Nitrogen-containing fused tricyclic compound and use thereof as agroforestry insecticide

专利摘要:
Disclosed are a nitrogen-containing fused tricyclic compound, an optical isomer, cis and trans isomers or an agromedically acceptable salt thereof, and the insecticidal use thereof in agroforestry. The delayed working effect of the compound on pests such as red imported fire ants can make the pests carry the drug to a nest, thereby having a better killing effect on the whole red imported fire ants nest and the queen ant.
公开号:EP3689877A1
申请号:EP18873292.9
申请日:2018-11-02
公开日:2020-08-05
发明作者:Hanhong Xu；Xunyuan JIANG；Xiaoyi Wei；Zhixiang Zhang；Fei Lin；Guangkai YAO；Chengju DENG；Chen Zhao；Shuai Yang；Weijing ZHAO
申请人:South China Agricultural University；
IPC主号:C07D487-00

专利说明:
[0001] The present invention belongs to the field of heterocyclic compounds, and more particularly, relates to a fused heterocyclic compound, and an optical isomer, cis and trans isomers or an agromedically acceptable salt thereof, as well as a preparation method and use thereof. BACKGROUND
[0002] New heterocyclic pesticides represented by nitrogen-containing heterocycles have the advantages of high insecticidal activity, wide insecticidal spectrum, low toxicity to mammals and appropriate field stability, so that heterocyclic compounds have become an important hotspot field in the development of new pesticides. In recent years, newly developed pesticides such as Flupyrimin, flupyradifurone, cycloxaprid, sulfoxaflor, flonicamid, spirotetramat, cyflumetofen, cyenopyrafen, cyantraniliprole and the like, all belong to the nitrogen-containing heterocyclic compounds (with reference to patents US2013150414 , CN103960242 , CN103254125 , CN102892290 , DE102006015467 , WO2010069266 , WO2007095229 , EP580374 , WO9805638 , WO2002014263 , JP2003201280 and WO2004067528 ).
[0003] However, the problems of serious resistance and cross resistance are caused due to excessive and frequent use of a single pesticide and a high toxicity of the existing insecticide to the environment while killing pests, which reduces an efficacy of the pesticide and greatly restricts use of the pesticide, thus restricting the development of agriculture and forestry. Therefore, how to develop a new pesticide that is more efficient and environmentally friendly and how to solve the problem of resistance become technical problems to be urgently solved in this field.
[0004] New structural molecules with big structural differences from previous pesticide molecules are believed to have no cross resistance with the existing pesticides, and may be used to control the development of pest resistance (Pestide Biochemistry and Physiology, 2015, 121: 22). In recent years, multiple series of fused heterocyclic compounds have been synthesized and reported to have an extensive bioactivity (such as Computational Biology and Chemistry, 2018, 74: 218; Bioorganic & Medicinal Chemistry Letters, 2017, 27: 3201; Journal of Medicinal Chemistry, 2017, 60: 9691; Journal of Heterocyclic Chemistry, 2017, 54: 2788; Organic & Biomolecular Chemistry, 2016, 14: 8721; Journal of Enzyme Inhibition and Medicinal Chemistry, 2015, 31: 195; New Journal of Chemistry, 2015, 39: 1060; Chemistry-A European Journal, 2015, 21: 16859; Bioorganic & Medicinal Chemistry Letters, 2014, 24: 2693; Journal of Medicinal Chemistry, 2013, 56: 7458; Bioorganic & Medicinal Chemistry Letters, 2009, 19: 4196; Chemistry & Biology, 2007, 14: 153; Journal of Biological Chemistry, 2003, 278: 25990; and Journal of Medicinal Chemistry, 2002, 45: 1035). Based on this, a large number of new fused heterocyclic compounds have been designed, synthesized and screened in this study. These compounds with novel structures have excellent control effects on a variety of pests and even on pests with resistence. SUMMARY
[0005] An object of the present invention is to provide a nitrogen-containing fused tricyclic compound, and an optical isomer, cis and trans isomers or an agromedically acceptable salt thereof. The fused heterocyclic compound and the optical isomer, the cis and trans isomers or the agromedically acceptable salt thereof have a high killing activity on agroforestry pests and sanitary insect pests and sanitary pests, and more surprisingly, have a delayed working effect on pests such as Solenopsis invicta, thereby having a better killing effect.
[0006] Another object of the present invention is to provide a method for preparing the fused tricyclic compound, and the optical isomer, the cis and trans isomers or the agromedically acceptable salt thereof.
[0007] Another object of the present invention is to provide use of the fused heterocyclic compound and the optical isomer, the cis and trans isomers or the agromedically acceptable salt thereof in preparing an insecticide.
[0008] In order to achieve the above objects, the technical solutions adopted by the present invention are as follows.
[0009] A fused heterocyclic compound, and an optical isomer, cis and trans isomers or an agromedically acceptable salt thereof, wherein the fused heterocyclic compound has a structure shown in formula (I):
[0010] Preferably, when Z¹, Z², Z³ and Z⁴ are all C, one or more R¹⁶ are provided, and each R¹⁶ is independently hydrogen, halogen, alkyl, heteroalkyl, alkenyl, -S(O) R¹⁷, - S(O)₂R¹⁷, -COR¹⁷, -NR¹⁷R¹⁸, -CONR¹⁷R¹⁸, -NR¹⁷COR¹⁸ or -NR¹⁷S(O)₂R¹⁸;R¹¹ is halogen, -CN, -COR¹⁷, -CONR¹⁷R¹⁸, -S(O)R¹⁷, -NR¹⁷R¹⁸, -NR¹⁷COR¹⁸, aryl, heterocyclyl or heteroaryl; wherein the alkyl, the heterocyclyl or the heteroaryl is unsubstituted or substituted with one or more substituents R¹⁰;R¹² is -CONR¹⁷R¹⁸, -S(O)R¹⁷, -S(O)₂R¹⁷, -NR¹⁷R¹⁸, -NR¹⁷COR¹⁸, -NR¹⁷CON R¹⁸R¹⁹, aryl, heterocyclyl or heteroaryl; wherein the alkyl, the heterocyclyl or the heteroaryl is unsubstituted or substituted with one or more substituents R¹⁰;R¹³ is hydrogen, -COR¹⁷, alkyl or alkenyl; andR¹⁴ and R¹⁵ are each independently halogen, -CN, -NR¹⁷ R¹⁸, -OR¹⁷, -COR¹⁷, - CO₂R¹⁷, -CONR¹⁷R¹⁸, -NR¹⁷COR¹⁸, -NR¹⁷CO₂R¹⁸, alkyl, heteroalkyl and alkenyl; wherein the alkyl, the heteroalkyl and the alkenyl are unsubstituted or substituted with one or more substituents R¹⁰.
[0011] More preferably,when Y is N or CH;R¹¹ is halogen, -CN, -COR¹⁷, -CONR¹⁷R¹⁸, -S(O)R¹⁷, -NR¹⁷R¹⁸ or -NR¹⁷CO R¹⁸;R¹² is -S(O)R¹⁷, -S(O)₂R¹⁷, -NR¹⁷R¹⁸, -NR¹⁷COR¹⁸, aryl or heteroaryl; wherein the aryl or the heteroaryl is unsubstituted or substituted with one or more substituents R¹⁰;R¹³ is hydrogen, -COR¹⁷, alkyl or alkenyl;R¹⁴ and R¹⁵ are each independently halogen, -CN, -NR¹⁷R¹⁸, -OR¹⁷, -COR¹⁷,-CO₂R¹⁷, -CONR¹⁷R¹⁸, -NR¹⁷COR¹⁸, -NR¹⁷CO₂R¹⁸, alkyl, heteroalkyl or alkenyl; wherein the alkyl or the alkenyl is unsubstituted or substituted with one or more substituents R¹⁰; andZ¹, Z², Z³ and Z⁴ are all C, one or more R¹⁶ are provided, and each R¹⁶ is independently halogen, alkyl, heteroalkyl, -S(O)R¹⁷, -S(O)₂R¹⁷, -COR¹⁷, -NR¹⁷R¹⁸, -N R¹⁷COR¹⁸ or -NR¹⁷S(O)₂R¹⁸.
[0012] More preferably,R¹¹ is halogen, -CN, -COR¹⁷ or -CONR¹⁷R¹⁸;R¹² is -S(O)R¹⁷, -S(O)₂R¹⁷, -NR¹⁷COR¹⁸, aryl or heteroaryl; wherein the aryl or the heteroaryl is unsubstituted or substituted with one or more substituents R¹⁰;R¹³ is hydrogen, -COR¹⁷ or alkyl; andZ¹, Z², Z³ and Z⁴ are all C, one or more R¹⁶ are provided, and each R¹⁶ is independently halogen, heteroalkyl, -S(O)R¹⁷, -NR¹⁷R¹⁸ or -NR¹⁷COR¹⁸.
[0013] More preferably,R¹¹ is -CN or -COR¹⁷;R¹² is -S(O)R¹⁷ or aryl; wherein the aryl is substituted with one or more substituents R¹⁰;R¹³ is hydrogen, -COR¹⁷, methyl or ethyl;R¹⁴ and R¹⁵ are each independently halogen, -OR¹⁷, -COR¹⁷, -CO₂R¹⁷, - CONR¹⁷R¹⁸, -NR¹⁷COR¹⁸, -NR¹⁷CO₂R¹⁸, alkyl, heteroalkyl or alkenyl; wherein the alkyl or the alkenyl is unsubstituted or substituted with one or more substituents R¹⁰; andZ¹, Z², Z³ and Z⁴ are all C, one or more R¹⁶ are provided, and each R¹⁶ is independently halogen or heteroalkyl.
[0014] More preferably,R¹¹ is -CN or -COR¹⁷, and R¹⁷ is alkyl or heteroalkyl;R¹² is -S(O)R¹⁷, and R¹⁷ is alkyl or heteroalkyl;R¹³ is hydrogen, -COR¹⁷, methyl or ethyl, and R¹⁷ is alkyl;R¹⁴ and R¹⁵ are each independently halogen, -OR¹⁷, -COR¹⁷, -CO₂R¹⁷, - CONR¹⁷R¹⁸, -NR¹⁷COR¹⁸, -NR¹⁷CO₂R¹⁸, alkyl, heteroalkyl or alkenyl; wherein the alkyl or the alkenyl is unsubstituted or substituted with one or more substituents R¹⁰; andZ¹, Z², Z³ and Z⁴ are all C, one or more R¹⁶ are provided, and each R¹⁶ is independently halogen or heteroalkyl.
[0015] The present invention further discloses a pyrazole-ring-containing fused heterocyclic compound, and an optical isomer, cis and trans isomers or an agromedically acceptable salt thereof, wherein the pyrazole-ring-containing fused heterocyclic compound has a structure shown in formula (II):
[0016] Preferably, when Z¹ is N and Z² is C, R⁶ is a monosubstituent -CF₃ at a 5-position of a pyridine ring, and a general formula of the compound is shown in formula (a):
[0017] Preferably, R⁴ and R⁵ are each independently hydrogen, halogen, -CN, -COR⁷,-CO₂R⁷, -CH₂COR⁷, -CH₂COOR⁷, amino, alkyl, heteroalkyl, aryl or heteroaryl; wherein R⁷ is hydrogen, halogen, hydroxyl, C_1-4 alkyl, C_1-4 haloalkyl, C_1-4 alkenyl, C_1-4 haloalkenyl, amino or substituted amino.
[0018] Preferably, when the compound is shown in the formula (a) or the formula (b), and any one of R⁴ and R⁵ is hydrogen, R¹ is -CN, and R² is -SOCF₃ or -OCF₃; or R¹ is -CF₃, and R² is -SOCF₃;or, when neither R⁴ nor R⁵ is hydrogen, R¹ is -CN or -CF₃; and R² is -SOCF₃, - SOCH₂CH₃, -OCF₃, -CF₃, -CN or halogen.
[0019] Preferably, when the compound is shown in the formula (c), R³ is -CH₃, -Ac or - CH₂CH₂Cl, R² is -SOCF₃, R¹ is -CN, and both R⁴ and R⁵ are -CO₂Me;or, when R³ is hydrogen, and R² is -CN, -CF₃ or -SOCH₂CH₃, R¹ is -CN or -CF₃, and R⁴ and R⁵ are independently -CO₂Me or- -CH₂CO₂Me;or, when R³ is hydrogen, and R² is -OCF₃ or -SOCF₃, R¹ is -CN or -CF₃, R⁴ and R⁵ are each independently hydrogen, halogen, -CN, -COR⁷, -CO₂R⁷, -CH₂COR⁷, - CH₂COOR⁷, amino, alkyl, heteroalkyl, aryl or heteroaryl; wherein the amino, the alkyl, the aryl or the heteroaryl is unsubstituted or substituted with one or more substituents R⁹.
[0020] Preferably, when the compound is shown in the formula (d), R³ is hydrogen, and R² is -CN, -CF₃, -SOPh, -SOCH₂Ph, -SOC₆H₁₃,
[0021] Preferably, when the compound is shown in the formula (e), R⁶ is 3-Cl and 6-CF₃, 3-Cl and 4-CF₃, 4-Cl and 5-CF₃, or 5-Cl and 6-CF₃ on the benzene ring; and R⁴ and R⁵ are each independently -CO₂Me, -CH₂CO₂Me, -CO₂Et, -CH₂CO₂Et, - CH₂CO₂CH₂CF₃ or -CH₂CO₂CH₂CHF₂.
[0022] An agricultural composition includes:(a) 0.001 to 99.99% by weight of the compound above, the optical isomer, the cis and trans isomers or the agromedically acceptable salt thereof, or a combination thereof; and (b) an agromedically acceptable carrier and/or excipient.
[0023] Use of the agricultural composition according to the present invention in preparing an insecticide for killing or preventing agroforestry pests, sanitary insect pests and pests harmful to animal health.
[0024] A specific use method is that the insecticide is directly applied to the pests or places contacted by the pests (for example, plants suffering from or probably suffering from pest damages, soil or environment therearound).
[0025] Compared with the prior art, the present invention has the following beneficial effects.
[0026] The present invention discloses the fused heterocyclic compounds with a new structure and the pyrazole-ring-containing fused heterocyclic compound. The fused heterocyclic compound and the pyrazole-ring-containing fused heterocyclic compound, and the optical isomer, cis and trans isomers or the agromedically acceptable salt thereof have high killing activity on agroforestry pests and sanitary insect pests and the like, and the compound according to the present invention has a delayed effect on pests such as Solenopsis invicta and the like, which enables the pests to carry the compound to a nest, thereby having a better killing effect on the whole Solenopsis invicta nest and a queen Solenopsis invicta. The compound according to the present invention has a good application prospect in pest control. The compound according to the present invention has lower toxicity to environmental organisms such as bees, Bombyx mori L. and the like, thus having a good application prospect. DETAILED DESCRIPTION
[0027] The inventor of the present invention designs, synthesizes and screens a new fused heterocyclic compound and a pyrazole-ring-containing fused heterocyclic compound based on the problems of increasingly serious resistance and harmness to the environment and the like of the existing heterocyclic pesticides upon long-term and in-depth research. An insecticidal activity of the compound is obviously improved, and the compound has an expanded insecticidal spectrum. The present invention is further illustrated hereinafter with reference to the specific embodiments, but the embodiments are not intended to limit the present invention in any form. Unless otherwise specified, all the reagents and methods involved in the embodiments are frequently-used reagents and methods in the field.
[0028] In the present invention, unless otherwise specified in the context, meanings expressed by words, phrases and symbols to be used below are regulated as follows. The meanings of the following abbreviations and terms are used throughout the text.
[0029] The term "halogen" refers to fluorine, chlorine, bromine and iodine, and the term "halogen" in front of a group name refers to that the group is partially or completely halogenated, i.e., the group is substituted by F, Cl, Br or I in any combination, for example, monofluorodichloromethyl, difluoromethyl, trichloromethyl, pentafluoroethyl, or similar groups.
[0030] The term "alkyl" refers to hydrocarbyl, and the hydrocarbyl is selected from a saturated linear-chain or branched-chain hydrocarbyl. The alkyl preferably includes 1 to 12 carbon atoms, and more preferably includes 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or similar groups.
[0031] The term "alkenyl" refers to a hydrocarbyl selected from a linear-chain or a branched-chain, and includes at least one C=C double bond. The alkenyl preferably includes 2 to 12 carbon atoms, and more preferably includes 2 to 6 carbon atoms, such as vinyl, prop-1-alkenyl, prop-2-alkenyl, 2-methylprop-1-alkenyl, buta-1,3-dialkylene, 2-methyl-1,3-butadiene, hex-1,3-dialkylene, or similar groups.
[0032] The term "cycloalkyl" refers to be selected from to a saturated cyclohydrocarbyl, and includes a monocyclic or polycyclic group. The cycloalkyl preferably has 3 to 12 carbon atoms. For example, the cycloalkyl may be a monocyclic group having 3 to 12 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl, or similar groups. The cycloalkyl may also be a bicyclic group having 4 to 12 carbon atoms, such as a bicyclic group in [4,5], [5,5], [5,6] and [6,6] ring systems, a bridged bicyclic group selected from bicyclic[2.2.1]heptane, bicyclic[2.2.2]octane and bicyclic[3.2.2]nonane, or similar groups.
[0033] The term "cycloalkenyl" refers to be selected from an unsaturated cyclohydrocarbyl, and contains at least one C=C double bond, but is not completely conjugated, and the cycloalkenyl does not belong to an aromatic series (the aromatic series as defined herein), and includes a monocyclic or polycyclic group. The cycloalkenyl preferably has 3 to 12 carbon atoms, such as cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cyclooctene, and cyclopentadiene, or similar groups.
[0034] The term "aryl" refers to be selected from the groups as follows: (a) 5 membered and 6 membered carbocyclic aromatic rings, such as phenyl, furan ring or thiophene ring; (b) bicyclic systems such as 7 to 12 membered bicyclic systems, wherein at least one ring is a carboatomic ring and an aromatic ring, such as naphthalene or 1,2,3,4-tetrahydroquinoline; (c) tricyclic systems, such as a 10 to 15 membered tricyclic systems, wherein at least one ring is a carboatomic ring and an aromatic ring, such as fluorene.
[0035] For example, the aryl is selected from 5-membered and 6-membered carbocyclic aromatic rings, wherein the carbocyclic aromatic ring is fused to 5 to 7 membered cycloalkyl or a heterocycle optionally containing at least one heteroatom selected from N, O and S,under the conditions that a connection point is on the carbocyclic aromatic ring when the carbocyclic aromatic ring is fused to the heterocycle, and the connection point may be on the carbocyclic aromatic ring or on the cycloalkyl when the carbocyclic aromatic ring is fused to the cycloalkyl. A divalent group formed from a substituted benzene derivative and having a free valence on a ring atom is called a substituted phenylene group. A divalent group derived from a monovalent polycyclic hydrocarbon with a name ended with "yl" by removing a hydrogen atom from a carbon atom having a free valence is named by adding "subunit" to the name of the corresponding monovalent group, for example, a naphthyl having two connection points is called a naphthylene. However, the aryl does not include heterocyclyl or overlaps with heteroaryl, which are defined separately below. Therefore, if one or more carbocyclic aromatic rings are fused with a heterocyclic aromatic ring, a resulting ring system is the heteroaryl as defined herein, rather than the aryl.
[0036] The term "heteroalkyl" refers to an alkyl including at least one heteroatom, and the heteroatom refers to a non-C atom. The heteroatom is preferably N, O, S, P or Se, etc.
