orthoptera, hemiptera, thysanoptera or pest mites.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Synthesis of terpene ester Compound SDH-33:
accurately weighing 1.78g (0.01mol) of p-tert-butylbenzoic acid, 1.54g (0.01mol) of (+) -fenchyl alcohol and 0.244g (0.002mol) of 4-Dimethylaminopyridine (DMAP) in a 50mL single-neck round-bottom flask, adding 25mL Dichloromethane (DCM) for dissolving and stirring, and cooling to 0 ℃ in ice bath to obtain a mixed solution; accurately weighing 1.648g of Dicyclohexylcarbodiimide (DCC) (0.008mol), dissolving in 5mL of dichloromethane, slowly dripping into the mixed solution in an ice bath, removing the ice bath after dripping is finished, cooling to room temperature, carrying out esterification reaction for 6 hours under the stirring condition, carrying out Thin Layer Chromatography (TLC) detection reaction, completely eliminating the raw materials, and stopping the reaction; removing solid substances from the obtained reaction system by adopting a decompression suction filter funnel, collecting a liquid part, and removing a solvent by using a rotary evaporator to obtain a crude product; and (3) performing column chromatography on the crude product, eluting by a developing agent (petroleum ether: ethyl acetate, 60:1), sequentially collecting eluates by using test tubes, merging and drying to obtain a white powdery solid with the mass of 2.76g and the yield of 88%, and marking as SDH-33.
Example 2
Synthesis of terpene ester Compound SDH-36
Accurately weighing 1.66g of o-ethoxybenzoic acid, 1.54g of (+) -fenchyl alcohol and 0.244g of 4-Dimethylaminopyridine (DMAP) in a 50mL single-neck round-bottom flask, adding 25mL of Dichloromethane (DCM) for dissolving and stirring, and cooling to 0 ℃ in ice bath to obtain a mixed solution; accurately weighing 1.648g of Dicyclohexylcarbodiimide (DCC), dissolving in 5mL of dichloromethane, slowly dropping the mixture into the mixed solution in an ice bath, removing the ice bath after dropping, cooling to room temperature, carrying out esterification reaction for 5 hours under the stirring condition, carrying out thin-layer chromatography (TLC) detection reaction, completely eliminating the raw materials, and stopping the reaction; removing solid substances from the obtained reaction system by adopting a decompression suction filter funnel, collecting a liquid part, and removing a solvent by using a rotary evaporator to obtain a crude product; and (3) performing column chromatography on the crude product, eluting by a developing agent (petroleum ether: ethyl acetate, 60:1), sequentially collecting eluates by using test tubes, merging and drying to obtain a white powdery solid with the mass of 2.72g and the yield of 90 percent, and marking as SDH-36.
Example 3
Synthesis of terpene ester Compound SDH-41
Accurately weighing 1.76g of 2,3, 4-trifluorobenzoic acid, 1.54g of (+) -fenchyl alcohol and 0.244g of 4-Dimethylaminopyridine (DMAP) in a 50mL single-neck round-bottom flask, adding 25mL of Dichloromethane (DCM) for dissolving and stirring, and cooling to 0 ℃ in ice bath to obtain a mixed solution; accurately weighing 1.648g of Dicyclohexylcarbodiimide (DCC), dissolving in 5mL of dichloromethane, slowly dropping the mixture into the mixed solution in an ice bath, removing the ice bath after dropping, cooling to room temperature, carrying out esterification reaction for 12 hours under the stirring condition, carrying out thin-layer chromatography (TLC) detection reaction, completely eliminating the raw materials, and stopping the reaction; removing solid substances from the obtained reaction system by adopting a decompression suction filter funnel, collecting a liquid part, and removing a solvent by using a rotary evaporator to obtain a crude product; and (3) performing column chromatography on the crude product, eluting by a developing agent (petroleum ether: ethyl acetate, 60:1), sequentially collecting eluates by using test tubes, and mixing to obtain colorless oily liquid with the mass of 2.43g and the yield of 78%, wherein the weight is recorded as SDH-41.