[0037] The term "heteroaryl" refers to be selected from the groups as follows: 5 to 7 membered aromatic monocyclic ring containing 1, 2, 3 or 4 heteroatoms selected from N, O and S, and the rest ring atoms being carbon; 8 to 12 membered bicyclic ring containing 1, 2, 3 or 4 heteroatoms selected from N, O and S, the remaining ring atoms being carbon, and wherein at least one ring is aromatic and at least one heteroatom is present in the aromatic ring; 11 to 14 membered bicyclic ring containing 1, 2, 3 or 4 heteroatoms selected from N, O and S, the remaining ring atoms being carbon, and wherein at least one ring is aromatic and at least one heteroatom is present in the aromatic ring;
[0038] For example, the heteroaryl includes a 5 to 7 membered heterocyclic aromatic ring fused to a 5 to 7 membered cycloalkyl ring. For the fused bicyclic heteroaryl ring system, only one ring therein contains at least one heteroatom, and a connection point may be located on the heterocyclic aromatic ring or the cycloalkyl ring.
[0039] When a total number of S and O atoms in the heteroaryl exceeds 1, these heteroatoms are not adjacent to each other.
[0040] The term "heterocyclyl" refers to be selected from the rings as follows: saturated and partially unsaturated rings of 4 to 12 memberd monocyclic, bicyclic and tricyclic rings, which contain at least one carbon atom in addition to 1, 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen. The term "heterocyclyl" also refers to an aliphatic spiro ring containing at least one heteroatom selected from N, O and S under the condition that a connection point is located on a heterocycle. The ring may be saturated or contain at least one double bond. The heterocycle may be oxidatively substituted. A connection point may be a carbon atom or a heteroatom in the heterocycle.
[0041] The term "alkoxy" refers to a hydrocarbonoxy selected from saturated linear or branched hydrocarbonoxy. The alkoxy includes 1 to 12 carbon atoms, and preferably includes 1 to 6 carbon atoms, such as methoxyl, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, or similar groups.
[0042] The substituents are selected from halogen, -R''''', -OR''''', =O, =NR''''', =NOR''''', -NR'''''R'''''', -SR''''', -OC(O)R'''', -C(O)R'''', -CO₂R'''',-CONR'''''R'''''', -OC(O)NR'''''R'''''', -NR'''''C(O)R'''''', -NR'''''-SO₂NR'''''', -NR''''''CO₂R''''', -NH-C(NH₂)=NH, -NR'''''C(NH₂)=NH, -NH-C(NH₂)=NR''''', -S(O)R''''', -SO₂R''''', -SO₂NR'''''R'''''', -NR''''''SO₂R''''',-CN and -NO₂, -CH(Ph)₂, halogenated (C₁-C₄) alkoxy and halogenated (C₁-C₄)alkyl. A number of the substituents ranges from 0 to 3, and preferably, 0, 1 or 2 substituents are provided. R''''' and R''''' are independently selected from hydrogen, unsubstituted (C₁-C₆) alkyl and heteroalkyl, unsubstituted aryl, aryl substituted with 1 to 3 halogens, unsubstituted alkyl, alkoxy or thioalkoxy, or aryl-(C₁-C₄) alkyl. When being connected to the same nitrogen atom, R''''' and R'''''' can combine with the nitrogen atom to form a 5, 6 or 7 membered ring. Therefore, -NR'''''R'''''' includes 1-pyrrolidinyl and 4-morpholinyl. The "alkyl" includes, for example, trihaloalkyl (e.g., -CF₃ and -CH₂CF₃).
[0043] Preferably, the substituents are selected from halogen, -R''''', -OR''''', =O,-NR'''''R'''''', -SR''''', -OC(O)R''''', -C(O)R''''', -CO₂R''''', -CONR'''''R'''''',-OC(O)NR'''''R'''''', -NR''''''C(O)R''''', -NR''''''CO₂R''''', -S(O)R''''', -SO₂R''''',-SO₂NR'''''R'''''', -NR''''''SO₂R''''', -CN and -NO₂, halogenated (C₁-C₄) alkoxy and halogenated (C₁-C₄) alkyl, wherein R''''' and R'''''' are defined as above.
[0044] The term "fused heterocycle" herein refers to a following cyclic system, such as a bicyclic or tricyclic system, in which two rings share only two ring atoms and one bond, and the ring atoms thereof contain at least one non-C atom. Examples of the fused heterocycle may include fused bi-heterocycloalkyl, such as bi-heterocycles selected from the above [4,4], [4,5], [5,5], [5,6] and [6,6] ring systems composed by arrangement of 7 to 12 ring atoms; fused bicyclic heteroaryl rings, such as the 8 to 12 membered bicyclic heteroaryl rings described above; fused tricyclic heteroaryl rings, such as the 11 to 14 membered tricyclic heteroaryl rings described above, for example, pyrazolo[1,5-a]quinazoline, pyrazolo[1,5-c]quinazoline, pyrrolo[1,2-a]quinazoline, pyrazolo[1,5-a]pyrido[3,2-e]pyrimidine, pyrazolo[1,5-a]pyrido[3,4-e]pyrimidine, pyrazolo[1,5-a]pyrido[2,3-e]pyrimidine, and pyrazolo[1,5-a]pyrido[4,3-e]pyrimidine, etc.; and the fused bicyclic or tricyclic heterocyclic rings.
[0045] The compound may contain an asymmetric center, and thus may exist as an enantiomer. When the compound has two or more asymmetric centers, they may additionally exist as diastereomers. The enantiomers and the diastereomers belong to a broader category of stereomers. All these possible stereomers include substantially pure resolved enantiomers (meaning that a target stereomer contains no more than 10% by weight of any other stereomer), racemic mixtures thereof, and diastereomeric mixtures thereof. Unless otherwise stated, one of the mentioned isomers applies to any possible isomer. When isomer components are not specified, all possible isomers are included.
[0046] When the compound contains olefinic double bonds, these double bonds refer to geometric isomers containing E and Z, unless otherwise stated.
[0047] Some compounds may have different hydrogen connection points, which are called tautomers. For example, a compound containing a carbonyl-CH₂C(O)-group (keto form) may undergo tautomerism to form a hydroxyl-CH=C(OH)-group (enol form). During application, the compound also includes the keto form and enol form alone and mixtures thereof.
[0048] The term "acceptable salt" refers to a salt with known cations or aions, and may be applied to form use in the field.
[0049] Suitable salts with bases, for example, salts formed from compounds of formula (I) and formula (II) containing carboxyl groups, include salts of alkali metals (such as sodium and potassium), alkali earth metals (such as calcium and magnesium), ammonium and amines.
[0050] Suitable salts with acid radical additives, such as salts formed from compounds of formula (I) and formula (II) containing amino, include salts formed with inorganic acids such as hydrochloride, sulphate, sulphite, phosphate, hydrogen phosphate and nitrate, and salts formed with organic acids such as acetic acid, malic acid, tartaric acid, citric acid, lactic acid, salicylic acid, oxalic acid, etc.
[0051] Moreover, if the compound is obtained as an acid addition salt, free alkalis can be obtained by alkalizing a solution of the acid salt. In contrast, if a product is a free alkali, the addition salt can be prepared by dissolving the free alkali in a suitable organic solvent and treating the solution with an acid, which is consistent with a conventional process of preparing an acid addition salt from an alkaline compound. Those skilled in the art should understand various synthesis methods that can be used to prepare agromedically acceptable addition salts without undue experimentation.
[0052] The compound of the present invention can be used to control and kill various agroforestry pests, sanitary insect pests and pests harmful to animal health. In this specification, the "insecticide" is a general designation of substances that have the effect of preventing and controlling all the pests mentioned above. Examples of the pests include, but are not limited to: coleoptera insects such as Sitophilus zeamais, Tribolium castaneum, Henosepilachna vigintioctomacta, Henosepilachna sparsa, Agrarius fusillis, Anomala cupripes, Popillia quadriguttata, Monolepta hieroglyphica, Monochamus alternatus, Echinocnemus squameus, Basiprionota bisignata, Anoplophora chinensis, Apripona germari, Soclytus schevy, or Agriotes fuscicollis; lepidoptera insects such as Lymantria dispar, Malacosoma neustria testacea, Diaphania perspectalis, Clania variegata, Cnidocampa flauescens, Dendrolimus punctatus, Orgyia antiqua, Paranthrene tabaniformis, Spodoptera litura, Chilo suppressalis, Ostrinia nubilalis, Ephestia cautella, Adoxophyes orana, Laspyresia splendana, Agrotis fucosa, Galleria mellonella, Plutella xylostella, Phyllocnistis citrella, or Mythimna separata; hemiptera insects such as Stephanitis nashi; homoptera insects such as Nephotettix cincticeps, Unaspis yanonensis, Myzus persicae, Aphis gossydii, or Bemisia tabaci; orthoptera insects such as Gryllotalpa africana, or Locus migratoria; hymenoptera insects such as Solenopsis invicta, or Tremex fuscicornis; blattaria insects such as Blattella germanica, Periplaneta american, or Copotermes formosamus; diptera insects such as Musca domestica, Aedes aegypti, Delia platura, Culex sp., or Anopheles sinensis; and plant parasitic nematodes such as Meloidogyne, Pratylenchus spp., Aphelenchoides besseyi Christie, Bursaphelenchus xylophilus, etc. The pests harmful to animal health include Boophilus microplus, Haemaphysalis longicornis, Hyalomma anatolicum, Hypoderma spp., Fasciola hepatica, Moniezia blanchard, Ostertagia spp., Trypanosoma enansi, Babesia bigemina, etc.
[0053] The compound related to the present invention preferably has a high activity on agroforestry pests such as lepidoptera, hymenoptera, hemiptera, coleoptera, diptera and blattaria pests, as well as animal parasitic fleas and/or ticks and mites and sanitary insect pest, and more preferably has a high activity on piercing-sucking or chewing mouthpart pests. Insecticide composition containing the active substances of the present invention
[0054] The active substances of the present invention may be prepared into an insecticide composition by a conventional method. These active compounds may be combined into conventional preparations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with the active substances, microcapsules in polymers, coating compounds for seeds, and preparations for use with firing units (such as smoking cartridges, smoking cans, and smoking pans), as well as ultra-low volume (ULV) Cloud mist and Warm mist preparations.
[0055] These preparations may be produced by known methods, for example, the active compounds are mixed with extenders, which are liquid or liquefied gas or solid diluents or carriers, and optionally surfactants, i.e., emulsifiers and/or dispersants and/or foam formers. For example, when water is used as the extender, organic solvents may also be used as auxiliaries.
[0056] It is basically suitable to use liquid solvents as the diluents or carriers, such as aromatic hydrocarbons, for example, xylene, toluene or alkyl naphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride or methylene chloride; aliphatic hydrocarbons such as cyclohexane, paraffin or mineral oil fractions; alcohols such as ethanol or glycol as well as ethers and lipids thereof; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or polar solvents that are not frequently used such as dimethylformamide, dimethyl sulphoxide, and water. The liquefied gas diluents or carriers refer to liquids that will become gas at normal temperature and pressure, such as aerosol propellants, for example, halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.
[0057] The solid carriers may be ground natural minerals such as kaolin, clay, talc, quartz, activated clay, montmorillonite, or diatomite, and ground synthetic minerals such as highly dispersed silicic acid, alumina, and silicates. The solid carriers for granules are crushed and graded natural zircon, such as calcite, marble, pumice, sepiolite and dolomite, as well as granules synthesized from inorganic and organic coarse powders, and organic materials such as granules of sawdust, coconut shells, corn cobs and tobacco stems, etc.
[0058] Non-ionic and anionic emulsifiers may be used as emulsifiers and/or foam formers, for example, polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, such as alkaryl polyethylene glycol ethers, alkyl sulfonic acid esters, alkyl sulfates, aryl sulfonic esters, and albumin hydrolysates. The dispersants include, for example, lignin sulfite lye and methylcelluloses.
[0059] Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or emulsions, such as Arabic gum, polyvinyl alcohol and polyvinyl acetate, may be used in the preparations. Colorants such as inorganic fuels, for example, iron oxide, cobalt oxide and Prussian blue; organic dyes, such as dichloro dyes or metal cyanine dyes; and trace nutrients such as salts of iron, manganese, boron, cop, cobalt, aluminum and zinc may be used.
[0060] These active compounds of the present invention may be mixed with other active compounds to prepare a mixture that can be present in commercial preparations or in use preparation forms prepared from these preparations. The other active compounds include, but are not limited to: insecticides, baits, fungicides, acaricides, nematicides, fungicides, growth control agents, and the like. The insecticides include, for example, phosphates, carbamates, pyrethroids, chlorinated hydrocarbons, benzamides, nereistoxin and substances produced by microorganisms, such as abamectin.
[0061] Furthermore, these active compounds of the present invention may also be mixed with synergists to prepare a mixture that can be present in commercial preparations or in use preparation forms prepared from these preparations. The synergist is a compound that enhances the effect of the active compounds. Since the active compounds have activity, it is not necessary to add the synergist.
[0062] These preparations generally contain 0.001 to 99.99% by weight, preferably 0.01 to 99.9% by weight, more preferably 0.05 to 90% by weight of the active compound of the present invention in the insecticide composition. Concentration of the active compounds in the use preparation form prepared from the commercial preparations may vary within a wide range. The concentrations of the active compounds in the use preparation forms may range from 0.0000001 to 100% (g/v), and may preferably be between 0.0001 and 1%.
[0063] The present invention wil be described in further detail below with reference to the specific embodiments, and the specific embodiments are only used to explain the present invention and are not used to limit the scope of the present invention. The experimental methods used in the following embodiments are conventional unless otherwise specified. The materials and reagents used are commercially available materials and reagents unless otherwise specified. Synthesis embodiments: Embodiment 1: Synthesis of compounds A1 to A47 by using a method A
[0064]
[0065] For instance, synthesis of a compound A1: S1: 5-amino-1H-pyrazole-3-cyano
[0066] Ethyl 2,3-dicyanopropionate (1.0 mmol) was added to 20.0 ml of ethanol and stirred vigorously, then hydrazine hydrate (2.0 mmol) was added to the reaction solution, heated and refluxed, then the heating was stopped after 3 hours, and the mixture was cooled to room temperature. The mixture was concentrated in vacuum and extracted with ethyl acetate and water, then the obtained ethyl acetate was concentrated and extracted in vacuum to obtain white solid 5-amino-1H-pyrazole-3-cyano, and the intermediate was directly used for next step without further purification. S2: 5,5-dimethyl-4,5-dihydropyrazole[1,5-α]quinazoline-2-cyano
[0067] Under the protection of nitrogen, a DMF mixture of 5-amino-1H-pyrazole-3-cyano (1.0 mmol), 1-bromo-2-(1-bromo-1-methylethyl)benzene (1.0 mmol), cuprous iodide (0.2 mmol) and cesium carbonate (0.5 mmol) was stirred at 100°C for 24 hours. The mixture was cooled to room temperature, and then filtered, and concentrated in vacuum, and the residues were purified by column chromatography to obtain the target compound 5,5-dimethyl-4,5-dihydropyrazole[1,5-a]quinazoline-2-cyano (yield of the two steps: 45%).
[0068] The compounds A2 to A47 were synthesized with reference to the method of the compound A1 (wherein cyclization steps also included similar cyclization methods mentioned in documents such as Tetrahedron Letters (2015) 56: 1367; WO2016046404 , and WO2013174822 ), with a difference that different raw materials were selected for reaction according to different target compounds, or the compounds were derived from the synthesized target products. Specific compounds were as shown in Table 1: Table 1 Compound Structural formula R¹¹ R¹² R¹³ R¹⁴ R¹⁵ R¹⁶ A1
[0069]
[0070] For instance, synthesis of a compound B1: S1: 2-amino-4-(4-methoxybenzene)-1H-pyrrole-3-cyano
[0071] 2-bromo-1-(4-methoxyphenyl)-acetyl (1.0 mmol) was added to 15 ml of DMF, and then sodium azide (10.0 mmol) was added to the reaction solution. After the reaction mixture was stirred for 48 hours, the reaction mixture was filtered, and an obtained filtrate was extracted with ethyl ether for multiple times. Concentration in vacuum was performed, the residues were dissolved with methanol, and then 10% palladium carbon (0.2 mmol) was added thereto in a hydrogen atmosphere. The reaction mixture was stirred for 24 hours, and then filtered. An obtained filtrate was concentrated in vacuum, the residues were dissolved with tetrahydrofuran, and then acetic anhydride (2.0 mmol) and triethylamine (2.0 mmol) were added thereto. The reaction mixture was stirred for 5 hours, and then concentrated in vacuum, and the residues were purified by column chromatography to obtain N-(2-(4-methoxyphenyl)-2-ethoxy)-acetamide (yield: 78%).
[0072] N-(2-(4-methoxyphenyl)-2-ethoxy)-acetamide (1.0 mmol) was added to 15 ml of ethanol, and then malononitrile (2.0 mmol) and sodium ethoxide (1.5 mmol) were added thereto. The mixture was heated and refluxed for 12 hours, and then concentrated in vacuum, and the residues were purified by column chromatography to obtain the target compound (yield: 89%). S2: 2-bromo-2-(2-chloro-4-nitrophenyl)malononitrile
[0073] Under nitrogen protection, 2-chloro-4-nitro-benzoyl chloride (1.0 mmol) was dissolved in 10 ml of dry pyridine, cooled to 0°C, then trimethylsilylnitrile (1.1 mmol) was slowly added dropwise to the reaction solution, and the reaction solution was naturally heated to room temperature. After stirring for 10 hours, the reaction mixture was cooled to 0°C again, and 2 ml of phosphorous oxybromide was added to the reaction mixture. After stirring for 12 hours, the solution was removed in vacuum, and the residues were extracted with water and ethyl acetate. Then the ethyl acetate was obtained by concentration and extraction in vacuum, and the residues were purified by column chromatography to obtain the 2-bromo-2-(2-chloro-4-nitrophenyl)malononitrile (yield: 56%). S3: 2-(4-methoxybenzene)-8-nitropyrrole[1,2-α]quinazoline-3,5,5(4H)-tricyano
[0074] Under the protection of nitrogen, a DMF mixture of 2-amino-4-(4-methoxybenzene)-1H-pyrrole-3-cyano (1.0 mmol), 2-bromo-2-(2-chloro-4-nitrophenyl)malononitrile (1.1 mmol), cuprous iodide (0.2 mmol) and sodium ethoxide (0.5 mmol) was stirred at 120°C for 24 hours. The mixture was cooled to room temperature, and then filtered, and concentrated in vacuum, and the residues were purified by column chromatography to obtain the 2-(4-methoxybenzene)-8-nitropyrrole[1,2-α]quinazoline-3,5,5(4H)-tricyano (yield: 53%).
[0075] The compounds B2 to B12 were synthesized with reference to the method of the compound B1 (similar cyclization methods mentioned in documents such as Synthetic Communications (2015) 45: 2426; Tetrahedron (2014) 55: 4997; and WO2007149907 ), with a difference that different raw materials were selected for reaction according to different target compounds, and some compounds, such as compounds B9, B10, B11, B12, etc., could be obtained by modifying B7. Specific compounds were as shown in Table 2: Table 2 Compound Structural formula R¹¹ R¹² R¹³ R¹⁴ R¹⁵ R¹⁶ B1
[0076]
[0077] For instance, synthesis of a compound C1: S1: (2-amino-3-chloro-5-(trifluoromethyl)phenyl)boric acid
[0078] Under the protection of nitrogen, 2-bromo-6-chloro-4-trifluoromethylaniline (1.0 mmol) was dissolved in 20 ml of dry tetrahydrofuran, and cooled to 0°C, then n-butyl lithium (2.5 mmol, 1.6 M n-hexane solution) was slowly added dropwise to the reaction mixture, and stirred for 2 hours. Trimethylchlorosilane (2.5 mmol) was slowly added dropwise to the reaction mixture for reaction, and then the reaction mixture was naturally heated and stirred for 12 hours, the solvent was removed by vacuum concentration, and the target compound (2-amino-3-chloro-5-(trifluoromethyl)phenyl)boric acid (yield: 87%) was obtained by reduced pressure distillation. S2: 2-chloro-6-(1,2-dichloro-3-butene-2-yl)-4-(trifluoromethyl)phenylamine
[0079] Under the protection of nitrogen, a DMF mixture (3.0 ml) of 3-bromo-3,4-dichloro-1-butene (1.0 mmol), Pd(dppf)Cl₂ (0.15 mmol), sodium carbonate (0.15 mmol) and (2-amino-3-chloro-5-(trifluoromethyl)phenyl)boric acid (1.5 mmol) and water (0.5 ml) were stirred at 100°C for 10 hours. After the solution was removed in vacuum, the residues were diluted with water (10 ml). Then a water layer was extracted with ethyl acetate, and the ethyl acetate was obtained by concentration and extraction in vacuum, and the residues were purified by column chromatography to obtain the target compound 2-chloro-6-(1,2-dichloro-3-butene-2-yl)-4-(trifluoromethyl)phenylamine (yield: 85%). S3: 2-bromo-1-chloro-3-(1,2-dichloro-3-butene-2-yl)-5-(trifluoromethyl)phenyl
[0080] Under the protection of nitrogen, 2-bromo-1-chloro-3-(1,2-dichloro-3-butene-2-yl)-5-(trifluoromethyl)phenyl (1.0 mmol) and cupric bromide (1.5 mmol) were dissolved in 10 ml of acetonitrile, cooled to -5°C, and then isoamyl nitrite (1.3 mmol) was slowly added thereto, and the reaction mixture was heated to 50°C. After three hours, the mixture was filtered, and the filtrate was concentrated in vacuum, and the residues were purified by column chromatography to obtain the target compound 2-bromo-1-chloro-3-(1,2-dichloro-3-butene-2-yl)-5-(trifluoromethyl)phenyl (yield: 91%). S4: 9-chloro-7-trifluoromethylphenyl-5-chloromethyl-5-vinyl-4,5-dihydropyrrole[1,5-α]quinazoline-2-cyano
[0081] Under the protection of nitrogen, a DMF mixture of 5-amino-1H-pyrazole-3-cyano (1.0 mmol), 2-bromo-1-chloro-3-(1,2-dichloro-3-butene-2-yl)-5-(trifluoromethyl)phenyl (1.1 mmol), cuprous iodide (0.2 mmol) and sodium ethoxide (0.5 mmol) was stirred at 120°C for 24 hours. The mixture was cooled to room temperature, and then filtered. The filtrate was concentrated in vacuum, and the residues were purified by column chromatography to obtain the target compound 9-chloro-7-trifluoromethylphenyl-5-chloromethyl-5-vinyl-4,5-dihydropyrrole[1,5-α]quinazoline-2-cyano (yield: 52%).
[0082] The compounds C2 to C64 were synthesized with reference to the method of the compound C1 (similar cyclization methods were mentioned in documents such as WO2007144669 ), with a difference that different raw materials were selected for reaction according to different target compounds. Specific compounds were as shown in Table 3. Table 3 Compound Structural formula R¹¹ R¹² R¹³ R¹⁴ R¹⁵ R¹⁶ C1
[0083]
[0084] Taking a compound a-44 for example, a specific preparation process was as follows: S1: 5-amino-1H-pyrazole-3-cyano
[0085] Ethyl 2,3-dicyanopropionate (1.0 mmol) was added to 20.0 mL of ethanol and stirred vigorously, then hydrazine hydrate (2.0 mmol) was added to the reaction solution, heated and refluxed, then the heating was stopped after 3 hours, and the mixture was cooled to room temperature. The mixture was concentrated in vacuum and extracted with ethyl acetate and water, then the obtained ethyl acetate was concentrated and extracted in vacuum to obtain white solid 5-amino-1H-pyrazole-3-cyano, and the intermediate was directly used for next step without further purification. S2: 5,5-dichloro-7-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline[3,2-e]pyridine-2-cyano
[0086] Under the protection of nitrogen, a DMF mixture of 5-amino-1H-pyrazole-3-cyano (1.0 mmol), 2-bromo-3-(trichloromethyl)-5-trifluoromethylpyridine (1.0 mmol), cuprous iodide (0.2 mmol) and cesium carbonate (0.5 mmol) was stirred at 120°C for 24 hours. The mixture was cooled to room temperature, and then filtered, and concentrated in vacuum, and the residues were purified by column chromatography to obtain the target compound 5,5-dichloro-7-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline[3,2-e]pyridine-2-cyano (yield of the two steps: 25%). S3: 5,5-dichloro-7-trifluoromethyl-3-trifluoromethylsulfinyl-4,5-dihydropyrazole[1,5-α]quinazoline[3,2-e]pyridine-2-cyano
[0087] Under the protection of nitrogen, an anhydrous toluene mixture of 5,5-dichloro-7-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline[3,2-e]pyridine-2-cyano (0.2 mmol), trifluoromethylsulfinyl chloride (0.5 mmol) and dimethylamine p-toluenesulfonate was stirred and heated at 100°C for 24 hours. The mixture was cooled to room temperature, and then filtered, and concentrated in vacuum, and the residues were purified by column chromatography to obtain the target compound 5,5-dichloro-7-trifluoromethyl-3-trifluoromethylsulfinyl-4,5-dihydropyrazole[1,5-α]quinazoline[3,2-e]pyridine-2-cyano (yield: 77%).
[0088] The compounds a-1 to a-138 were synthesized with reference to the method of the compound a-44 (wherein cyclization steps also included similar cyclization methods mentioned in documents such as Tetrahedron Letters (2015) 56: 1367; WO2016046404 , and WO2013174822 ), with a difference that different raw materials were selected for reaction according to different target compounds, or the compounds were derived from the synthesized target products through hydrolysis, simple esterification or amidation or reduction-oxidation. Specific compounds were as shown in Table 7. Table 7: Compound Structure with a General Formula Shown in Formula (a) Structural formula Compound R¹ R² R³ R⁴ R⁵ R⁶a-1 H -CH₂CO₂Me a-2 -CH₂CN a-3 -CH₂CONH₂a-4 -CH₂CONHCH₃a-5 -CH₂CH₂OH a-6 -CH(CO₂Me)CH₃ Formula a-7 -CH₃-CH₂CO₂Me (a) a-8 -CN -SOCF₃ -CH₂CH₂Cl -CO₂Me -CH₂CO₂Me 5-CF₃ a-9 H -CH₂CO₂Et a-10 -CH₂CO₂CH₂CF₃a-11 -CH₂CO₂CH₂CHF₂a-12 -CH₂CO₂CH(CF₃)₂a-13 -CH₂CO₂C(CH₃)₂CF₃a-14 -CH₂CO₂C(CF₃)₂CH₃a-15 -CH₂CO₂CH(CF₃)OCH₃a-16 -CH₂Ph a-17 -CH₂COCH₃a-18 -CH₂Br a-19 -CH₂CF₃a-20 -CH₂COCF₃a-21 -SOCH₂CH₃ -CH₂CO₂Me a-22 -CO₂Et -CH₂CO₂Et a-23 -CH₂CO₂Me a-24 -CH₂CO₂CH₂CF₃a-25 -COCF₃ -CH₂COCF₃a-26 -CH₂COCH₃a-27 -CH₂Ph a-28 -CH₂CO₂Me a-29 -CH₂Br a-30 -CH₂CN a-31 -CH₂CF₃a-32 -COCH₃ -CH₂COCH₃a-33 -CH₂CO₂Me a-34 -CH₂Br a-35 -CH₂CN a-36 -SOCF₃ H -CH₂CF₃a-37 -CH₂COCF₃a-38 -CONHMe -CH₂COCH₃a-39 -CH₂CO₂Me a-40 -CH₂Br a-41 -CH₂CF₃a-42 -CH₂COCF₃a-43 -NHMe -CH₂CN a-44 -Cl -Cl a-45 -CH₂Br a-46 -CH₂Cl a-47 -CH₂CN a-48 -CH₂CF₃a-49 -Br -CH₂Cl a-50 -CH₂COCF₃a-51 -CH₃ -CH₃a-52 -CN -CN a-53 -CH₂CN a-54 -CH₂CF₃a-55 -CH₂Cl a-56 -CH₂CO₂Me a-57 -CH₂COCF₃a-58 CF₃ -CF₃a-59 -CH₂CN a-60 -CH₂CF₃a-61 -CH₂Cl a-62 -CH₂CO₂Me a-63 -CH₂COCF₃a-64 -CO₂Me a-65 -CH₂CO₂Me a-66 -CH(CO₂Me)CH₃a-67 -CH₂CO₂CH₂CF₃a-68 -CO₂CH₂CF₃a-69 -CH₂CO₂CH(CF₃)₂a-70 -CH₂COCF₃a-71 -COCF₃a-72 -CN a-73 -CH₂CN a-74 -CN -SOCF₃ H H -CF₃a-75 -CH₂CF₃a-76 -CONHMe a-77 -CH₂CONHCH₃a-78 -CH₂COCH₃a-79 -COCH₃a-80 -Cl a-81 -Br a-82 -CH₂Cl a-83 -CH₂CH₂Cl a-84 -CHCHCl a-85 -CH(CH₃)₂a-86 -CH=CHCH₃a-87 -CO₂Me a-88 -CH₂CO₂Me a-89 -CH(CO₂Me)CH₃a-90 -CH₂CO₂CH₂CF₃a-91 -CO₂CH₂CF₃a-92 -CH₂CO₂CH(CF₃)₂a-93 -CH₂COCF₃a-94 -COCF₃a-95 -CN a-96 -CH₂CN a-97 -CF₃a-98 -CF₃ -SOCF₃ H H -CH₂CF₃a-99 -CONHMe a-100 -CH₂CONHCH₃a-101 -CH₂COCH₃a-102 -COCH₃a-103 -Cl a-104 -Br a-105 -CH₂Cl a-106 -CH₂CH₂Cl a-107 -CHCHCl a-108 -CH(CH₃)₂a-109 -CH=CHCH₃a-110 -CN -OCF₃ H H -CO₂Me a-111 -CH₂CO₂Me a-112 -CH(CO₂Me)CH₃a-113 -CH₂CO₂CH₂CF₃a-114 -CO₂CH₂CF₃a-115 -CH₂CO₂CH(CF₃)₂a-116 -CH₂COCF₃a-117 -COCF₃a-118 -CN a-119 -CH₂CN a-120 -CF₃a-121 -CH₂CF₃a-122 -CONHMe a-123 -CH₂CONHCH₃a-124 -CH₂COCH₃a-125 -COCH₃a-126 -Cl a-127 -Br a-128 -CH₂Cl a-129 -CH₂CH₂Cl a-130 -CHCHCl a-131 -CH(CH₃)₂a-132 -CH=CHCH₃a-133 -CN -Cl H -CO₂Me -CH₂CO₂Me a-134 -CF₃a-135 -OCF₃a-136 -CF₃ -CN a-137 -OCF₃a-138 -SOCF₃ Embodiment 5: Synthesis of compounds b-1 to b-138 by using a method EMethod E:
[0089]
[0090] Taking a compound b-87 for example, a specific synthesis process was as follows: S1: 5-amino-1H-pyrazole-3-trifluoromethyl (referring to document Journal of Medical Chemistry (2017) 60: 5099)
[0091] Under the protection of nitrogen, sodium hydride (2.5 mmol) was added to 20 ml of anhydrous tetrahydrofuran at 0°C, then anhydrous acetonitrile (2.0 mmol) and ethyl trifluoroacetate (1.0 mmol) were added to the reaction solution, heated and refluxed, and then the heating was stopped after 20 hours. The mixture was cooled to room temperature, and concentrated in vacuum. The mixture was extracted with ethyl ether and water, and diluted hydrochloric acid was added to adjust a pH to 2, then the mixture was extracted with ethyl ether, and concentrated in vacuum to obtain brown oily matter 4,4,4-trifluoro-3-carbonyl butyronitrile. The intermediate was directly used in next step without further purification.
[0092] Methanesulfonic acid (2.0 ml) was added to a mixture of 4,4,4-trifluoro-3-carbonyl butyronitrile (1.0 mmol) and hydrazine hydrate (1.0 ml), and the mixture was heated to 80°C and reacted for 10 hours. Then, water and ethyl acetate were added for extraction, and concentrated in vacuum. The residues obtained were purified by column chromatography to obtain the target compound 5-amino-1H-pyrazole-3-trifluoromethyl which was as a yellow liquid (yield of the two steps: 15%), 1H NMR (400 MHz, DMSO-d6): δ 12.15 (s, 1H), 5.53 (s, 1H), 5.35 (s, 2H). S2: 6-chloro-2-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline[4,3-e]pyridine-5-methyl formate
[0093] Under the protection of nitrogen, a DMF mixture of 5-amino-1H-pyrazole-3-trifluoromethyl (1.0 mmol), 2-bromo-2-(3-bromo-5-chloropyridine-4-yl)-methyl acetate (1.0 mmol), cuprous iodide (0.2 mmol) and sodium ethoxide (0.5 mmol) was stirred at 100°C for 24 hours. The mixture was cooled to room temperature, and then concentrated in vacuum, and the residues were purified by column chromatography to obtain the target compound 6-chloro-2-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline[4,3-e]pyridine-5-methyl formate (yield: 35%). S3: 6-chloro-2-trifluoromethyl-3-trifluoromethylsulfinyl-4,5-dihydropyrazole[1,5-α]quinazoline[4,3-e]pyridine-5-methyl formate
[0094] Under the protection of nitrogen, an anhydrous toluene mixture of 6-chloro-2-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline[4,3-e]pyridine-5-methyl formate (0.2 mmol), trifluoromethylsulfinyl chloride (0.5 mmol) and dimethylamine p-toluenesulfonate was stirred and heated at 100°C for 24 hours. The mixture was cooled to room temperature, and then concentrated in vacuum, and the residues were purified by column chromatography to obtain the target compound 6-chloro-2-trifluoromethyl-3-trifluoromethylsulfinyl-4,5-dihydropyrazole[1,5-α]quinazoline[4,3-e]pyridine-5-methyl formate, wherein the yield was 85%.
[0095] The compounds b-1 to b-138 were synthesized with reference to the method of the compound b-87 (wherein cyclization steps also included similar cyclization methods mentioned in documents such as Synthetic Communications (2015) 45: 2426; Tetrahedron Letters (2014) 55: 4997; and WO2007149907 ) with a difference that different raw materials were selected for reaction according to different target compounds, or the compounds were derived from the synthesized target products through hydrolysis, simple esterification or amidation or reduction-oxidation. Specific compounds were as shown in Table 8. Table 8: Compound Structure with a General Formula Shown in Formula (b) Structural formula Compound R¹ R² R³ R⁴ R⁵ R⁶b-1 H -CH₂CO₂Me b-2 -CH₂CN b-3 -CH₂CONH₂b-4 -CH₂CONHCH₃b-5 -CH₂CH₂OH b-6 -CH(CO₂Me)CH₃b-7 -CH₃-CH₂CO₂Me b-8 -CH₂CH₂Cl -CH₂CO₂Me b-9 H -CH₂CO₂Et Formula b-10 -SOCF₃-CH₂CO₂CH₂CF₃ (b) b-11 -CN -CO₂Me -CH₂CO₂CH₂CHF₂ 5-Cl b-12 -CH₂CO₂CH(CF₃)₂b-13 -CH₂CO₂C(CH₃)₂CF₃b-14 -CH₂CO₂C(CF₃)₂CH₃b-15 -CH₂CO₂CH(CF₃)OCH₃b-16 -CH₂Ph b-17 -CH₂COCH₃b-18 -CH₂Br b-19 -CH₂CF₃b-20 -CH₂COCF₃b-21 -SOCH₂CH₃-CH₂CO₂Me b-22 -CO₂Et -CH₂CO₂Et b-23 -CH₂CO₂Me b-24 -CH₂CO₂CH₂CF₃b-25 -COCF₃ -CH₂COCF₃b-26 -CH₂COCH₃b-27 -CH₂Ph b-28 -CH₂CO₂Me b-29 -CH₂Br b-30 -CH₂CN b-31 -CH₂CF₃b-32 -COCH₃ -CH₂COCH₃b-33 -CH₂CO₂Me b-34 -CH₂Br b-35 -CH₂CN b-36 -CH₂CF₃b-37 -CH₂COCF₃b-38 -CONHMe -CH₂COCH₃b-39 -SOCF₃ H -CH₂CO₂Me b-40 -CH₂Br b-41 -CH₂CF₃b-42 -CH₂COCF₃b-43 -NHMe -CH₂CN b-44 -Cl -Cl b-45 -CH₂Br b-46 -CH₂Cl b-47 -CH₂CN b-48 -CH₂CF₃b-49 -Br -CH₂Cl b-50 -CH₂COCF₃b-51 -CH₃ -CH₃b-52 -CN -CN b-53 -CH₂CN b-54 -CH₂CF₃b-55 -CH₂Cl b-56 -CH₂CO₂Me b-57 -CH₂COCF₃b-58 CF₃ -CF₃b-59 -CH₂CN b-60 -CH₂CF₃b-61 -CH₂Cl b-62 -CH₂CO₂Me b-63 -CH₂COCF₃b-64 -CO₂Me b-65 -CH₂CO₂Me b-66 -CH(CO₂Me)CH₃b-67 -CH₂CO₂CH₂CF₃b-68 -CO₂CH₂CF₃b-69 -CH₂CO₂CH(CF₃)₂b-70 -CH₂COCF₃b-71 -COCF₃b-72 -CN b-73 -CH₂CN b-74 -CF₃b-75 -CN -SOCF₃ H H -CH₂CF₃b-76 -CONHMe b-77 -CH₂CONHCH₃b-78 -CH₂COCH₃b-79 -COCH₃b-80 -Cl b-81 -Br b-82 -CH₂Cl b-83 -CH₂CH₂Cl b-84 -CHCHCl b-85 -CH(CH₃)₂b-86 -CH=CHCH₃b-87 -CF₃ -SOCF₃ H H -CO₂Me b-88 -CH₂CO₂Me b-89 -CH(CO₂Me)CH₃b-90 -CH₂CO₂CH₂CF₃b-91 -CO₂CH₂CF₃b-92 -CH₂CO₂CH(CF₃)₂b-93 -CH₂COCF₃b-94 -COCF₃b-95 -CN b-96 -CH₂CN b-97 -CF₃b-98 -CH₂CF₃b-99 -CONHMe b-100 -CH₂CONHCH₃b-101 -CH₂COCH₃b-102 -COCH₃b-103 -Cl b-104 -Br b-105 -CH₂Cl b-106 -CH₂CH₂Cl b-107 -CHCHCl b-108 -CH(CH₃)₂b-109 -CH=CHCH₃b-110 -CO₂Me b-111 -CH₂CO₂Me b-112 -CH(CO₂Me)CH₃b-113 -CH₂CO₂CH₂CF₃b-114 -CO₂CH₂CF₃b-115 -CH₂CO₂CH(CF₃)₂b-116 -CH₂COCF₃b-117 -COCF₃b-118 -CN -OCF₃ H H -CN b-119 -CH₂CN b-120 -CF₃b-121 -CH₂CF₃b-122 -CONHMe b-123 -CH₂CONHCH₃b-124 -CH₂COCH₃b-125 -COCH₃b-126 -Cl b-127 -Br b-128 -CH₂Cl b-129 -CH₂CH₂Cl b-130 -CHCHCl b-131 -CH(CH₃)₂b-132 -CH=CHCH₃b-133 -CN -Cl H -CO₂Me -CH₂CO₂Me b-134 -CF₃b-135 -OCF₃b-136 -CF₃ -CN b-137 -OCF₃b-138 -SOCF₃ Embodiment 6: Synthesis of compounds c-1 to c-349 by using a method FMethod F:
[0096]
[0097] Taking a compound c-27 for example, a specific synthesis process was as follows: S1: 6-chloro-2-cyano-5-(2'2-diethoxy)-8-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-ethyl formate
[0098] Under the protection of nitrogen, a DMF mixture of 5-amino-1H-pyrazole-3-cyano (1.0 mmol), 2-bromo-2-(2-bromo-6-chloro-4-trifluoromethylphenyl)diethyl malate (1.0 mmol), cuprous iodide (0.2 mmol) and caesium carbonate (0.5 mmol) was stirred at 100°C for 24 hours. The mixture was cooled to room temperature, and then filtered. The filtrate was concentrated in vacuum, and the residues were purified by column chromatography to obtain the target compound 6-chloro-2-cyano-5-(2'2-diethoxy)-8-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-ethyl formate (yield: 30%). S2: 6-chloro-2-cyano-5-(2'2-diethoxy)-8-trifluoromethyl-3-trifluoromethylsulfinyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-ethyl formate
[0099] Under the protection of nitrogen, an anhydrous toluene mixture of 6-chloro-2-cyano-5-(2'2-diethoxy)-8-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-ethyl formate (0.2 mmol), trifluoromethylsulfinyl chloride (0.5 mmol) and dimethylamine p-toluenesulfonate was stirred and heated at 100°C for 24 hours. The mixture was cooled to room temperature, and then concentrated in vacuum, and the residues were purified by column chromatography to obtain the target compound 6-chloro-2-cyano-5-(2'2-diethoxy)-8-trifluoromethyl-3-trifluoromethylsulfinyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-ethyl formate, wherein the yield was 82%. S3: 2-(6-chloro-2-cyano-5-(2'2-diethoxy)-8-trifluoromethyl-3-trifluoromethylsulfinyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-yl)-acetic acid
[0100] 6-chloro-2-cyano-5-(2'2-diethoxy)-8-trifluoromethyl-3-trifluoromethylsulfinyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-ethyl formate (1.0 mmol) was dissolved in 5 ml of dioxane, and then 10 ml of IN HCl was added thereto. The mixture was heated and refluxed for 5 hours, and then ethyl acetate was added for extraction. Then the mixture was concentrated in vacuum, and the residues were purified by column chromatography to obtain the target compound 2-(6-chloro-2-cyano-5-(2'2-diethoxy)-8-trifluoromethyl-3-trifluoromethylsulfiny1-4,5-dihydropyrazole[1,5-α]quinazoline-5-yl)-acetic acid, wherein the yield was 78%.