Example 4
Synthesis of terpene ester Compound SDH-51
Accurately weighing 1.90g of p-trifluoromethylbenzoic acid, 1.54g of (+) -fenchyl alcohol and 0.244g of 4-Dimethylaminopyridine (DMAP) in a 50mL single-neck round-bottom flask, adding 25mL of Dichloromethane (DCM) for dissolving and stirring, and cooling to 0 ℃ in ice bath to obtain a mixed solution; accurately weighing 1.648g of Dicyclohexylcarbodiimide (DCC), dissolving in 5mL of dichloromethane, slowly dropping the mixture into the mixed solution in an ice bath, removing the ice bath after dropping, cooling to room temperature, carrying out esterification reaction for 10 hours under the stirring condition, carrying out thin-layer chromatography (TLC) detection reaction, completely eliminating the raw materials, and stopping the reaction; removing solid substances from the obtained reaction system by adopting a decompression suction filter funnel, collecting a liquid part, and removing a solvent by using a rotary evaporator to obtain a crude product; and (3) performing column chromatography on the crude product, eluting by a developing agent (petroleum ether: ethyl acetate, 80:1), sequentially collecting eluates by using test tubes, merging and drying to obtain a white solid with the mass of 2.61g and the yield of 77 percent, and marking as SDH-51.
Example 5
Synthesis of terpene ester Compound SDH-54
Accurately weighing 2.00g of 4-methylsulfonylbenzoic acid, 1.54g of (+) -fenchyl alcohol and 0.244g 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 an ice bath to obtain a mixed solution; accurately weighing 1.648g of Dicyclohexylcarbodiimide (DCC), dissolving in 5mL of dichloromethane, slowly dropping the mixture into the mixed solution in an ice bath, removing the ice bath after dropping, cooling to room temperature, carrying out esterification reaction for 12 hours under the stirring condition, carrying out thin-layer chromatography (TLC) detection reaction, completely eliminating the raw materials, and stopping the reaction; removing solid substances from the obtained reaction system by adopting a decompression suction filter funnel, collecting a liquid part, and removing a solvent by using a rotary evaporator to obtain a crude product; and (3) performing column chromatography on the crude product, eluting by a developing agent (petroleum ether: ethyl acetate, 80:1), sequentially collecting eluates by using test tubes, merging and drying to obtain a light yellow solid with the mass of 2.28g and the yield of 68 percent, and marking as SDH-54.
Example 6
Synthesis of terpene ester compound SDH-58
Accurately weighing 1.72g of 2-naphthoic acid, 1.54g of (+) -fenchyl alcohol and 0.244g of 4-Dimethylaminopyridine (DMAP) in a 50mL single-neck round-bottom flask, adding 25mL of Dichloromethane (DCM) for dissolving and stirring, and cooling to 0 ℃ in ice bath to obtain a mixed solution; accurately weighing 1.648g of Dicyclohexylcarbodiimide (DCC), dissolving in 5mL of dichloromethane, slowly dropping the mixture into the mixed solution in an ice bath, removing the ice bath after dropping, cooling to room temperature, carrying out esterification reaction for 8 hours under the stirring condition, carrying out thin-layer chromatography (TLC) detection reaction, completely eliminating the raw materials, and stopping the reaction; removing solid substances from the obtained reaction system by adopting a decompression suction filter funnel, collecting a liquid part, and removing a solvent by using a rotary evaporator to obtain a crude product; and (3) performing column chromatography on the crude product, eluting by a developing agent (petroleum ether: ethyl acetate, 60:1), sequentially collecting eluates by using test tubes, merging and drying to obtain a white solid with the mass of 2.40g and the yield of 78%, and marking as SDH-58.
Structure and characterization
Performing nuclear magnetic characterization on the terpene ester compounds prepared in examples 1-6, wherein the results are shown in Table 1; meanwhile, the terpene ester compound information of other structures is shown in table 1.
TABLE 1 characterization information of terpene ester compounds prepared in examples 1-6 and terpene ester compounds of other structures
Application example 1
The insecticidal activity of the terpene ester compounds with partial structures in the table 1 on cotton bollworms is determined by adopting a leaf soaking method, which comprises the following steps:
accurately weighing 20mg of terpene ester compounds in Table 1, respectively, dissolving in 2mL of acetone to obtain 10000 μ g/mL of mother liquor, and diluting with 0.05% triton to obtain 200mg/L of liquid medicine to be tested. Meanwhile, a 0.05% triton solution is set as a blank control;
soaking bollworm 3-instar larvae in the above medicinal solutions for 5s, sucking off the residual medicinal liquid with filter paper, separately loading into insect-breeding tubes, inoculating normal feed, sealing with absorbent cotton, and transferring into insect incubator for normal growth. Each treatment was repeated 3 times with 10 replicates each. The cotton bollworm mortality was investigated after 24h and 48h of treatment, respectively, the cotton bollworm was spotted with the tip of a writing brush and considered dead if the body was not moved, and the mortality and corrected mortality were calculated according to formulas (1) and (2).