[0101] The compounds c-1 to c-349 were synthesized with reference to the method of the compound c-27 (wherein cyclization steps also included similar cyclization methods mentioned in documents such as WO2007144669 ) with a difference that different raw materials were selected for reaction according to different target compounds, or the compounds were derived from the synthesized target products through hydrolysis, simple esterification or amidation or reduction-oxidation. Specific compounds were as shown in Table 9. Table 9: Compound Structure with a General Formula Shown in Formula (c) Structural formula Compound R¹ R² R³ R⁴ R⁵ R⁶c-1 -CN -CN H -CO₂Me -CH₂CO₂Me c-2 -CF₃c-3 -OCF₃c 4 -CF₃ -CN c-5 -CF₃c-6 -OCF₃c-7 -SOCF₃c-8 H -CH₂CO₂Me c-9 -CH₂CN c-10 -CH₂CONH₂c-11 -CH₂CONHCH₃c-12 -CH₂CH₂OH c-13 -CH(CO₂Me)CH₃c-14 -CH₃-CO₂Me c-15 -Ac General c-16 -CH₂CH₂Cl -CO₂Me 3-Cl, and formula c-17 -CH₂CO₂Et 5-CF₃(c) c-18 -COOH c-19 -CH₂CO₂CH₂CF₃c-20 -CN -SOCF₃ -CH₂CO₂CH₂CHF₂c-21 -CH₂CO₂CH(CF₃)₂c-22 -CH₂CO₂C(CH₃)₂CF₃c-23 -CH₂CO₂C(CF₃)₂CH₃c-24 -CH₂CO₂C(CF₃)OCH₃c-25 H -CO₂Et -CH₂CO₂Me c-26 -CH₂CO₂Et c-27 -CH₂CO₂H c-28 -CH₂CO₂CH₂CF₃c-29 -CH₂CO₂CH₂CHF₂c-30 -CH₂CO₂CH(CF₃)₂c-31 -CH₂CO₂C(CH₃)₂CF₃c-32 -CH₂CO₂C(CF₃)₂CH₃c-33 -CH₂CO₂C(CF₃)OCH₃c-34 -COCF₃ -CH₂COCF₃c-35 -CH₂COCH₃c-36 -CH₂Ph c-37 -CH(CH₃)₂c-38 -CH₂CO₂Me c-39 -COCH₃c-40 -CO₂Me c-41 -CH₂Br c-42 -CH₂CH₂Cl c-43 -CN c-44 -CH₂CN c-45 -CF₃c-46 -CH₂CF₃c-47 -COCH₃ -CH₂COCF₃c-48 -CH₂COCH₃c-49 -CH₂Ph c-50 -CH(CH₃)₂c-51 -CH₂CO₂Me c-52 -COCH₃c-53 -CO₂Me c-54 -CH₂Br c-55 -CH₂CH₂Cl c-56 -CN c-57 -CH₂CN c-58 -CF₃c-59 -CH₂CF₃c-60 -CO₂Me -CO₂Me c-61 -CH₂Ph c-62 -CH₃c-63 -CH₂COCH₃c-64 -CH₂Br c-65 -CH₂CH₂Cl c-66 -Br c-67 -CN c-68 -CF₃c-69 -CH₂CF₃c-70 -CH₂COCF₃c-71 -CH₂COCH₃c-72 -COCH₃c-73 -CO₂Me c-74 -CH₂CO₂Me c-75 -CH₂Ph c-76 -CH₃c-77 -Br c-78 -CONHMe -CH₂Br c-79 -CH₂CH₂Cl c-80 -CN c-81 -CH₂CN c-82 -CF₃c-83 -CH₂CF₃c-84 -CH₂COCF₃c-85 -COCF₃c-86 -F -F c-87 -Cl -Cl c-88 -CH₂Br c-89 -CH₂Cl c-90 -CN c-91 -CH₂CN c-92 -CF₃c-93 -CH₂CF₃c-94 -Br -Br c-95 -CH₂Cl c-96 -CH₂COCF₃c-97 -COCF₃c-98 -CH₃ -CH₃c-99 -CH₂CH₃c-100 -CN -CN c-101 -CH₂CN c-102 -CF₃c-103 -CH₂CF₃c-104 -CH₂Cl c-105 -CH₂CO₂Me c-106 -COCH₃c-107 -COCF₃c-108 -CH₂COCF₃c-109 -CF₃ -CF₃c-110 -CH₂CF₃c-111 -CH₂CN c-112 -CH₂Cl c-113 -CH₂CO₂Me c-114 -COCH₃c-115 -COCF₃c-116 -CH₂COCF₃c-117 -CO₂nBu -CH₂CO₂nBu c-118 -SOCH₂CH₃-CO₂Me -CH₂CO₂Me c-119 -CO₂Me c-120 -CH₂CO₂Me c-121 -C(CO₂Me)CH₃c-122 -CH₂CO₂CH₂CF₃c-123 -CO₂CH₂CF₃c-124 -CH₂CO₂CH(CF₃)₂c-125 -CH₂COCF₃c-126 -COCF₃c-127 -CN c-128 -CN -SOCF₃ H H -CH₂CN c-129 -CF₃c-130 -CH₂CF₃c-131 -CONHMe c-132 -CH₂CONHCH₃c-133 -CH₂COCH₃c-134 -COCH₃c-135 -Cl c-136 -Br c-137 -CH₂Cl c-138 -CH₂CH₂Cl c-139 -CH=CHCl c-140 -CH(CH₃)₂c-141 -CH=CHCH₃c-142 -CO₂Me c-143 -CH₂CO₂Me c-144 -C(CO₂Me)CH₃c-145 -CH₂CO₂CH₂CF₃c-146 -CO₂CH₂CF₃c-147 -CH₂CO₂CH(CF₃)₂c-148 -CH₂COCF₃c-149 -COCF₃c-150 -CN c-151 -CH₂CN c-152 -CF₃c-153 -CF₃ -SOCF₃ H H -CH₂CF₃c-154 -CONHMe c-155 -CH₂CONHCH₃c-156 -CH₂COCH₃c-157 -COCH₃c-158 -Cl c-159 -Br c-160 -CH₂Cl c-161 -CH₂CH₂Cl c-162 -CH=CHCl c-163 -CH(CH₃)₂c-164 -CH=CHCH₃c-165 -CN -OCF₃ H H -CO₂Me c-166 -CH₂CO₂Me c-167 -C(CO₂Me)CH₃c-168 -CH₂CO₂CH₂CF₃c-169 -CO₂CH₂CF₃c-170 -CH₂CO₂CH(CF₃)₂c-171 -CH₂COCF₃c-172 -COCF₃c-173 -CN c-174 -CH₂CN c-175 -CF₃ c-176 -CH₂CF₃ c-177 -CONHMe c-178 -CH₂CONHCH₃ c-179 -CH₂COCH₃ c-180 -COCH₃ c-181 -Cl c-182 -Br c-183 -CH₂Cl c-184 -CH₂CH₂Cl c-185 -CH=CHCl c-186 -CH(CH₃)₂ c-187 -CH=CHCH₃ c-188 -CO₂Me -CH₂CO₂Me 3-Br, and 5-CF₃ c-189 -CH₂CO₂Et c-190 -CH₂CO₂CH₂CF₃ c-191 -CH₂CO₂CH₂CHF₂ c-192 -CO₂Et -CH₂CO₂Me c-193 -CH₂CO₂Et c-194 -CO₂Me -CH₂CO₂Me 3-CF₃, and 5-CF₃ c-195 -CH₂CO₂Et c-196 -CH₂CO₂CH₂CF₃ c-197 -CH₂CO₂CH₂CHF₂ c-198 -CN -SOCF₃ H -CO₂Et -CH₂CO₂Me c-199 -CH₂CO₂Et c-200 -CO₂Me -CH₂CO₂Me 3-Me, and 5-CF₃ c-201 -CH₂CO₂Et c-202 -CH₂CO₂CH₂CF₃ c-203 -CH₂CO₂CH₂CHF₂ c-204 -CO₂Et -CH₂CO₂Me c-205 -CH₂CO₂Et c-206 -CO₂Me -CH₂CO₂Me 3-CN, and 5-CF₃ c-207 -CH₂CO₂Et c-208 -CH₂CO₂CH₂CF₃ c-209 -CH₂CO₂CH₂CHF₂c-210 -CO₂Et -CH₂CO₂Me c-211 -CH₂CO₂Et c-212 -CO₂Me -CH₂CO₂Me 3-CO₂Me, and 5-CF₃ c-213 -CH₂CO₂Et c-214 -CH₂CO₂CH₂CF₃ c-215 -CH₂CO₂CH₂CHF₂ c-216 -CO₂Et -CH₂CO₂Me c-217 -CH₂CO₂Et c-218 -CO₂Me -CH₂CO₂Me 3-NO₂, and 5-CF₃ c-219 -CH₂CO₂Et c-220 -CH₂CO₂CH₂CF₃ c-221 -CH₂CO₂CH₂CHF₂ c-222 -CO₂Et -CH₂CO₂Me c-223 -CH₂CO₂Et c-224 -CO₂Me -CH₂CO₂Me 3-Cl, and 5-OCF₃ c-225 -CH₂CO₂Et c-226 -CH₂CO₂CH₂CF₃ c-227 -CH₂CO₂CH₂CHF₂ c-228 -CO₂Et -CH₂CO₂Me c-229 -CH₂CO₂Et c-230 -CO₂Me -CH₂CO₂Me 3-Br, and 5-OCF₃ c-231 -CH₂CO₂Et c-232 -CH₂CO₂CH₂CF₃ c-233 -CN -SOCF₃ H -CH₂CO₂CH₂CHF₂ c-234 -CO₂Et -CH₂CO₂Me c-235 -CH₂CO₂Et c-236 -CO₂Me -CH₂CO₂Me 3-Me, and 5-OCF₃ c-237 -CH₂CO₂Et c-238 -CH₂CO₂CH₂CF₃ c-239 -CH₂CO₂CH₂CHF₂ c-240 -CO₂Et -CH₂CO₂Me c-241 -CH₂CO₂Et c-242 -CO₂Me -CH₂CO₂Me c-243 -CH₂CO₂Et c-244 -CH₂CO₂CH₂CF₃ 3-CN, and 5-OCF₃ c-245 -CH₂CO₂CH₂CHF₂ c-246 -CO₂Et -CH₂CO₂Me c-247 -CH₂CO₂Et c-248 -CO₂Me -CH₂CO₂Me 3-CH₃, and 5-OCF₃ c-249 -CH₂CO₂Et c-250 -CH₂CO₂CH₂CF₃ c-251 -CH₂CO₂CH₂CHF₂ c-252 -CO₂Et -CH₂CO₂Me c-253 -CH₂CO₂Et c-254 -CO₂Me -CH₂CO₂Me 3-CO₂Me, and 5-OCF₃ c-255 -CH₂CO₂Et c-256 -CH₂CO₂CH₂CF₃ c-257 -CH₂CO₂CH₂CHF₂ c-258 -CO₂Et -CH₂CO₂Me c-259 -CH₂CO₂Et c-260 -CO₂Me -CH₂CO₂Me 3-NO₂, and 5-OCF₃ c-261 -CH₂CO₂Et c-262 -CH₂CO₂CH₂CF₃ c-263 -CH₂CO₂CH₂CHF₂ c-264 -CO₂Et -CH₂CO₂Me c-265 -CH₂CO₂Et c-266 -CN -SOCF₃ H -CO₂Me -CH₂CO₂Me 3-Cl, and 5-NO₂ c-267 -CH₂CO₂Et c-268 -CH₂CO₂CH₂CF₃ c-269 -CH₂CO₂CH₂CHF₂ c-270 -CO₂Et -CH₂CO₂Me c-271 -CH₂CO₂Et c-272 -CO₂Me -CH₂CO₂Me 3-Br, and 5-NO₂ c-273 -CH₂CO₂Et c-274 -CH₂CO₂CH₂CF₃ c-275 -CH₂CO₂CH₂CHF₂ c-276 -CO₂Et -CH₂CO₂Me c-277 -CH₂CO₂Et c-278 -CO₂Me -CH₂CO₂Me c-279 -CH₂CO₂Et 3-Me, and 5-NO₂ c-280 -CH₂CO₂CH₂CF₃ c-281 -CH₂CO₂CH₂CHF₂ c-282 -CO₂Et -CH₂CO₂Me c-283 -CH₂CO₂Et c-284 -CO₂Me -CH₂CO₂Me 3-CN, and 5-NO₂ c-285 -CH₂CO₂Et c-286 -CH₂CO₂CH₂CF₃ c-287 -CH₂CO₂CH₂CHF₂ c-288 -CO₂Et -CH₂CO₂Me c-289 -CH₂CO₂Et c-290 -CO₂Me -CH₂CO₂Me 3-CF₃, and 5-NO₂ c-291 -CH₂CO₂Et c-292 -CH₂CO₂CH₂CF₃ c-293 -CH₂CO₂CH₂CHF₂ c-294 -CO₂Et -CH₂CO₂Me c-295 -CH₂CO₂Et c-296 -CO₂Me -CH₂CO₂Me 3-CO₂Me, and 5-NO₂ c-297 -CH₂CO₂Et c-298 -CH₂CO₂CH₂CF₃ c-299 -CH₂CO₂CH₂CHF₂ c-300 -CO₂Et -CH₂CO₂Me c-301 -CH₂CO₂Et c-302 -CO₂Me -CH₂CO₂Me 3-NO₂, and 5-NO₂ c-303 -CH₂CO₂Et c-304 -CH₂CO₂CH₂CF₃ c-305 -CH₂CO₂CH₂CHF₂ c-306 -CO₂Et -CH₂CO₂Me c-307 -CH₂CO₂Et c-308 -CN -SOCF₃ H -CO₂Me -CH₂CO₂Me 3-Cl, and 5-Cl c-309 -CH₂CO₂Et c-310 -CH₂CO₂CH₂CF₃ c-311 -CH₂CO₂CH₂CHF₂ c-312 -CO₂Et -CH₂CO₂Me c-313 -CH₂CO₂Et c-314 -CO₂Me -CH₂CO₂Me 3-Br, and 5-Cl c-315 -CH₂CO₂Et c-316 -CH₂CO₂CH₂CF₃ c-317 -CH₂CO₂CH₂CHF₂ c-318 -CO₂Et -CH₂CO₂Me c-319 -CH₂CO₂Et c-320 -CO₂Me -CH₂CO₂Me 3-Me, and 5-Cl c-321 -CH₂CO₂Et c-322 -CH₂CO₂CH₂CF₃ c-323 -CH₂CO₂CH₂CHF₂ c-324 -CO₂Et -CH₂CO₂Me c-325 -CH₂CO₂Et c-326 -CO₂Me -CH₂CO₂Me 3-CN, and 5-Cl c-327 -CH₂CO₂Et c-328 -CH₂CO₂CH₂CF₃ c-329 -CH₂CO₂CH₂CHF₂ c-330 -CO₂Et -CH₂CO₂Me c-331 -CH₂CO₂Et c-332 -CO₂Me -CH₂CO₂Me 3-CF₃, and 5-Cl c-333 -CH₂CO₂Et c-334 -CH₂CO₂CH₂CF₃ c-335 -CH₂CO₂CH₂CHF₂ c-336 -CO₂Et -CH₂CO₂Me c-337 -CH₂CO₂Et c-338 -CO₂Me -CH₂CO₂Me 3-CO₂Me, and 5-Cl c-339 -CH₂CO₂Et c-340 -CH₂CO₂CH₂CF₃ c-341 -CH₂CO₂CH₂CHF₂ c-342 -CO₂Et -CH₂CO₂Me c-343 -CH₂CO₂Et c-344 -CO₂Me -CH₂CO₂Me 3-NO₂, and 5-Cl c-345 -CH₂CO₂Et c-346 -CH₂CO₂CH₂CF₃ c-347 -CH₂CO₂CH₂CHF₂ c-348 -CO₂Et -CH₂CO₂Me c-349 -CH₂CO₂Et Embodiment 7: Synthesis of compounds d-1 to d-142 by using a method GMethod G:
[0102]
[0103] Taking a compound d-12 for example, a specific synthesis process was as follows: S1: 9-chloro-2-cyano-3-cyclohexanethiol -5-(2'2-dimethoxy)-7-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-methyl formate (referring to document Synthetic Communications (2012) 42: 3472)
[0104] Under the protection of nitrogen, an anhydrous acetonitrile mixture of 9-chloro-2-cyano-5-(2'2-dimethoxy)-7-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-methyl formate (2.0 mmol, synthesized with a method similar to S1 of the compound c-27, with a yield of 26%), dicyclohexyl disulfide (1.0 mmol), ferric tribromide (0.5 mmol) and elemental iodine (0.5 mmol) was stirred at 85°C for 24 hours. The mixture was cooled to room temperature, and then concentrated in vacuum, and the residues were purified by column chromatography to obtain the target compound 9-chloro-2-cyano-3-cyclohexanethiol-5-(2'2-dimethoxy)-7-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-methyl formate (yield: 90%). S2: 9-chloro-2-cyano-3-cyclohexanesulfinyl-5-(2'2-dimethoxy)-7-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-methyl formate
[0105] 9-chloro-2-cyano-3-cyclohexanethiol-5-(2'2-dimethoxy)-7-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-methyl formate (1.0 mmol) was dissolved in anhydrous methylene chloride, and cooled to -15°C. Then, m-chloroperoxybenzoic acid (85%, 1.1 mmol) was added thereto, and the mixture was reacted at low temperature for 1 hour under stirring. The mixture was cooled to room temperature, added with an aqueous solution of sodium hydrogen carbonate, extracted with methylene chloride, and concentrated in vacuum. The residues were purified by column chromatography to obtain the target compound 9-chloro-2-cyano-3-cyclohexanesulfinyl-5-(2'2-dimethoxy)-7-trifluoromethyl-4,5-dihydropyrazole[1,5-α]quinazoline-5-methyl formate, wherien the yield was 97%.
[0106] The compounds d-1 to d-142 were synthesized with reference to the method of the compound d-12 (wherein cyclization steps also included similar cyclization methods mentioned in documents such as Tetrahedron Letters (2015) 56: 1367; WO2016046404 ; Synthetic Communications (2015) 45: 2426; Tetrahedron Letters (2014) 55: 4997; and WO2007149907 ), with a difference that different raw materials were selected for reaction according to different target compounds, or the compounds were derived from the synthesized target products through hydrolysis, simple esterification or amidation or reduction-oxidation. Specific compounds were as shown in Table 10. Table 10: Compound Structure with a General Formula Shown in Formula (d) Structural formula Compound R¹ R² R³ R⁴ R⁵ R⁶ General formula (d) d-1 -CN -CF₃ H -CO₂Me -CH₂CO₂Me 4-CF₃, and 6-Cl d-2 -Br d-3 -OCF₃d-4 -Cl d-5 -CF₃ -CF₃d-6 -OCF₃d-7 -CN d-8 -COCH₃ -SOCF₃ H -CO₂Me -CH₂CO₂Me d-9 -CH₂NH₂d-10 -CN -SOPh d-11 -SOCH₂Ph d-12 -SOC₆H₁₃ d-13 -SOCH₃ d-14 -SOCH₂CH₃d-15
[0107]
[0108] The compounds e-1 to e-24 were synthesized with the methods of the compound series c and d (wherein cyclization steps also included similar cyclization methods mentioned in documents such as WO2016046404 ; WO2013174822 ; Synthetic Communications (2015) 45: 2426; Tetrahedron Letters (2014) 55: 4997; and WO2007149907 ), with a difference that different raw materials were selected for reaction according to different target compounds, or the compounds were derived from the synthesized target products through hydrolysis, simple esterification or amidation or reduction-oxidation. Specific compounds were as shown in Table 11. Table 11: Compound Structure with a General Formula Shown in Formula (e) Structural formula Compound R¹ R² R³ R⁴ R⁵ R⁶ General formula (e) e-1 -CN -SOCF₃ H -CO₂Me -CH₂CO₂Me 3-Cl, and 6-CF₃e-2 -CH₂CO₂Et e-3 -CH₂CO₂CH₂CF₃e-4 -CH₂CO₂CH₂CHF₂e-5 -CO₂Et -CH₂CO₂Et e-6 -CH₂CO₂Me e-7 -CN -SOCF₃ H -CO₂Me -CH₂CO₂Me 3-Cl, and 4-CF₃e-8 -CH₂CO₂Et e-9 -CH₂CO₂CH₂CF₃e-10 -CH₂CO₂CH₂CHF₂e-11 -CO₂Et -CH₂CO₂Et e-12 -CH₂CO₂Me e-13 -CN -SOCF₃ H -CO₂Me -CH₂CO₂Me 5-Cl, and 6-CF₃e-14 -CH₂CO₂Et e-15 -CH₂CO₂CH₂CF₃e-16 -CH₂CO₂CH₂CHF₂e-17 -CO₂Et -CH₂CO₂Et e-18 -CH₂CO₂Me e-19 -CN -SOCF₃ H -CO₂Me -CH₂CO₂Me 4-Cl, and 5-CF₃e-20 -CH₂CO₂Et e-21 -CH₂CO₂CH₂CF₃e-22 -CH₂CO₂CH₂CHF₂e-23 -CO₂Et -CH₂CO₂Et e-24 -CH₂CO₂Me
[0109] Hydrogen spectrum and mass spectrum data of nuclear magnetic resonance of some compounds shown in the general formula (a) of Table 7 were shown in Table 12. Table 12: Hydrogen Spectrum and Mass Spectrum Data of Nuclear Magnetic Resonance of Some Compounds Shown in General Formula (a) Compound ¹H-NMR(600 MHz) MS (ESI) a-1 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 3.74 (s, 3H), 3.60(s, 3H), 3.33-3.25(m, 2H). [M+H]⁺ 512.1 a-2 ¹H NMR (600 MHz, CDCl₃) δ 8.43 (s, 1H), 7.60 (s, 1H), 7.20 (brs, 1H), 3.61(s, 3H), 3.31-3.26(m, 2H). [M+H]⁺ 479.0 a-3 ¹H NMR (600 MHz, CDCl₃) δ 8.36 (s, 1H), 7.50 (s, 1H), 7.49 (brs, 1H), 6.98 (brs, 2H), 3.74(s, 3H), 3.33-3.25(m, 2H). [M+H]⁺ 497.1 a-4 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.55 (s, 1H), 7.49 (brs, 1H), 7.24 (brs, 1H), 3.74(s, 3H), 3.33-3.25(m, 2H), 2.80(s, 3H). [M+H]⁺ 510.9 a-5 ¹H NMR (600 MHz, CDCl₃) δ 8.37 (s, 1H), 7.45 (s, 1H), 7.39 (brs, 1H), 4.34 (brs, 1H), 3.80(dd, J = 6.4, 2.0 Hz, 2H), 3.74(s, 3H), 3.34-3.25(dd, J = 6.4, 2.0 Hz, 2H). [M+H]⁺ 484.2 a-6 ¹H NMR (600 MHz, CDCl₃) δ 8.37 (s, 1H), 7.45 (s, 1H), 7.39 (brs, 1H), 3.84 (s, 3H), 3.74(s, 3H), 3.25(dd, J = 5.4, 1.80 Hz, 1H), 1.14(d, J = 8.0, 3H). [M+H]⁺ 526.0 a-7 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 3.74 (s, 3H), 3.60(s, 3H), 3.33-3.25(m, 2H), 3.04 (s, 3H). [M+H]⁺ 526.1 a-8 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 3.74 (s, 3H), 3.60(s, 3H), 3.63-3.55(m, 2H), 3.53-3.48(m, 2H), 3.33-3.25(m, 2H). [M+H]⁺ 574.1 a-9 ¹H NMR (600 MHz, CDCl₃) δ 8.37 (s, 1H), 7.45 (s, 1H), 7.39 (brs, 1H), 3.84 (dd, J = 5.4, 1.80 Hz, 2H), 3.74(s, 3H), 3.34-3.25(m, 2H), 1.14(t, J = 8.0, 3H). [M+H]⁺ 526.0 a-10 ¹H NMR (600 MHz, CDCl₃) δ 8.36 (s, 1H), 8.15 (s, 1H), 7.54 (t, J = 2.3 Hz, 1H), 4.78 - 4.63 (m, 2H), 4.49 - 4.29 (m, 2H), 3.82 (d, J = 4.8 Hz, 3H), 3.71 - 3.46 (m, 2H). [M+H]⁺ 580.0 a-11 ¹H NMR (600 MHz, CDCl₃) δ 8.34 (s, 1H), 7.59 (s, 1H), 6.92 (s, 1H), 5.87 (tdt, J = 54.7, 24.2, 3.9 Hz, 1H), 4.35 - 4.12 (m, 2H), 3.83 (d, J = 6.8 Hz, 3H), 3.63 - 3.35 (m, 2H). [M+H]⁺ 562.1 a-12 ¹H NMR (600 MHz, CDCl₃) δ 8.16 (s, 1H), 7.61 (s, 1H), 6.95 (s, 1H), 5.69 - 5.59 (m, 1H), 3.85 (d, J = 21.5 Hz, 3H), 3.81 - 3.62 (m, 2H). [M+H]⁺ 648.2 a-14 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (d, J = 1.8 Hz, 1H), 7.60 (d, J = 1.3 Hz, 1H), 6.87 (s, 1H), 3.83 (s, 3H), 3.71 - 3.50 (m, 2H), 1.87 (s, 1H). [M+H]⁺ 662.2 a-16 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 7.23-7.19(m, 5H), 3.74 (s, 3H), 3.33-3.25(m, 2H). [M+H]⁺ 530.1 a-17 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 3.74 (s, 3H), 3.33-3.25(m, 2H), 2.10 (s, 3H). [M+H]⁺ 496.0 a-18 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 3.72 (s, 3H), 3.13-3.05(m, 2H). [M+H]⁺ 531.9 a-19 H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 3.68 (s, 3H), 3.03-2.95(m, 2H). [M+H]⁺ 521.9 a-20 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 3.72 (s, 3H), 3.10-3.04(m, 2H). [M+H]⁺ 549.9 a-21 ¹H NMR (600 MHz, CDCl₃) δ 8.07 (S, 1H), 7.57 (S, 1H), 7.40 (s, 1H), 3.80 (d, J = 16.4 Hz, 3H), 3.61 (d, J = 31.8 Hz, 3H), 3.51 - 3.40 (m, 1H), 3.46 - 3.29 (m, 1H), 3.20 - 2.98 (m, 2H), 1.38 - 1.29 (m, 3H). [M+H]⁺ 472.0 a-22 ¹H NMR (600 MHz, CDCl₃) δ8.10 (m, 1H), 7.57 (s, 1H), 7.27 (s, 1H), 4.38 - 4.21 (m, 2H), 4.15 - 4.00 (m, 2H), 3.69 - 3.30 (m, 2H), 1.25 (td, J = 7.1, 1.4 Hz, 3H), 1.17 (dt, J = 16.7, 7.1 Hz, 3H). [M+H]⁺ 540.0 a-26 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 3.33-3.25(m, 2H), 2.10 (s, 3H). [M+H]⁺534.0 a-27 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.55 (s, 1H), 7.44 (brs, 1H), 7.23-7.19(m, 5H), 3.33-3.25(m, 2H). [M+H]⁺ 568.1 a-28 ¹H NMR (600 MHz, CDCl₃) δ 8.38 (s, 1H), 7.53 (s, 1H), 7.45 (brs, 1H), 3.74 (s, 3H), 3.33-3.25(m, 2H). [M+H]⁺ 550.1 a-29 ¹H NMR (600 MHz, CDCl₃) δ 8.36 (s, 1H), 7.49 (s, 1H), 7.46 (brs, 1H), 3.13-3.06(m, 2H). [M+H]⁺ 569.9 a-30 ¹H NMR (600 MHz, CDCl₃) δ 8.39 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 3.13-3.05(m, 2H). [M+H]⁺ 516.9 a-36 ¹H NMR (600 MHz, CDCl₃) δ 8.39 (s, 1H), 7.53 (s, 1H), 7.40 (brs, 1H), 3.13-3.05(m, 2H), 2.40 (s, 3H). [M+H]⁺ 506.0 a-37 ¹H NMR (600 MHz, CDCl₃) δ 8.37 (s, 1H), 7.46 (s, 1H), 7.39 (brs, 1H), 3.11-3.06(m, 2H), 2.38 (s, 3H). [M+H]⁺ 534.0 a-44 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H). [M+H]⁺ 449.9 a-45 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 3.13-3.05(m, 2H). [M+H]⁺ 507.8 a-47 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.55 (s, 1H), 7.45 (brs, 1H), 3.10-3.02(m, 2H). [M+H]⁺ 544.8 a-51 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H),1.37 (s, 6H). [M+H]⁺ 409.9 a-52 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H). [M+H]⁺ 432.0 a-53 ¹H NMR (600 MHz, CDCl₃) δ 8.33 (s, 1H), 7.50 (s, 1H), 7.40 (brs, 1H), 3.10-3.02(m, 2H). [M+H]⁺ 544.8 a-56 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 3.60(s, 3H), 3.33-3.25(m, 2H). [M+H]⁺ 479.1 a-57 ¹H NMR (600 MHz, CDCl₃) δ 8.36 (s, 1H), 7.58 (s, 1H), 7.47 (brs, 1H), 3.13-3.05(m, 2H). [M+H]⁺ 517.1 a-59 ¹H NMR (600 MHz, CDCl₃) δ 8.23 (s, 1H), 7.47 (s, 1H), 7.20 (brs, 1H), 3.00-2.92(m, 2H). [M+H]⁺ 488.8 a-62 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 3.60(s, 3H), 3.31-3.23(m, 2H). [M+H]⁺ 522.1 a-63 ¹H NMR (600 MHz, CDCl₃) δ 8.33 (s, 1H), 7.55 (s, 1H), 7.40 (brs, 1H), 3.14-3.05(m, 2H). [M+H]⁺ 559.9 a-64 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 4.74 (s, 1H), 3.60(s, 3H). [M+H]⁺ 440.1 a-65 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 4.74 (s, 1H), 3.60(s, 3H), 3.33-3.25(m, 2H). [M+H]⁺ 454.1 a-71 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.58 (s, 1H), 7.43 (brs, 1H), 4.75 (s, 1H). [M+H]⁺ 477.9 a-72 ¹H NMR (600 MHz, CDCl₃) δ 8.30 (s, 1H), 7.50 (s, 1H), 7.41 (brs, 1H), 4.65 (s, 1H). [M+H]⁺ 407.0 a-80 ¹H NMR (600 MHz, CDCl₃) δ 8.38 (s, 1H), 7.61 (s, 1H), 7.38 (brs, 1H), 4.81 (s, 1H). [M+H]⁺ 415.9 a-83 ¹H NMR (600 MHz, CDCl₃) δ 8.38 (s, 1H), 7.61 (s, 1H), 7.38 (brs, 1H), 4.81 (s, 1H), 3.63-3.55(m, 2H), 3.53-3.48(m, 2H). [M+H]⁺ 444.1 a-86 ¹H NMR (600 MHz, CDCl₃) δ 8.39 (s, 1H), 7.58 (s, 1H), 7.48 (brs, 1H), 6.23(d, J = 8.3 Hz, 1H), 6.02(dd, J = 1.3, 8.3 Hz, 1H), 4.81 (s, 1H). [M+H]⁺ 441.9 a-87 ¹H NMR (600 MHz, CDCl₃) δ 8.25 (s, 1H), 7.55 (s, 1H), 7.35 (brs, 1H), 4.74 (s, 1H), 3.60(s, 3H). [M+H]⁺ 483.1 a-88 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 4.74 (s, 1H), 3.60(s, 3H), 3.33-3.25(m, 2H). [M+H]⁺ 497.1 a-95 ¹H NMR (600 MHz, CDCl₃) δ 8.30 (s, 1H), 7.50 (s, 1H), 7.41 (brs, 1H), 4.65 (s, 1H). [M+H]⁺ 449.9 a-109 ¹H NMR (600 MHz, CDCl₃) δ 8.39 (s, 1H), 7.58 (s, 1H), 7.48 (brs, 1H), 6.23(d, J = 8.3 Hz, 1H), 6.02(dd, J = 1.3, 8.3 Hz, 1H), 4.81 (s, 1H), 1.63(d, J = 9.3 Hz, 3H). [M+H]⁺ 464.9 a-111 ¹H NMR (600 MHz, CDCl₃) δ 8.36 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 4.74 (s, 1H), 3.60(s, 3H), 3.32-3.25(m, 2H). [M+H]⁺ 422.1 a-118 ¹H NMR (600 MHz, CDCl₃) δ 8.30 (s, 1H), 7.50 (s, 1H), 7.41 (brs, 1H), 4.65 (s, 1H). [M+H]⁺ 375.1 a-122 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.65 (s, 1H), 7.50 (brs, 1H), 7.42 (brs, 1H), 4.65 (s, 1H), 2.82 (s, 3H). [M+H]⁺ 407.1 a-132 ¹H NMR (600 MHz, CDCl₃) δ 8.40 (s, 1H), 7.58 (s, 1H), 7.48 (brs, 1H), 6.23(d, J = 8.3 Hz, 1H), 6.02(dd, J = 1.3, 8.3 Hz, 1H), 4.81 (s, 1H), 1.63(d, J = 9.3 Hz, 3H). [M+H]⁺ 389.9 a-133 ¹H NMR (600 MHz, CDCl₃) δ 8.45 (s, 1H), 7.51 (s, 1H), 7.43 (brs, 1H), 3.76 (s, 3H), 3.61(s, 3H), 3.31-3.25(m, 2H). [M+H]⁺ 430.1 a-134 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 3.71 (s, 3H), 3.64(s, 3H), 3.32-3.26(m, 2H). [M+H]⁺ 464.1 a-136 ¹H NMR (600 MHz, CDCl₃) δ 8.30 (s, 1H), 7.55 (s, 1H), 7.47 (brs, 1H), 3.74 (s, 3H), 3.66(s, 3H), 3.35-3.29(m, 2H). [M+H]⁺ 464.1