In formula (1): p1Representing mortality; k represents the number of dead insects; n represents the total number of treated insects.
In formula (2): p2Represents corrected mortality; ptRepresenting treatment mortality; p0Representing blank control mortality.
In the test, if the mortality of the blank control group is between 5 and 20 percent, the corrected mortality must be obtained, if the mortality of the blank control group is less than 5 percent, the corrected mortality is expressed by the mortality, and if the mortality of the blank control group is more than 20 percent, the test fails; the results of the determination of the relevant enzyme systems after 48h of treatment are shown in Table 2.
TABLE 2 insecticidal Activity of some of the terpene ester compounds of Table 1 against Helicoverpa armigera
Remarking: "-" indicates that no test was performed to determine the activity data, and does not indicate no activity. "dysplasia" means that after the action of the agent, the cotton bollworm larvae develop slowly, are difficult to molt, and have a significantly smaller insect status than the larvae treated with the control agent.
As can be seen from Table 2, the SDH-33 compound is taken as an example, the direct lethality to cotton bollworm is obviously higher, and all the terpene ester compounds in Table 2 have larger influence on the growth and development of cotton bollworm.
Application example 2
1) The growth regulating activity of the compound SDH-33 on cotton bollworm is verified:
20mg SDH-33 is accurately weighed and dissolved in 2mL dimethylformamide to prepare 10000 mug/mL mother liquor, and then the mother liquor is diluted into 500 mug/mL liquid medicine to be tested by 0.05 percent triton. 500 mug/mL lufenuron solution was used as the drug control and 0.05% triton solution was used as the blank control. Selecting 3-year-old cotton bollworms with similar sizes, carrying out grouping numbering, measuring the weight and the body length of the cotton bollworms by using an electronic vernier caliper and an analytical balance respectively, recording data and numbering, soaking cotton bollworm larvae in different liquid medicines for 5s in sequence, then sucking the redundant liquid medicines of the cotton bollworms by using filter paper, respectively putting the cotton bollworm larvae into separate culture boxes, inoculating normal feed, transferring the cotton bollworm larvae into an insect culture box for normal growth, weighing the weight and the body length of the cotton bollworms 3 days, 5 days and 7 days after the cotton bollworm larvae are soaked in the different liquid medicines respectively, calculating the growth inhibition rate, continuously culturing and observing, and carrying out statistics on the death rate, the pupation rate, the malformed pupation rate, the eclosion rate and the. Each treatment was repeated 3 times, with 20 replicates each.
2) After the SDH-33 acts on the cotton bollworm larvae, tracking feeding can discover that the cotton bollworm larvae are slow in development, long in age and hindered in molting because the group of larvae are treated by the SDH-33; pupating the old larva to form deformed pupa which can not be eclosized; the symptoms of incomplete wing shape, wing malformation, etc. after eclosion of some imagoes are shown in FIG. 1 (in FIG. 1, CK represents blank control, A represents bollworm larva, B represents bollworm pupa, and C represents bollworm imago).
3) 7 days after the application, the cotton bollworms in the blank control group normally develop, the average body length can reach 19.59mm, the weight can reach 100.09mg, the average body length of the cotton bollworms treated by the control medicament lufenuron is 11.27mm, the weight is 42.88mg, the average body length of the cotton bollworm larvae in the SDH-33 treatment group can only reach 11.51mm, the average body weight is only 38.64mg, the body length of the body weight is obviously lower than that of the blank control group, and the cotton bollworm larvae are equivalent to that of the cotton bollworm larvae treated by the control medicament lufenuron; the body length inhibition rate of the larvae of the Helicoverpa armigera treated by SDH-33 reaches 99.84% on the 7 th day after the drug application, the body length inhibition rate reaches 69.28% on the 7 th day after the drug application, and the specific numerical values are shown in Table 3.