[0110] Hydrogen spectrum and mass spectrum data of nuclear magnetic resonance of some compounds shown in the general formula (b) of Table 8 were shown in Table 13. Table 13: Hydrogen Spectrum and Mass Spectrum Data of Nuclear Magnetic Resonance of Some Compounds Shown in General Formula (b) Compound ¹H-NMR(600 MHz) MS (ESI) b-1 ¹H NMR (600 MHz, CDCl₃) δ 8.85 (s, 1H), 7.96 (s, 1H), 7.45 (brs, 1H), 3.74 (s, 3H), 3.60(s, 3H), 3.32-3.25(m, 2H). [M+H]⁺ 478.0 b-2 ¹H NMR (600 MHz, CDCl₃) δ 8.86 (s, 1H), 7.97 (s, 1H), 7.21 (brs, 1H), 3.62(s, 3H), 3.31-3.27(m, 2H). [M+H]⁺ 445.0 b-3 ¹H NMR (600 MHz, CDCl₃) δ 8.86 (s, 1H), 7.95 (s, 1H), 7.49 (brs, 1H), 6.28 (brs, 2H), 3.73(s, 3H), 3.33-3.26(m, 2H). [M+H]⁺ 463.1 b-4 ¹H NMR (600 MHz, CDCl₃) δ 8.85 (s, 1H), 7.95 (s, 1H), 7.50 (brs, 1H), 7.25 (brs, 1H), 3.73(s, 3H), 3.35-3.26(m, 2H), 2.81(s, 3H). [M+H]⁺ 476.9 b-5 ¹H NMR (600 MHz, CDCl₃) δ 8.87 (s, 1H), 7.85 (s, 1H), 7.49 (brs, 1H), 4.44 (brs, 1H), 3.81(dd, J = 6.4, 2.0 Hz, 2H), 3.77(s, 3H), 3.34-3.27(dd, J = 6.3, 2.1 Hz, 2H). [M+H]⁺ 450.1 b-6 ¹H NMR (600 MHz, CDCl₃) δ 8.87 (s, 1H), 7.95 (s, 1H), 7.37 (brs, 1H), 3.85 (s, 3H), 3.75(s, 3H), 3.25(dd, J = 5.5, 1.8 Hz, 1H), 1.15(d, J = 8.1, 3H). [M+H]⁺ 492.0 b-7 ¹H NMR (600 MHz, CDCl₃) δ 8.85 (s, 1H), 7.96 (s, 1H), 3.76 (s, 3H), 3.61(s, 3H), 3.35-3.28(m, 2H), 3.06 (s, 3H). [M+H]⁺ 492.0 b-8 ¹H NMR (600 MHz, CDCl₃) δ 8.86 (s, 1H), 7.98 (s, 1H), 3.75 (s, 3H), 3.59(s, 3H), 3.69-3.59(m, 2H), 3.54-3.48(m, 2H), 3.35-3.2(m, 2H). [M+H]⁺ 540.0 b-9 ¹H NMR (600 MHz, CDCl₃) δ 8.89 (s, 1H), 7.47 (s, 1H), 7.34 (brs, 1H), 3.83 (dd, J = 5.4, 1.8 Hz, 2H), 3.76(s, 3H), 3.35-3.26(m, 2H), 1.13(t, J= 8.0, 3H). [M+H]⁺ 492.0 b-10 ¹H NMR (600 MHz, CDCl₃) δ 8.86 (s, 1H), 8.15 (s, 1H), 7.54 (t, J = 2.5 Hz, 1H), 4.79 - 4.63 (m, 2H), 4.49 - 4.26 (m, 2H), 3.82 (d, J = 4.6 Hz, 3H), 3.72 - 3.46 (m, 2H). [M+H]⁺545.9 b-11 ¹H NMR (600 MHz, CDCl₃) δ 8.84 (s, 1H), 7.99 (s, 1H), 6.95 (s, 1H), 5.89 (tdt, J = 54.7, 24.2, 3.9 Hz, 1H), 4.36 - 4.13 (m, 2H), 3.83 (d, J = 6.9 Hz, 3H), 3.64-3.35 (m, 2H). [M+H]⁺ 528.0 b-12 ¹H NMR (600 MHz, CDCl₃) δ 8.96 (s, 1H), 7.67 (s, 1H), 6.96 (s, 1H), 5.68 - 5.57 (m, 1H), 3.85 (d, J = 22.5 Hz, 3H), 3.81 - 3.62 (m, 2H). [M+H]⁺ 613.9 b-14 ¹H NMR (600 MHz, CDCl₃) δ 8.95 (d, J = 1.8 Hz, 1H), 7.90 (d, J = 1.3 Hz, 1H), 6.97 (s, 1H), 3.85 (s, 3H), 3.72 - 3.54 (m, 2H), 1.86 (s, 1H). [M+H]⁺ 628.0 b-16 ¹H NMR (600 MHz, CDCl₃) δ 8.85 (s, 1H), 7.86 (s, 1H), 7.49 (brs, 1H), 7.22-7.18(m, 5H), 3.75 (s, 3H), 3.32-3.25(m, 2H). [M+H]⁺ 496.1 b-17 ¹H NMR (600 MHz, CDCl₃) δ 8.95 (s, 1H), 7.58 (s, 1H), 7.46 (brs, 1H), 3.75 (s, 3H), 3.31-3.23(m, 2H), 2.13 (s, 3H). [M+H]⁺ 462.0 b-18 ¹H NMR (600 MHz, CDCl₃) δ 8.95 (s, 1H), 7.86 (s, 1H), 7.44 (brs, 1H), 3.72 (s, 3H), 3.13-3.05(m, 2H). [M+H]⁺ 497.9 b-19 H NMR (600 MHz, CDCl₃) δ 8.86 (s, 1H), 7.77 (s, 1H), 7.51 (brs, 1H), 3.68 (s, 3H), 3.06-2.98(m, 2H). [M+H]⁺ 487.9 b-20 ¹H NMR (600 MHz, CDCl₃) δ 8.95 (s, 1H), 7.86 (s, 1H), 7.45 (brs, 1H), 3.73 (s, 3H), 3.17-3.11(m, 2H). [M+H]⁺ 515.9 b-21 ¹H NMR (600 MHz, CDCl₃) δ 8.97 (S, 1H), 7.97 (S, 1H), 7.48 (s, 1H), 3.81 (d, J = 16.5 Hz, 3H), 3.62 (d, J = 31.2 Hz, 3H), 3.50 - 3.40 (m, 1H), 3.45 - 3.29 (m, 1H), 3.31 - 3.08 (m, 2H), 1.39 - 1.30 (m, 3H). [M+H]⁺ 438.0 b-23 ¹H NMR (600 MHz, CDCl₃) δ 8.93 (s, 1H), 7.97 (d, J = 1.9 Hz, 1H), 6.86 (brs, 1H), 4.40 - 4.20 (m, 2H), 3.63 (s, 3H), 3.53 - 3.31 (m, 2H), 1.25 (td, J = 7.2, 3.0 Hz, 3H). [M+H]⁺ 491.1 b-25 ¹H NMR (600 MHz, CDCl₃) δ 8.93 (s, 1H), 7.97 (d, J= 1.9 Hz, 1H), 6.86 (brs, 1H), 4.30 - 4.10 (m, 2H). [M+H]⁺ 553.9 b-27 ¹H NMR (600 MHz, CDCl₃) δ 8.99 (s, 1H), 7.95 (s, 1H), 7.44 (brs, 1H), 7.23-7.19(m, 5H), 3.35-3.25(m, 2H). [M+H]⁺ 534.0 b-28 ¹H NMR (600 MHz, CDCl₃) δ 8.98 (s, 1H), 7.93 (s, 1H), 7.45 (brs, 1H), 3.75 (s, 3H), 3.33-3.25(m, 2H). [M+H]⁺ 515.9 b-30 ¹H NMR (600 MHz, CDCl₃) δ 8.99 (s, 1H), 7.86 (s, 1H), 7.46 (brs, 1H), 3.13-3.05(m, 2H). [M+H]⁺ 482.9 b-34 ¹H NMR (600 MHz, CDCl₃) δ 8.99 (s, 1H), 7.83 (s, 1H), 7.41 (brs, 1H), 3.14-3.06(m, 2H), 2.44 (s, 3H). [M+H]⁺ 481.9 b-37 ¹H NMR (600 MHz, CDCl₃) δ 8.97 (s, 1H), 7.86 (s, 1H), 7.39 (brs, 1H), 3.11-3.06(m, 2H), 2.9 (s, 3H). [M+H]⁺ 499.9 b-43 ¹H NMR (600 MHz, CDCl₃) δ 8.85 (s, 1H), 7.76 (s, 1H), 7.45 (brs, 1H), 5.45 (brs, 1H), 3.37 (s, 3H), 3.01-2.96(m, 2H). [M+H]⁺ 416.0 b-47 ¹H NMR (600 MHz, CDCl₃) δ 8.95 (s, 1H), 7.85 (s, 1H), 7.40 (brs, 1H), 3.18-3.09(m, 2H). [M+H]⁺ 420.9 b-48 ¹H NMR (600 MHz, CDCl₃) δ 8.95 (s, 1H), 7.85 (s, 1H), 7.40 (brs, 1H), 3.01-2.89(m, 2H). [M+H]⁺ 463.9 b-50 ¹H NMR (600 MHz, CDCl₃) δ 8.89 (s, 1H), 7.75 (s, 1H), 7.32 (brs, 1H), 2.91-2.79(m, 2H). [M+H]⁺ 535.8 b-54 ¹H NMR (600 MHz, CDCl₃) δ 8.85 (s, 1H), 7.70 (s, 1H), 7.30 (brs, 1H), 2.81-2.68(m, 2H). [M+H]⁺ 454.9 b-56 ¹H NMR (600 MHz, CDCl₃) δ 8.95 (s, 1H), 7.86 (s, 1H), 7.45 (brs, 1H), 3.61(s, 3H), 3.35-3.25(m, 2H). [M+H]⁺ 445.0 b-57 ¹H NMR (600 MHz, CDCl₃) δ 8.96 (s, 1H), 7.78 (s, 1H), 7.49 (brs, 1H), 3.14-3.05(m, 2H). [M+H]⁺ 482.9 b-59 ¹H NMR (600 MHz, CDCl₃) δ 8.93 (s, 1H), 7.77 (s, 1H), 7.21 (brs, 1H), 3.01-2.95(m, 2H). [M+H]⁺ 454.9 b-62 ¹H NMR (600 MHz, CDCl₃) δ 8.95 (s, 1H), 7.76 (s, 1H), 7.47 (brs, 1H), 3.61(s, 3H), 3.31-3.23(m, 2H). [M+H]⁺ 487.9 b-63 ¹H NMR (600 MHz, CDCl₃) δ 8.93 (s, 1H), 7.75 (s, 1H), 7.42 (brs, 1H), 3.15-3.07(m, 2H). [M+H]⁺ 525.9 b-66 ¹H NMR (600 MHz, CDCl₃) δ 8.87 (s, 1H), 7.95 (s, 1H), 7.37 (brs, 1H), 4.74 (s, 1H), 3.75(s, 3H), 3.25(dd, J = 5.5, 1.9 Hz, 1H), 1.15(d, J = 8.1, 3H). [M+H]⁺ 434.0 b-68 ¹H NMR (600 MHz, CDCl₃) δ 8.80 (s, 1H), 7.90 (s, 1H), 7.41 (brs, 1H), 4.65 (m, 1H), 4.47 (s, 2H), 2.95-2.77(m, 2H). [M+H]⁺ 487.9 b-70 ¹H NMR (600 MHz, CDCl₃) δ 8.81 (s, 1H), 7.91 (s, 1H), 7.42 (brs, 1H), 4.65 (m, 1H), 2.95-2.77(m, 2H). [M+H]⁺ 457.9 b-73 ¹H NMR (600 MHz, CDCl₃) δ 8.82 (s, 1H), 7.92 (s, 1H), 7.41 (brs, 1H), 4.65 (m, 1H), 2.93-2.73(m, 2H). [M+H]⁺ 386.9 b-80 ¹H NMR (600 MHz, CDCl₃) δ 8.89 (s, 1H), 7.95 (s, 1H), 7.42 (brs, 1H), 4.66 (m, 1H). [M+H]⁺ 381.9 b-86 ¹H NMR (600 MHz, CDCl₃) δ 8.89 (s, 1H), 7.98 (s, 1H), 7.49 (brs, 1H), 6.24(d, J = 8.4 Hz, 1H), 6.03(dd, J = 1.4, 8.4 Hz, 1H), 4.82 (s, 1H). [M+H]⁺ 388.0 b-87 ¹H NMR (600 MHz, CDCl₃) δ 8.85 (s, 1H), 7.95 (s, 1H), 7.41 (brs, 1H), 4.75 (s, 1H), 3.60(s, 3H). [M+H]⁺ 448.9 b-88 ¹H NMR (600 MHz, CDCl₃) δ 8.85 (s, 1H), 7.96 (s, 1H), 7.45 (brs, 1H), 4.76 (s, 1H), 3.61(s, 3H), 3.34-3.26(m, 2H). [M+H]⁺ 462.9 b-94 ¹H NMR (600 MHz, CDCl₃) δ 8.80 (s, 1H), 7.80 (s, 1H), 7.47 (brs, 1H), 4.66 (s, 1H). [M+H]⁺ 486.9 b-99 ¹H NMR (600 MHz, CDCl₃) δ 8.81 (s, 1H), 7.82 (s, 1H), 7.27 (brs, 1H), 5.27 (brs, 1H), 4.66 (s, 1H), 2.86 (s, 3H). [M+H]⁺ 447.9 b-104 ¹H NMR (600 MHz, CDCl₃) δ 8.80 (s, 1H), 7.78 (s, 1H), 7.38 (brs, 1H), 4.89 (s, 1H). [M+H]⁺ 468.8 b-111 ¹H NMR (600 MHz, CDCl₃) δ 8.86 (s, 1H), 7.86 (s, 1H), 7.41 (brs, 1H), 4.68 (s, 1H), 3.61(s, 3H), 3.33-3.28(m, 2H). [M+H]⁺ 388.0 b-116 ¹H NMR (600 MHz, CDCl₃) δ 8.83 (s, 1H), 8.01 (s, 1H), 7.39 (brs, 1H), 4.66 (m, 1H), 2.96-2.77(m, 2H). [M+H]⁺ 426.0 b-118 ¹H NMR (600 MHz, CDCl₃) δ 8.90 (s, 1H), 7.80 (s, 1H), 7.37 (brs, 1H), 4.65 (s, 1H). [M+H]⁺ 341.0 b-123 ¹H NMR (600 MHz, CDCl₃) δ 8.95 (s, 1H), 7.95 (s, 1H), 7.42 (brs, 1H), 7.36 (brs, 1H), 4.75 (s, 1H), 3.11-3.06(m, 2H), 2.82 (s, 3H). [M+H]⁺ 387.0 b-131 ¹H NMR (600 MHz, CDCl₃) δ 8.87 (s, 1H), 7.91 (s, 1H), 7.42 (brs, 1H), 4.75 (d, J = 8.1, 1H), 2.11-2.06(m, 1H), 0.92 (d, J = 10.1, 6H). [M+H]⁺ 358.0 b-134 ¹H NMR (600 MHz, CDCl₃) δ 8.85 (s, 1H), 7.96 (s, 1H), 7.45 (brs, 1H), 3.71 (s, 3H), 3.64(s, 3H), 3.32-3.26(m, 2H). [M+H]⁺ 430.1 b-135 ¹H NMR (600 MHz, CDCl₃) δ 8.89 (s, 1H), 7.96 (s, 1H), 7.43 (brs, 1H), 3.73 (s, 3H), 3.63(s, 3H), 3.31-3.27(m, 2H). [M+H]⁺ 446.0 b-136 ¹H NMR (600 MHz, CDCl₃) δ 8.90 (s, 1H), 7.95 (s, 1H), 7.47 (brs, 1H), 3.74 (s, 3H), 3.66(s, 3H), 3.35-3.29(m, 2H). [M+H]⁺ 430.0 b-138 ¹H NMR (600 MHz, CDCl₃) δ 8.87(s, 1H), 7.96 (s, 1H), 7.43 (brs, 1H), 3.72 (s, 3H), 3.66(s, 3H), 3.32-3.26(m, 2H). [M+H]⁺ 521.1
[0111] Hydrogen spectrum and mass spectrum data of nuclear magnetic resonance of some compounds shown in the general formula (c) of Table 9 were shown in Table 14. Table 14: Hydrogen Spectrum and Mass Spectrum Data of Nuclear Magnetic Resonance of Some Compounds Shown in General Formula (c) Compound ¹H-NMR(600 MHz) MS (ESI) c-2 ¹H NMR (600 MHz, CDCl₃) δ 8.14 (s, 1H), 7.57 (s, 1H), 7.05 (brs, 1H), 3.82 (s, 3H), 3.64 (s, 3H), 3.57 - 3.25 (m, 2H). [M+H]⁺ 497.1 c-4 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.60 (s, 1H), 7.05 (brs, 1H), 3.82 (s, 3H), 3.64 (s, 3H), 3.57 - 3.25 (m, 2H). [M+H]⁺ 497.2 c-7 ¹H NMR (600 MHz, CDCl₃) δ 8.20 (s, 1H), 7.60 (s, 1H), 7.05 (brs, 1H), 3.82 (s, 3H), 3.64 (s, 3H), 3.57 - 3.25 (m, 2H). [M+H]⁺ 587.9 c-8 ¹H NMR (600 MHz, CDCl₃) δ 8.13 (s, 1H), 7.58 (s, 1H), 7.28 (s, 1H), 3.82 (s, 3H), 3.66 (s, 3H), 3.55 - 3.23 (m, 2H). [M+H]⁺ 544.9¹H NMR (600 MHz, CDCl₃) δ 8.14 (s, 1H), 7.57 (s, 1H), 6.82 (s, 1H), 3.82 (s, 3H), 3.62 (s, 3H), 3.49 (d, J = 1.5 Hz, 2H). c-14 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.56 (s, 1H), 3.84 (s, 3H), 3.60(s, 3H), 3.33-3.25(m, 2H), 3.04 (s, 3H). [M+H]⁺ 559.1 c-15 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.56 (s, 1H), 3.84 (s, 3H), 3.60(s, 3H), 3.33-3.25(m, 2H), 2.12 (s, 3H). [M+H]⁺ 587.1 c-17 ¹H NMR (600 MHz, CDCl₃) δ 8.13 (d, J = 1.3 Hz, 1H), 7.57 (d, J = 1.2 Hz, 1H), 6.84 (s, 1H), 4.11 - 3.99 (m, 2H), 3.81 (s, 3H), 3.48 (d, J = 2.2 Hz, 2H), 1.16 (t, J = 7.1 Hz, 3H). [M+H]⁺ 559.0 c-18 ¹H NMR (600 MHz, CDCl₃) δ 8.12 (d, J = 1.8 Hz, 1H), 7.57 (d, J = 1.8 Hz, 1H), 7.03 (s, 1H), 3.81 (s, 3H), 3.59 - 3.33 (m, 2H), 2.27 (s, 1H). [M+H]⁺ 530.9 c-19 ¹H NMR (600 MHz, CDCl₃) δ 8.18 - 8.13 (m, 1H), 7.66 - 7.56 (m, 1H), 6.87 (s, 1H), 4.48 - 4.31 (m, 2H), 3.83 (d, J = 6.7 Hz, 3H), 3.70 - 3.48 (m, 2H). [M+H]⁺ 612.9 c-20 ¹H NMR (600 MHz, CDCl₃) δ 8.14 (dd, J = 4.8, 1.7 Hz, 1H), 7.59 (d, J = 0.3 Hz, 1H), 5.87 (tdt, J = 54.7, 23.8, 3.9 Hz, 1H), 4.33 - 4.14 (m, 2H), 3.83 (d, J = 7.3 Hz, 3H), 3.60 - 3.37 (m, 2H). [M+H]⁺ 595.0 c-21 ¹H NMR (600 MHz, CDCl₃) δ 8.16 (s, 1H), 7.61 (s, 1H), 6.95 (s, 1H), 5.69 - 5.59 (m, 1H), 3.85 (d, J = 21.5 Hz, 3H), 3.81 - 3.62 (m, 2H). [M+H]⁺ 680.9 c-25 ¹H NMR (600 MHz, CDCl₃) δ 8.13 (dd, J = 4.9, 1.8 Hz, 1H), 7.57 (d, J = 1.8 Hz, 1H), 6.86 (s, 1H), 4.40 - 4.20 (m, 2H), 3.63 (d, J = 23.3 Hz, 3H), 3.53 - 3.31 (m, 2H), 1.25 (td, J = 7.1, 3.0 Hz, 3H). [M+H]⁺ 559.0 c-26 ¹H NMR (600 MHz, CDCl₃) δ 8.15 - 8.10 (m, 1H), 7.57 (s, 1H), 7.27 (s, 1H), 4.38 - 4.21 (m, 2H), 4.15 - 4.00 (m, 2H), 3.69 - 3.30 (m, 2H), 1.25 (td, J = 7.1, 1.4 Hz, 3H), 1.17 (dt, J = 16.7, 7.1 Hz, 3H). [M+H]⁺ 572.9 c-28 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (dd, J = 4.5, 1.8 Hz, 1H), 7.65 - 7.57 (m, 1H), 6.84 (s, 1H), 4.48 - 4.22 (m, 4H), 3.71 - 3.46 (m, 2H), 1.25 (td, J = 7.1, 1.1 Hz, 3H). [M+H]⁺ 627.0 c-29 ¹H NMR (600 MHz, CDCl₃) δ 8.14 (dd, J = 4.1, 1.8 Hz, 1H), 7.59 (t, J = 2.4 Hz, 1H), 5.88 (tdt, J = 54.7, 26.4, 3.9 Hz, 1H), 4.43 - 4.16 (m, 4H), 3.60 - 3.35 (m, 2H), 1.25 (t, J = 7.1 Hz, 3H). [M+H]⁺ 609.0 c-34 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 3.33-3.25(m, 2H). [M+H]⁺ 620.9 c-36 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.55 (s, 1H), 7.44 (brs, 1H), 7.23-7.19(m, 5H), 3.33-3.25(m, 2H). [M+H]⁺ 601.0 c-39 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.55 (s, 1H), 7.44 (brs, 1H), 2.43(s, 3H). [M+H]⁺ 552.9 c-42 ¹H NMR (600 MHz, CDCl₃) δ 8.18 (s, 1H), 7.61 (s, 1H), 7.38 (brs, 1H), 3.63-3.55(m, 2H), 3.53-3.48(m, 2H). [M+H]⁺ 572.9 c-47 ¹H NMR (600 MHz, CDCl₃) δ 8.18 (s, 1H), 7.61 (s, 1H), 7.38 (brs, 1H), 3.53-3.48(m, 2H), 2.49 (s, 3H). [M+H]⁺ 566.9 c-53 ¹H NMR (600 MHz, CDCl₃) δ 8.20 (s, 1H), 7.61 (s, 1H), 7.38 (brs, 1H), 3.59 (s, 3H), 2.49 (s, 3H). [M+H]⁺ 514.9 c-54 ¹H NMR (600 MHz, CDCl₃) δ 8.18 (s, 1H), 7.61 (s, 1H), 7.38 (brs, 1H), 3.23-3.19(m, 2H), 2.49 (s, 3H). [M+H]⁺ 549.0 c-57 ¹H NMR (600 MHz, CDCl₃) δ 8.18 (s, 1H), 7.61 (s, 1H), 7.38 (brs, 1H), 3.13-3.08(m, 2H), 2.49 (s, 3H). [M+H]⁺ 495.9 c-61 ¹H NMR (600 MHz, CDCl₃) δ 8.13 (d, J = 1.3 Hz, 1H), 7.57 (d, J = 1.2 Hz, 1H), 7.35-7.19 (m, 5H), 6.84 (s, 1H), 3.81 (s, 3H), 3.53-3.38(m, 2H). [M+H]⁺ 563.1 c-64 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (d, J = 1.5 Hz, 1H), 7.57 (d, J = 1.2 Hz, 1H), 6.84 (s, 1H), 3.81 (s, 3H), 3.33-3.20(m, 2H). [M+H]⁺ 564.9 c-67 ¹H NMR (600 MHz, CDCl₃) δ 8.16 (d, J = 1.8 Hz, 1H), 7.57 (d, J = 1.2 Hz, 1H), 6.84 (s, 1H). [M+H]⁺ 497.9 c-72 ¹H NMR (600 MHz, CDCl₃) δ 8.06 (d, J = 2.0 Hz, 1H), 7.67 (d, J = 1.2 Hz, 1H), 7.54 (s, 1H), 6.84 (s, 1H), 2.94 (s, 3H), 2.46 (s, 3H). [M+H]⁺ 512.9 c-73 ¹H NMR (600 MHz, CDCl₃) δ 8.06 (d, J = 2.0 Hz, 1H), 7.67 (d, J = 1.2 Hz, 1H), 7.54 (s, 1H), 6.84 (s, 1H), 3.74 (s, 3H), 2.86 (s, 3H). [M+H]⁺ 530.0 c-77 ¹H NMR (600 MHz, CDCl₃) δ 8.06 (d, J = 2.0 Hz, 1H), 7.67 (d, J = 1.2 Hz, 1H), 7.54 (s, 1H), 6.84 (s, 1H), 2.86 (s, 3H). [M+H]⁺ 550.0 c-80 ¹H NMR (600 MHz, CDCl₃) δ 8.07 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 7.54 (s, 1H), 6.84 (s, 1H), 2.87 (s, 3H). [M+H]⁺ 496.9 c-84 ¹H NMR (600 MHz, CDCl₃) δ 8.06 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 7.54 (s, 1H), 6.84 (s, 1H), 3.13-3.08(m, 2H), 2.87 (s, 3H). [M+H]⁺ 581.9 c-86 ¹H NMR (600 MHz, CDCl₃) δ 8.07 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 6.84 (s, 1H). [M+H]⁺ 451.0 c-91 ¹H NMR (600 MHz, CDCl₃) δ 8.06 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 6.88 (s, 1H), 3.10-3.05(m, 2H). [M+H]⁺ 487.9 c-93 ¹H NMR (600 MHz, CDCl₃) δ 8.06 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 6.88 (s, 1H), 2.50-2.35(m, 2H). [M+H]⁺ 530.9 c-97 ¹H NMR (600 MHz, CDCl₃) δ 8.09 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 6.88 (s, 1H). [M+H]⁺ 588.8 c-98 ¹H NMR (600 MHz, CDCl₃) δ 8.19 (d, J = 2.0 Hz, 1H), 7.70 (d, J = 1.2 Hz, 1H), 6.88 (s, 1H), 1.38 (s, 6H). [M+H]⁺ 443.1 c-101 ¹H NMR (600 MHz, CDCl₃) δ 8.06 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 6.89 (s, 1H), 3.11-3.05(m, 2H). [M+H]⁺ 478.8 c-105 ¹H NMR (600 MHz, CDCl₃) δ 8.06 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 6.89 (s, 1H), 3.87 (s, 3H), 3.11-3.05(m, 2H). [M+H]⁺ 512.1 c-107 ¹H NMR (600 MHz, CDCl₃) δ 8.11 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 6.58 (s, 1H). [M+H]⁺ 535.9 c-110 ¹H NMR (600 MHz, CDCl₃) δ 8.07 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 6.89 (s, 1H), 2.91-2.75(m, 2H). [M+H]⁺ 565.1 c-111 ¹H NMR (600 MHz, CDCl₃) δ 8.08 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 6.95 (s, 1H), 3.11-2.95(m, 2H). [M+H]⁺ 520.9 c-114 ¹H NMR (600 MHz, CDCl₃) δ 8.10 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 6.95 (s, 1H), 2.45(s, 3H). [M+H]⁺ 524.9 c-117 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.59(s, 1H), 6.88 (s, 0H), 4.24 - 4.19 (m, 2H), 4.08 - 3.93 (m, 2H), 3.57 - 3.45 (m, 1H), 3.48 - 3.32 (m, 1H), 1.62 - 1.53 (m, 2H), 1.50 (dddd, J = 13.7, 6.9, 3.5, 2.3 Hz, 2H), 1.31 - 1.19 (m, 4H), 1.01 - 0.81 (m, 6H). [M+H]⁺ 629.0 c-118 ¹H NMR (600 MHz, CDCl₃) δ 8.18 (s, 1H), 7.57 (s, 1H), 7.45 (s, 1H), 3.80 (d, J = 16.4 Hz, 3H), 3.61 (d, J= 31.8 Hz, 3H), 3.51 - 3.40 (m, 1H), 3.46 - 3.29 (m, 1H), 3.20 - 2.98 (m, 2H), 1.38 - 1.29 (m, 3H). [M+H]⁺ 505.0 c-123 ¹H NMR (600 MHz, CDCl₃) δ 8.10 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.2 Hz, 1H), 6.95 (s, 1H), 4.89 (s, 1H), 4.45(dd, J = 4.8, 1.7 Hz, 2H). [M+H]⁺ 540.9 c-126 ¹H NMR (600 MHz, CDCl₃) δ 8.11 (d, J = 2.0 Hz, 1H), 7.69 (d, J = 1.2 Hz, 1H), 6.95 (s, 1H), 4.89 (s, 1H). [M+H]⁺ 510.9 c-128 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.69 (s, 1H), 6.95 (brs, 1H), 3.74 (d, J = 6.9 Hz, 1H), 2.33-2.25(m, 2H). [M+H]⁺ 453.9 c-135 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.61 (s, 1H), 6.39 (brs, 1H), 4.71 (s, 1H). [M+H]⁺ 448.9 c-139 ¹H NMR (600 MHz, CDCl₃) δ 8.16(s, 1H), 7.61 (s, 1H), 6.79 (brs, 1H), 6.59 (dd, J = 12.8, 8.9 Hz, 1H), 6.09 (d, J = 8.9 Hz, 1H), 4.71 (d, J = 6.9 Hz, 1H). [M+H]⁺ 474.9 c-149 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (d, J = 2.0 Hz, 1H), 7.69 (d, J = 1.2 Hz, 1H), 6.95 (s, 1H), 4.90 (s, 1H). [M+H]⁺ 553.9 c-150 ¹H NMR (600 MHz, CDCl₃) δ 8.20 (d, J = 2.0 Hz, 1H), 7.69 (d, J = 1.2 Hz, 1H), 6.35 (s, 1H), 4.91 (s, 1H). [M+H]⁺ 483.0 c-152 ¹H NMR (600 MHz, CDCl₃) δ 8.10 (d, J = 2.0 Hz, 1H), 7.65 (d, J = 1.2 Hz, 1H), 6.25 (s, 1H), 4.71 (s, 1H). [M+H]⁺ 525.9 c-154 ¹H NMR (600 MHz, CDCl₃) δ 8.10 (d, J = 2.0 Hz, 1H), 7.65 (d, J = 1.2 Hz, 1H), 6.75 (brs, 1H), 6.25 (brs, 1H), 4.70 (s, 1H), 2.93 (s, 3H). [M+H]⁺ 514.9 c-166 ¹H NMR (600 MHz, CDCl₃) δ 8.16 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.4 Hz, 1H), 6.89 (s, 1H), 3.87 (s, 3H), 3.11-3.05(m, 2H). [M+H]⁺ 455.0 c-169 ¹H NMR (600 MHz, CDCl₃) δ 8.06 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.4 Hz, 1H), 6.89 (s, 1H), 4.87 (d, J = 12.0 Hz, 1H), 4.67-4.60 (m, 2H), 3.11-3.05(m, 2H). [M+H]⁺ 523.0 c-173 ¹H NMR (600 MHz, CDCl₃) δ 8.05 (d, J = 2.0 Hz, 1H), 7.69 (d, J = 1.2 Hz, 1H), 6.95 (s, 1H), 4.91 (s, 1H). [M+H]⁺ 408.0 c-180 ¹H NMR (600 MHz, CDCl₃) δ 8.09 (d, J = 2.0 Hz, 1H), 7.68 (d, J = 1.4 Hz, 1H), 6.89 (s, 1H), 4.87 (d, J = 12.0 Hz, 1H), 3.11-3.05(m, 2H), 2.05(s, 2H). [M+H]⁺ 439.0 c-188 ¹H NMR (600 MHz, CDCl₃) δ 8.03 (s, 1H), 7.88 (s, 1H), 7.28 (s, 1H), 3.82 (s, 3H), 3.66 (s, 3H), 3.55 - 3.23 (m, 2H). [M+H]⁺ 589.0 c-196 ¹H NMR (600 MHz, CDCl₃) δ 8.08 - 8.13 (m, 1H), 7.86 - 7.84 (m, 1H), 6.87 (s, 1H), 4.48 - 4.31 (m, 2H), 3.83 (d, J = 6.7 Hz, 3H), 3.70 - 3.48 (m, 2H). [M+H]⁺ 647.0 c-203 ¹H NMR (600 MHz, CDCl₃) δ 8.04 (s, 1H), 7.89 (s, 1H), 5.87 (tdt, J = 54.7, 23.8, 3.9 Hz, 1H), 4.33 - 4.14 (m, 2H), 3.85 (d, J = 7.3 Hz, 3H), 3.60 - 3.37 (m, 2H). [M+H]⁺ 575.0 c-210 ¹H NMR (600 MHz, CDCl₃) δ 8.03 (dd, J= 4.9, 1.8 Hz, 1H), 7.87 (d, J= 1.8 Hz, 1H), 6.86 (s, 1H), 4.40 - 4.20 (m, 2H), 3.63 (d, J = 23.3 Hz, 3H), 3.53 - 3.31 (m, 2H), 1.25 (td, J = 7.1, 3.0 Hz, 3H). [M+H]⁺ 550.0 c-217 ¹H NMR (600 MHz, CDCl₃) δ 8.05 (m, 1H), 7.87 (s, 1H), 7.27 (s, 1H), 4.38 - 4.21 (m, 2H), 4.15 - 4.00 (m, 2H), 3.69 - 3.30 (m, 2H), 1.25 (td, J = 7.1, 1.4 Hz, 3H), 1.17 (dt, J = 16.7, 7.1 Hz, 3H). [M+H]⁺ 597.0 c-221 ¹H NMR (600 MHz, CDCl₃) δ 8.04 (dd, J = 4.8, 1.7 Hz, 1H), 7.59 (d, J = 0.3 Hz, 1H), 5.87 (tdt, J = 54.7, 23.8, 3.9 Hz, 1H), 4.33 - 4.14 (m, 2H), 3.83 (d, J = 7.3 Hz, 3H), 3.60 - 3.37 (m, 2H). [M+H]⁺ 606.0 c-224 ¹H NMR (600 MHz, CDCl₃) δ 7.33 (s, 1H), 6.86 (s, 1H), 5.28 (s, 1H), 3.82 (s, 3H), 3.66 (s, 3H), 3.55 - 3.23 (m, 2H). [M+H]⁺ 560.9 c-231 ¹H NMR (600 MHz, CDCl₃) δ 7.43 (d, J = 1.3 Hz, 1H), 6.92 (d, J = 1.2 Hz, 1H), 6.84 (s, 1H), 4.11 - 3.99 (m, 2H), 3.81 (s, 3H), 3.48 (d, J = 2.2 Hz, 2H), 1.16 (t, J = 7.1 Hz, 3H). [M+H]⁺ 618.9 c-238 ¹H NMR (600 MHz, CDCl₃) δ 6.88 (m, 1H), 6.76 (m, 1H), 6.57 (s, 1H), 4.48 - 4.31 (m, 2H), 3.83 (d, J = 6.7 Hz, 3H), 3.70 - 3.48 (m, 2H). [M+H]⁺ 609.0 c-245 ¹H NMR (600 MHz, CDCl₃) δ 7.75 (dd, J = 4.8, 1.7 Hz, 1H), 7.28 (d, J = 0.3 Hz, 1H), 5.87 (tdt, J = 54.7, 23.8, 3.9 Hz, 1H), 4.33 - 4.14 (m, 2H), 3.83 (d, J = 7.3 Hz, 3H), 3.60 - 3.37 (m, 2H). [M+H]⁺ 602.0 c-253 ¹H NMR (600 MHz, CDCl₃) δ 6.88 (m, 1H), 6.74 (s, 1H), 5.27 (s, 1H), 4.38 - 4.21 (m, 2H), 4.15 - 4.00 (m, 2H), 3.69 - 3.30 (m, 2H), 1.25 (td, J = 7.1, 1.4 Hz, 3H), 1.17 (dt, J = 16.7, 7.1 Hz, 3H). [M+H]⁺ 569.0 c-258 ¹H NMR (600 MHz, CDCl₃) δ 7.53 (s, 1H), 7.37 (s, 1H), 6.86 (s, 1H), 4.40 - 4.20 (m, 2H), 4.34 (dd, J = 23.3,7.8 Hz, 2H), 3.63 (s, 3H), 3.55 (s, 3H), 3.53 - 3.31 (m, 2H), 1.25 (td, J = 7.1, 3.0 Hz, 3H). [M+H]⁺ 599.0 c-262 ¹H NMR (600 MHz, CDCl₃) δ 7.77 (m, 1H), 7.36 (m, 1H), 6.87 (s, 1H), 4.48 - 4.31 (m, 2H), 3.83 (d, J = 6.7 Hz, 3H), 3.70 - 3.48 (m, 2H). [M+H]⁺ 640.0 c-266 ¹H NMR (600 MHz, CDCl₃) δ 8.23 (s, 1H), 7.88 (s, 1H), 7.58 (s, 1H), 3.82 (s, 3H), 3.66 (s, 3H), 3.55 - 3.23 (m, 2H). [M+H]⁺ 522.0 c-273 ¹H NMR (600 MHz, CDCl₃) δ 8.43 (s, 1H), 7.87 (s, 1H), 7.54 (s, 1H), 4.11 - 3.99 (m, 2H), 3.81 (s, 3H), 3.48 (d, J = 2.2 Hz, 2H), 1.16 (t, J = 7.1 Hz, 3H). [M+H]⁺ 579.9 c-286 ¹H NMR (600 MHz, CDCl₃) δ 8.55 (m, 1H), 8.26 (m, 1H), 6.87 (s, 1H), 4.48 - 4.31 (m, 2H), 3.83 (d, J = 6.7 Hz, 3H), 3.70 - 3.48 (m, 2H). [M+H]⁺ 581.0 c-306 ¹H NMR (600 MHz, CDCl₃) δ 8.49 (s, 1H), 8.27 (s, 1H), 6.86 (s, 1H), 4.40 - 4.20 (m, 2H), 3.63 (d, J = 23.3 Hz, 3H), 3.53 - 3.31 (m, 2H), 1.25 (td, J = 7.1, 3.0 Hz, 3H). [M+H]⁺ 549.0 c-317 ¹H NMR (600 MHz, CDCl₃) δ 7.59-7.46 (m, 2H), 5.87 (tdt, J = 54.7, 23.8, 3.9 Hz, 1H), 4.33 - 4.14 (m, 2H), 3.83 (d, J = 7.3 Hz, 3H), 3.60 - 3.37 (m, 2H). [M+H]⁺ 604.9 c-327 ¹H NMR (600 MHz, CDCl₃) δ 8.16 (d, J = 1.3 Hz, 1H), 7.50 (d, J = 1.2 Hz, 1H), 6.84 (s, 1H), 4.11 - 3.99 (m, 2H), 3.81 (s, 3H), 3.48 (d, J = 2.2 Hz, 2H), 1.16 (t, J= 7.1 Hz, 3H). [M+H]⁺ 516.0 c-346 ¹H NMR (600 MHz, CDCl₃) δ 8.58 - 8.43 (m, 2H), 6.87 (s, 1H), 4.48 - 4.31 (m, 2H), 3.83 (d, J = 6.7 Hz, 3H), 3.70 - 3.48 (m, 2H). [M+H]⁺ 589.9