TABLE 3 SDH-33 data on the growth regulating Activity of Helicoverpa armigera
4) The effect of using SDH-33 for treatment of cotton bollworm larvae after 28 days is shown in table 4, with lufenuron and blank as controls:
TABLE 4 Effect of SDH-33 on Helicoverpa armigera
Remarking: the pupation rate is the ratio of the pupation worm number to the survival worm number after the medicament treatment; the abnormal pupa rate is the ratio of the abnormal pupa to the pupa number; the eclosion rate is the ratio of the number of eclosion insects to the number of pupation insects; the abnormal wing rate is the ratio of the number of adult abnormal wings to the number of adult abnormal wings.
As can be seen from Table 4, SDH-33 has a high mortality rate for cotton bollworms, the mortality rate reaches 71.67%, the pupation rate and the eclosion rate of the cotton bollworms are both affected, the pupation rate and the eclosion rate are lower than those of a control group and are respectively 70% and 60%, the pupation rate and the eclosion rate are mainly used for causing deformed pupae and deformed wings of the cotton bollworms, the pupation rate is 28.57%, and the deformed wing rate is 66.67%.
Application example 3
Insecticidal activity of compound SDH-33 against four lepidopteran pests (diamond back moth, corn borer, beet armyworm and armyworm):
20mg SDH-33 is accurately weighed and dissolved in 2mL dimethylformamide to prepare 10mg/mL mother solution, and then the mother solution is diluted into 200 mug/mL liquid medicine to be tested by 0.05 percent triton. 200 ug/mL lufenuron solution was used as the drug control and 0.05% triton solution was used as the blank control.
Selecting four lepidoptera pests of 3-year-old armyworm, plutella xylostella, ostrinia nubilalis and asparagus caterpillar with similar sizes, grouping and numbering, soaking larvae of the pests in different liquid medicines for 5s in sequence, sucking redundant liquid medicines of the pests by using filter paper, respectively putting the pests into separate culture boxes, inoculating normal feed, transferring the pests into an insect incubator to grow normally, and investigating the death rate at 1 day, 3 days and 7 days after the pests are applied. Each treatment was repeated 3 times with 20 replicates per treatment and the results are shown in table 5.
TABLE 5 Effect of SDH-33 on four Lepidoptera pests
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A terpene ester compound having the structure of formula I:
in the formula I, X is positioned at any position on six carbons of a benzene ring; x is C, N or S;
n is 0 or 1; r1Is positioned at any position of six carbons on a benzene ring; m represents R1M is 1-5 and is an integer;
R1is hydrogen, halogen, cyano, hydroxyl, nitryl, carboxyl, C1-C10 saturated aliphatic alkyl, C1-C10 unsaturated aliphatic alkyl, C6-C20 aryl, C3-C20 heteroaryl, C1-C10 alkoxy, NR2R3、-CONR2R3、-COOR2or-SO2R4；
Wherein R is2、R3、R4Independently cyano, substituted cyano, hydroxyl, substituted hydroxyl, nitro, substituted nitro, amino, substituted amino, carboxyl, substituted carboxyl, C1-C10 saturated aliphatic hydrocarbyl, substituted C1-C10 saturated aliphatic hydrocarbyl, C1-C10 unsaturated aliphatic hydrocarbyl or substituted C1-C10 unsaturated aliphatic hydrocarbyl, wherein the substituent of the substituted cyano, substituted hydroxyl, substituted nitro, substituted amino, substituted carboxyl, substituted C1-C10 saturated aliphatic hydrocarbyl and substituted C1-C10 unsaturated aliphatic hydrocarbyl is independently C1-C10 saturated aliphatic hydrocarbyl, C1-C10 unsaturated aliphatic hydrocarbyl, C6-C20 aryl, C3-C20 heteroaryl or C1-C10 alkoxy.
2. The terpene ester compound according to claim 1, wherein R is1Is 3-CH3、2,4-(CH3)2、2,5-(CH3)2、3,5-(CH3)2、2,4,6-(CH3)3、4-t-Bu、2-C2H5、4-C2H5、2-OEt,4-OEt、3-NH2、4-NH2、2-OH、3-CN、3-(1-CH3CN)、2,3,4-F3、2,3,4,5-F4、4-Cl、2-Br、3-Br、2,5-Br2、2-I、3-I、2-CF3、3-CF3、4-CF3、4-CH2Cl、2-Cl-5-Br、4-SO2H、2-NO2-4-SO2H、2-OMe-5-SO2NH2、2-OH-4-SO2OH, 2-benzene, 2-naphthoic acid or naphthyridinic acid.
3. A process for producing a terpene ester compound according to claim 1 or 2, which comprises the steps of:
mixing a compound with a structure shown in a formula II, (+) -fenchyl alcohol, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and a first organic solvent, and carrying out a first esterification reaction to obtain a terpene ester compound with a structure shown in a formula I;
or mixing the compound with the structure shown in the formula II, a second organic solvent, thionyl chloride and N, N-dimethylformamide for substitution reaction to obtain a substituted benzoyl chloride compound;
mixing the substituted benzoyl chloride compound, (+) -fenchyl alcohol, triethylamine and a third organic solvent, and carrying out a second esterification reaction to obtain a terpene ester compound with a structure shown in formula I;
in the formula II, X is positioned at any position on six carbons of a benzene ring; x is C, N or S;
n is 0 or 1; r1Is positioned at any position of six carbons on a benzene ring; m represents R1M is 1-5 and is an integer;
R1is hydrogen, halogen, cyano, hydroxyl, nitryl, carboxyl, C1-C10 saturated aliphatic alkyl, C1-C10 unsaturated aliphatic alkyl, C6-C20 aryl, C3-C20 heteroaryl, C1-C10 alkoxy, NR2R3、-CONR2R3、-COOR2or-SO2R4；
Wherein R is2、R3、R4Independently cyano, substituted cyano, hydroxyl, substituted hydroxyl, nitro, substituted nitro, amino, substituted amino, carboxyl, substituted carboxyl, C1-C10 saturated aliphatic hydrocarbyl, substituted C1-C10 saturated aliphatic hydrocarbyl, C1-C10 unsaturated aliphatic hydrocarbyl or substituted C1-C10 unsaturated aliphatic hydrocarbyl, wherein the substituent of the substituted cyano, substituted hydroxyl, substituted nitro, substituted amino, substituted carboxyl, substituted C1-C10 saturated aliphatic hydrocarbyl and substituted C1-C10 unsaturated aliphatic hydrocarbyl is independently C1-C10 saturated aliphatic hydrocarbyl, C1-C10 unsaturated aliphatic hydrocarbyl, C6-C20 aryl, C3-C20 heteroaryl or C1-C10 alkoxy.
4. The method according to claim 3, wherein the molar ratio of the compound having the structure represented by formula II, (+) -fenchyl alcohol, 4-dimethylaminopyridine and dicyclohexylcarbodiimide is 1:1:0.2: 0.8.
5. The preparation method according to claim 3, wherein the temperature of the first esterification reaction is room temperature and the time is 3-24 h.
6. Use of the terpene ester compound according to claim 1 or 2 for controlling pests of agricultural and forestry crops.
7. The use according to claim 6, wherein the agricultural or forestry crop pests include lepidoptera, coleoptera, orthoptera, hemiptera, thysanoptera or pest mites.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011244656.XA CN112341334A (en) | 2020-11-10 | 2020-11-10 | Terpene ester compound, preparation method thereof and application thereof in pest control of agricultural and forestry crops |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011244656.XA CN112341334A (en) | 2020-11-10 | 2020-11-10 | Terpene ester compound, preparation method thereof and application thereof in pest control of agricultural and forestry crops |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112341334A true CN112341334A (en) | 2021-02-09 |
Family
ID=74362491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011244656.XA Pending CN112341334A (en) | 2020-11-10 | 2020-11-10 | Terpene ester compound, preparation method thereof and application thereof in pest control of agricultural and forestry crops |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112341334A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0059441A1 (en) * | 1981-03-02 | 1982-09-08 | Füssener Textil AG | Bioactive agent on terpene/alpha-cetocarboxylic-acid basis |
| JP2005082502A (en) * | 2003-09-05 | 2005-03-31 | S T Chem Co Ltd | Insect-proofing agent for grain and/or dried food and method for proofing insect pest for grain and/or dried food |
| CN102030680A (en) * | 2010-10-20 | 2011-04-27 | 湖北省生物农药工程研究中心 | Novel oxime ether or ester derivatives with insecticidal activity, preparation method and application thereof |
| WO2015075409A1 (en) * | 2013-11-21 | 2015-05-28 | Eden Research Plc | Pesticidal composition |
| CN106866419A (en) * | 2017-04-14 | 2017-06-20 | 石河子大学 | One terpenoid ester compounds and its production and use |
| CN110627759A (en) * | 2019-09-26 | 2019-12-31 | 中央民族大学 | Sesquiterpenoids and preparation method and application thereof |
-
2020
- 2020-11-10 CN CN202011244656.XA patent/CN112341334A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0059441A1 (en) * | 1981-03-02 | 1982-09-08 | Füssener Textil AG | Bioactive agent on terpene/alpha-cetocarboxylic-acid basis |
| JP2005082502A (en) * | 2003-09-05 | 2005-03-31 | S T Chem Co Ltd | Insect-proofing agent for grain and/or dried food and method for proofing insect pest for grain and/or dried food |
| CN102030680A (en) * | 2010-10-20 | 2011-04-27 | 湖北省生物农药工程研究中心 | Novel oxime ether or ester derivatives with insecticidal activity, preparation method and application thereof |
| WO2015075409A1 (en) * | 2013-11-21 | 2015-05-28 | Eden Research Plc | Pesticidal composition |
| CN106866419A (en) * | 2017-04-14 | 2017-06-20 | 石河子大学 | One terpenoid ester compounds and its production and use |
| CN110627759A (en) * | 2019-09-26 | 2019-12-31 | 中央民族大学 | Sesquiterpenoids and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| STN: "210548-91-7 et al", 《STN》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111909143B (en) | Isoxazoline substituted benzamide derivative and preparation method and application thereof | |
| CN110092776B (en) | Pyrazole oxime ester compound containing pyridine-difluoride pyrazole structure and preparation method and application thereof | |
| CN110128409B (en) | Preparation and application of difluoromethylpyrazole oxime derivative containing pyridine bipyrazole structure | |
| CN103524422A (en) | Benzimidazole derivative, and preparation method and purpose thereof | |
| WO2010060231A1 (en) | Condensed amino nitroguanidine compounds, synthesis and use as botanical insecticides thereof | |
| Yang et al. | Natural products-based pesticides: Design, synthesis and pesticidal activities of novel fraxinellone derivatives containing N-phenylpyrazole moiety | |
| CN110407828B (en) | Pyrazole-5-amide derivative containing oxazole structure and preparation method and application thereof | |
| CN106946856B (en) | Pyrazole oxime derivative containing tetrazole biphenyl structure and preparation method and application thereof | |
| CN109689644B (en) | Pyridazinone compound and application thereof | |
| TW201249815A (en) | Pesticidal compositions and processes related thereto | |
| US4699916A (en) | Substituted furazan pesticides | |
| CN114605324A (en) | Isoxazoline substituted benzamide derivative and preparation method and application thereof | |
| CN112457288B (en) | Piperine acid derivative and application thereof | |
| CN109879867B (en) | Preparation and application of pyrazole oxime ether compound containing 5-aryl oxazole structure | |
| CN109942561B (en) | 4- (2-thienyl) pyrimidine derivative and preparation method and application thereof | |
| CN104817587B (en) | Adjacent benzene dioxy acetic acid esters of a kind of Tricyclohexyltin and its preparation method and application | |
| CN112341334A (en) | Terpene ester compound, preparation method thereof and application thereof in pest control of agricultural and forestry crops | |
| CN110407813B (en) | Pyrazole oxime compound containing 1- (3-chloropyridine-2-yl) pyrazole structure and preparation method and application thereof | |
| Liu et al. | Evaluation of insecticidal activity of podophyllotoxin derivatives against Brontispa longissima | |
| CN111205223A (en) | Quinoline derivatives, preparation method and application thereof | |
| CN108689928B (en) | Quinoline derivative and preparation method and application thereof | |
| CN104910092B (en) | The contraposition of 4 phenyl contains aldoxime ether structure oxazoline compounds and its preparation and the application in terms of worm mite Juncao is prevented and treated | |
| Wimmer et al. | Insect juvenile hormones and their bioanalogues | |
| CN105924435B (en) | A kind of substituted pyrazoles acetamides and its preparation method and application | |
| EP0396215A1 (en) | 5-Substituted 3-arylisoxazole-derivatives their production and their use as pesticide |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210209 |
|
| RJ01 | Rejection of invention patent application after publication |