[0112] Hydrogen spectrum and mass spectrum data of nuclear magnetic resonance of some compounds shown in the general formula (d) of Table 10 were shown in Table 15. Table 15: Hydrogen Spectrum and Mass Spectrum Data of Nuclear Magnetic Resonance of Some Compounds Shown in General Formula (d) Compound ¹H-NMR(600 MHz) MS (ESI) d-3 ¹H NMR (600 MHz, CDCl₃) δ 8.12 (s, 1H), 7.69 (s, 1H), 7.57 (brs, 1H), 3.75 (s, 3H), 3.67(s, 3H), 3.36-3.29(m, 2H). [M+H]⁺ 513.1 d-7 ¹H NMR (600 MHz, CDCl₃) δ 8.01 (s, 1H), 7.75 (s, 1H), 7.58 (brs, 1H), 3.71 (s, 3H), 3.70(s, 3H), 3.35-3.29(m, 2H). [M+H]⁺ 497.1 d-8 ¹H NMR (600 MHz, CDCl₃) δ 7.91 (s, 1H), 7.65 (s, 1H), 7.58 (brs, 1H), 3.74 (s, 3H), 3.60(s, 3H), 3.24-3.06(m, 2H), 2.11(s, 3H). [M+H]⁺ 562.0 d-9 ¹H NMR (600 MHz, CDCl₃) δ 8.61 (brs, 2H), 7.61 (s, 1H), 7.55 (s, 1H), 7.54 (brs, 1H), 4.34 (s, 2H), 3.73 (s, 3H), 3.61(s, 3H), 3.25-3.06(m, 2H). [M+H]⁺ 548.9 d-12 ¹H NMR (600 MHz, CDCl₃) δ 8.13 (s, 1H), 7.57 - 7.49 (m, 1H), 7.35 (t, J = 2.2 Hz, 1H), 3.80 (d, J = 18.3 Hz, 3H), 3.61 (d, J = 35.5 Hz, 3H), 3.56 - 3.37 (m, 2H), 2.92 (tt, J = 11.8, 3.4 Hz, 1H), 2.07 - 1.98 (m, 2H), 1.97 - 1.86 (m, 2H), 1.77 - 1.69 (m, 1H), 1.52 - 1.43 (m, 2H), 1.44 - 1.34 (m, 3H). [M+H]⁺ 559.1 d-13 ¹H NMR (600 MHz, CDCl₃) δ 8.12 (s, 1H), 7.55 (s, 1H), 7.24 (d, J = 153.3 Hz, 1H), 3.82 (d, J = 16.2 Hz, 3H), 3.62 (d, J = 15.5 Hz, 3H), 3.48 - 3.36 (m, 1H), 3.45 - 3.29 (m, 1H), 2.99 (d, J = 13.9 Hz, 3H). [M+H]⁺ 491.1 d-14 ¹H NMR (600 MHz, CDCl₃) δ 8.14 (s, 1H), 7.57 (s, 1H), 7.40 (s, 1H), 3.80 (d, J = 16.4 Hz, 3H), 3.61 (d, J = 31.8 Hz, 3H), 3.51 - 3.40 (m, 1H), 3.46 - 3.29 (m, 1H), 3.20 - 2.98 (m, 2H), 1.38 - 1.29 (m, 3H). [M+H]⁺ 505.0 d-15 ¹H NMR (600 MHz, CDCl₃) δ 8.71 - 8.63 (m, 1H), 8.11 (s, 1H), 8.01 (dd, J = 18.1, 7.8 Hz, 1H), 7.95 (qd, J = 7.5, 1.7 Hz, 1H), 7.60 (s, 1H), 7.52 - 7.48 (m, 1H), 7.43 (dddd, J = 20.7, 7.5, 4.7, 1.1 Hz, 1H), 4.26 - 4.07 (m, 2H), 4.07 - 4.0 1 (m, 1H), 3.69 (t, J = 6.8 Hz, 1H), 3.56 - 3.29 (m, 2H), 1.59 (dq, J = 14.0, 7.2 Hz, 1H), 1.54 - 1.44 (m, 2H), 1.31 - 1.21 (m, 3H), 1.14 (ddd, J = 25.1, 15.4, 8.0 Hz, 2H), 0.93 - 0.79 (m, 6H). [M+H]⁺ 638.0 d-17 ¹H NMR (600 MHz, CDCl₃) δ 8.07 (s, 1H), 7.78 (s, 2H), 7.52 (dt, J = 6.6, 2.3 Hz, 3H), 6.99 (s, 1H), 4.14 (ddt, J = 45.1, 10.8, 6.8 Hz, 2H), 3.85 (t, J = 6.8 Hz, 2H), 3.36 (s, 2H), 1.60 - 1.51 (m, 2H), 1.45 - 1.37 (m, 2H), 1.25 - 1.18 (m, 4H), 0.86 (td, J = 7.4, 1.9 Hz, 6H). [M+H]⁺ 671.0 d-18 ¹H NMR (600 MHz, CDCl₃) δ 8.07 (s, 1H), 7.66 (s, 2H), 7.55 - 7.48 (m, 1H), 7.38 - 7.30 (m, 3H), 4.22 - 4.10 (m, 2H), 4.09 - 3.99 (m, 1H), 3.84 (td, J = 6.8, 2.7 Hz, 1H), 3.44 (d, J = 17.2 Hz, 1H), 3.32 (dd, J = 17.3, 8.4 Hz, 1H), 2.41 (d, J = 7.6 Hz, 3H), 1.62 - 1.49 (m, 3H), 1.41 - 1.34 (m, 1H), 1.24 - 1.15 (m, 4H), 0.87 - 0.82 (m, 6H). [M+H]⁺ 651.2 d-20 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.46 (s, 1H), 7.45 (brs, 1H), 5.45 (brs, 2H), 3.62 (s, 3H), 3.13-3.05(m, 2H). [M+H]⁺ 529.9 d-24 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.47 (s, 1H), 7.45 (brs, 1H), 3.64 (s, 3H), 3.62 (s, 3H), 3.395 (dd, J = 3.4, 1.8 Hz, 1H), 1.12 (d, J = 2.8 Hz, 3H). [M+H]⁺ 559.0 d-27 ¹H NMR (600 MHz, CDCl₃) δ 8.16 (s, 1H), 7.42 (s, 1H), 7.54 (t, J = 2.3 Hz, 1H), 4.78 - 4.63 (m, 2H), 4.49 - 4.29 (m, 2H), 3.82 (d, J = 4.8 Hz, 3H), 3.71 - 3.46 (m, 2H). [M+H]⁺ 612.9 d-33 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.46 (s, 1H), 7.45 (brs, 1H), 3.74 (s, 3H), 3.33-3.25(m, 2H), 2.10 (s, 3H). [M+H]⁺ 529.0 d-34 ¹H NMR (600 MHz, CDCl₃) δ 8.16 (s, 1H), 7.44 (s, 1H), 7.46 (brs, 1H), 3.72 (s, 3H), 3.13-3.05(m, 2H). [M+H]⁺ 564.9 d-35 H NMR (600 MHz, CDCl₃) δ 8.18 (s, 1H), 7.43 (s, 1H), 7.45 (brs, 1H), 3.68 (s, 3H), 3.03-2.95(m, 2H). [M+H]⁺ 554.9 d-38 ¹H NMR (600 MHz, DMSO) δ 9.57 (d, J = 57.9 Hz, 1H), 8.18 (m, 2H), 4.29 - 4.16 (m, 2H), 3.55 - 3.46 (m, 2H), 1.15 (dt, J = 15.9, 7.1 Hz, 3H). [M+H]⁺ 545.0 d-42 ¹H NMR (600 MHz, CDCl₃) δ 8.16 (s, 1H), 7.41 (s, 1H), 6.95 (brs, 1H), 5.69 - 5.59 (m, 1H), 3.85 (d, J = 21.5 Hz, 3H), 3.81 - 3.62 (m, 2H). [M+H]⁺ 694.9 d-46 ¹H NMR (600 MHz, CDCl₃) δ 8.10 (s, 1H), 7.44 (s, 1H), 7.46 (brs, 1H), 3.13-3.06(m, 2H), 2.43 (s, 3H), 2.10 (s, 3H).. [M+H]⁺ 513.0 d-48 ¹H NMR (600 MHz, CDCl₃) δ 8.09 (s, 1H), 7.43 (s, 1H), 7.40 (brs, 1H), 3.13-3.05(m, 2H), 2.40 (s, 3H). [M+H]⁺ 538.9 d-49 ¹H NMR (600 MHz, CDCl₃) δ 8.07 (s, 1H), 7.46 (s, 1H), 7.39 (brs, 1H), 3.11-3.06(m, 2H), 2.39 (s, 3H). [M+H]⁺ 566.9 d-50 ¹H NMR (600 MHz, CDCl₃) δ 8.05 (s, 1H), 7.46 (s, 1H), 7.45 (brs, 1H), 3.13-3.05(m, 2H). [M+H]⁺ 620.9 d-52 ¹H NMR (600 MHz, CDCl₃) δ 8.05 (s, 1H), 7.51 (s, 1H), 7.44 (brs, 1H), 7.23-7.19(m, 5H), 3.33-3.25(m, 2H). [M+H]⁺ 601.8 d-54 ¹H NMR (600 MHz, CDCl₃) δ 8.08 (s, 1H), 7.50 (s, 1H), 7.45 (brs, 1H), 3.74 (s, 3H), 3.33-3.25(m, 2H). [M+H]⁺ 582.8 d-60 ¹H NMR (600 MHz, CDCl₃) δ 8.05 (s, 1H), 7.55 (s, 1H), 7.41 (brs, 1H), 3.11-3.02(m, 2H). [M+H]⁺ 487.9 d-63 ¹H NMR (600 MHz, CDCl₃) δ 8.07 (s, 1H), 7.56 (s, 1H), 7.42 (brs, 1H), 3.31-3.22(m, 2H). [M+H]⁺ 602.8 d-64 ¹H NMR (600 MHz, CDCl₃) δ 8.06 (s, 1H), 7.58 (s, 1H), 7.43 (brs, 1H), 3.15-3.07(m, 2H). [M+H]⁺ 549.9 d-65 ¹H NMR (600 MHz, CDCl₃) δ 8.03 (s, 1H), 7.50 (s, 1H), 7.41 (brs, 1H), 3.12-3.07(m, 2H). [M+H]⁺ 521.9 d-67 ¹H NMR (600 MHz, CDCl₃) δ 8.05 (s, 1H), 7.56 (s, 1H), 7.44 (brs, 1H), 3.61(s, 3H), 3.33-3.25(m, 2H). [M+H]⁺ 511.9 d-69 ¹H NMR (600 MHz, CDCl₃) δ 8.03 (s, 1H), 7.47 (s, 1H), 7.20 (brs, 1H), 3.00-2.92(m, 2H). [M+H]⁺ 565.1 d-70 ¹H NMR (600 MHz, CDCl₃) δ 8.07 (s, 1H), 7.47 (s, 1H), 7.21 (brs, 1H), 3.01-2.93(m, 2H). [M+H]⁺ 521.9 d-72 ¹H NMR (600 MHz, CDCl₃) δ 8.13 (s, 1H), 7.57 (s, 1H), 6.88 (s, 0H), 4.24 - 4.19 (m, 2H), 4.08 - 3.93 (m, 2H), 3.57 - 3.45 (m, 1H), 3.48 - 3.32 (m, 1H), 1.62 - 1.53 (m, 2H), 1.50 (dddd, J = 13.7, 6.9, 3.5, 2.3 Hz, 2H), 1.31 - 1.19 (m, 4H), 1.01 - 0.81 (m, 6H). [M+H]⁺ 629.0 d-73 ¹H NMR (600 MHz, CDCl₃) δ 8.12 (s, 1H), 7.57 (s, 1H), 6.85 (s, 1H), 5.11 (tt, J = 12.5, 6.2 Hz, 1H), 4.93 (dp, J = 30.3, 6.3 Hz, 1H), 3.53 - 3.37 (m, 1H), 3.45 - 3.22 (m, 1H), 1.27 - 1.20 (m, 6H), 1.18 - 1.07 (m, 6H). [M+H]⁺ 601.0 d-74 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 4.75 (s, 1H), 3.65(s, 3H). [M+H]⁺ 486.9 d-81 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.58 (s, 1H), 7.47 (brs, 1H), 4.75 (s, 1H). [M+H]⁺ 510.9 d-82 ¹H NMR (600 MHz, CDCl₃) δ 8.16 (s, 1H), 7.50 (s, 1H), 7.49 (brs, 1H), 4.76 (s, 1H). [M+H]⁺ 439.9 d-85 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.66 (s, 1H), 7.45 (brs, 1H), 3.74 (d, J = 6.9 Hz, 1H), 2.33-2.25(m, 2H). [M+H]⁺ 497.1 d-90 ¹H NMR (600 MHz, CDCl₃) δ 8.18 (s, 1H), 7.61 (s, 1H), 7.39 (brs, 1H), 4.71 (s, 1H). [M+H]⁺ 448.9 d-98 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.56 (s, 1H), 7.35 (brs, 1H), 4.74 (s, 1H), 3.65(s, 3H), 3.31-3.25(m, 2H). [M+H]⁺ 530.1 d-103 ¹H NMR (600 MHz, CDCl₃) δ 8.18 (s, 1H), 7.56 (s, 1H), 7.35 (brs, 1H), 4.74 (s, 1H), 3.33-3.25(m, 2H). [M+H]⁺ 567.9 d-107 ¹H NMR (600 MHz, CDCl₃) δ 8.20 (s, 1H), 7.50 (s, 1H), 7.41 (brs, 1H), 4.65 (s, 1H). [M+H]⁺ 525.9 d-109 ¹H NMR (600 MHz, CDCl₃) δ 8.17 (s, 1H), 7.56 (s, 1H), 7.45 (brs, 1H), 7.35 (brs, 1H), 4.74 (s, 1H), 2.75(s, 3H). [M+H]⁺ 514.9 d-112 ¹H NMR (600 MHz, CDCl₃) δ 8.17 (s, 1H), 7.56 (s, 1H), 7.35 (brs, 1H), 4.74 (s, 1H), 2.45(s, 3H). [M+H]⁺ 499.9 d-114 ¹H NMR (600 MHz, CDCl₃) δ 8.20 (s, 1H), 7.56 (s, 1H), 7.35 (brs, 1H), 4.14 (s, 1H). [M+H]⁺ 535.8 d-119 ¹H NMR (600 MHz, CDCl₃) δ 8.19 (s, 1H), 7.58 (s, 1H), 7.44 (brs, 1H), 6.23(d, J = 8.3 Hz, 1H), 6.02(dd, J = 1.3, 8.4 Hz, 1H), 4.81 (s, 1H), 1.63(d, J = 9.2 Hz, 3H). [M+H]⁺ 497.8 d-122 ¹H NMR (600 MHz, CDCl₃) δ 8.23 (s, 1H), 7.67 (s, 1H), 7.44 (brs, 1H), 4.81 (dd, J = 1.3, 8.4 Hz, 1H), 3.81 (s, 3H), 2.82 (m, 1H), 1.13(d, J = 10.2 Hz, 3H). [M+H]⁺ 468.9 d-127 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.54 (s, 1H), 7.43 (brs, 1H), 4.74 (s, 1H). [M+H]⁺ 478.9 d-129 ¹H NMR (600 MHz, CDCl₃) δ 8.16 (s, 1H), 7.49 (s, 1H), 7.43 (brs, 1H), 3.74 (s, 1H), 3.13-3.05(m, 2H). [M+H]⁺ 421.9 d-133 ¹H NMR (600 MHz, CDCl₃) δ 8.16 (s, 1H), 7.53 (brs, 1H), 7.49 (s, 1H), 7.43 (brs, 1H), 4.14 (s, 1H), 3.34 (s, 3H), 3.13-3.05(m, 2H). [M+H]⁺ 453.9 d-141 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.43 (s, 1H), 7.43 (brs, 1H), 3.74 (d, J = 8.4 Hz, 1H), 2.04-1.96 (m, 1H), 0.98 (d, J = 12.9 Hz, 6H). [M+H]⁺ 424.9
[0113] Hydrogen spectrum and mass spectrum data of nuclear magnetic resonance of some compounds shown in the general formula (e) of Table 11 were shown in Table 16. Table 16: Hydrogen Spectrum and Mass Spectrum Data of Nuclear Magnetic Resonance of Some Compounds Shown in General Formula (e) Compound ¹H-NMR(600 MHz) MS (ESI) e-1 ¹H NMR (600 MHz, CDCl₃) δ 8.15 (dd, J = 5.3, 1.8 Hz, 1H), 7.58 (d, J = 1.7 Hz, 1H), 7.15 (brs, 1H), 3.82 (s, 3H), 3.64 (s, 3H), 3.57 - 3.25 (m, 2H). [M+H]⁺ 545.1 e-2 ¹H NMR (600 MHz, CDCl₃) δ 8.13 (d, J = 1.3 Hz, 1H), 7.57 (d, J = 1.2 Hz, 1H), 6.84 (brs, 1H), 4.11- 3.99 (m, 2H), 3.81 (s, 3H), 3.48 (d, J = 2.2 Hz, 2H), 1.16 (t, J = 7.1 Hz, 3H). [M+H]⁺ 559.0 e-3 ¹H NMR (600 MHz, CDCl₃) δ 8.36 (s, 1H), 7.62 (s, 1H), 7.54 (t, J = 2.3 Hz, 1H), 4.78 - 4.63 (m, 2H), 4.49 - 4.29 (m, 2H), 3.82 (d, J = 4.8 Hz, 3H), 3.71 - 3.46 (m, 2H). [M+H]⁺ 612.9 e-4 ¹H NMR (600 MHz, CDCl₃) δ 8.34 (s, 1H), 7.64 (s, 1H), 6.92 (brs, 1H), 5.87 (tdt, J = 54.7, 24.2, 3.9 Hz, 1H), 4.35 - 4.12 (m, 2H), 3.83 (s, 3H), 3.63 - 3.35 (m, 2H). [M+H]⁺ 594.9 e-5 ¹H NMR (600 MHz, CDCl₃) δ 8.25 (m, 1H), 7.67 (s, 1H), 7.27 (brs, 1H), 4.38 - 4.21 (m, 2H), 4.15 - 4.00 (m, 2H), 3.69 - 3.30 (m, 2H), 1.25 (td, J = 7.1, 1.4 Hz, 3H), 1.17 (dt, J = 16.7, 7.1 Hz, 3H). [M+H]⁺ 573.2 e-6 ¹H NMR (600 MHz, CDCl₃) δ 8.23 (dd, J = 4.9, 1.8 Hz, 1H), 7.67 (d, J = 1.8 Hz, 1H), 6.86 (brs, 1H), 4.40 - 4.20 (m, 2H), 3.63 (s, 3H), 3.53 - 3.31 (m, 2H), 1.25 (td, J = 7.1, 3.0 Hz, 3H). [M+H]⁺ 559.0 e-7 ¹H NMR (600 MHz, CDCl₃) δ 8.17 (dd, J = 5.3, 1.8 Hz, 1H), 7.59 (d, J = 1.7 Hz, 1H), 7.16 (brs, 1H), 3.83 (s, 3H), 3.65 (s, 3H), 3.57 - 3.25 (m, 2H). [M+H]⁺ 545.1 e-8 ¹H NMR (600 MHz, CDCl₃) δ 8.13 (d, J = 1.3 Hz, 1H), 7.55 (d, J = 1.2 Hz, 1H), 6.82 (brs, 1H), 4.11 - 3.97 (m, 2H), 3.81 (s, 3H), 3.49 (d, J = 2.2 Hz, 2H), 1.16 (t, J = 7.2 Hz, 3H). [M+H]⁺ 559.0 e-9 ¹H NMR (600 MHz, CDCl₃) δ 8.35 (s, 1H), 7.63 (s, 1H), 7.44 (t, J = 2.3 Hz, 1H), 4.78 - 4.62 (m, 2H), 4.50 - 4.29 (m, 2H), 3.82 (d, J = 4.8 Hz, 3H), 3.71 - 3.46 (m, 2H). [M+H]⁺ 612.9 e-10 ¹H NMR (600 MHz, CDCl₃) δ 8.34 (s, 1H), 7.64 (s, 1H), 6.96 (brs, 1H), 5.87 (tdt, J = 54.7, 24.2, 3.9 Hz, 1H), 4.35 - 4.12 (m, 2H), 3.93 (s, 3H), 3.64 - 3.35 (m, 2H). [M+H]⁺ 594.9 e-11 ¹H NMR (600 MHz, CDCl₃) δ 8.25 (m, 1H), 7.67 (s, 1H), 7.27 (brs, 1H), 4.39 - 4.21 (m, 2H), 4.15 - 4.01 (m, 2H), 3.68 - 3.30 (m, 2H), 1.25 (td, J = 7.1, 1.5 Hz, 3H), 1.17 (dt, J = 16.7, 7.2 Hz, 3H). [M+H]⁺ 573.2 e-12 ¹H NMR (600 MHz, CDCl₃) δ 8.22 (dd, J = 4.9, 1.8 Hz, 1H), 7.68 (d, J = 1.8 Hz, 1H), 6.96 (brs, 1H), 4.40-4.20 (m, 2H), 3.63 (s, 3H), 3.53 - 3.31 (m, 2H), 1.25 (td, J = 7.1, 3.1 Hz, 3H). [M+H]⁺ 559.0 e-13 ¹H NMR (600 MHz, CDCl₃) δ 8.16 (dd, J = 5.3, 1.9 Hz, 1H), 7.58 (d, J = 1.8 Hz, 1H), 7.13 (brs, 1H), 3.82 (s, 3H), 3.64 (s, 3H), 3.59 - 3.25 (m, 2H). [M+H]⁺ 545.1 e-14 ¹H NMR (600 MHz, CDCl₃) δ 8.11 (d, J = 1.4 Hz, 1H), 7.47 (d, J = 1.2 Hz, 1H), 6.84 (brs, 1H), 4.11- 3.99 (m, 2H), 3.83 (s, 3H), 3.48 (d, J = 2.2 Hz, 2H), 1.16 (t, J = 7.5 Hz, 3H). [M+H]⁺ 559.0 e-15 ¹H NMR (600 MHz, CDCl₃) δ 8.32 (s, 1H), 7.62 (s, 1H), 7.54 (t, J = 2.4 Hz, 1H), 4.78 - 4.63 (m, 2H), 4.49 - 4.29 (m, 2H), 3.81 (d, J = 4.8 Hz, 3H), 3.71 - 3.46 (m, 2H). [M+H]⁺ 612.9 e-16 ¹H NMR (600 MHz, CDCl₃) δ 8.33 (s, 1H), 7.64 (s, 1H), 6.92 (brs, 1H), 5.87 (tdt, J = 54.7, 24.2, 3.9 Hz, 1H), 4.34 - 4.12 (m, 2H), 3.83 (s, 3H), 3.64 - 3.35 (m, 2H). [M+H]⁺ 594.9 e-17 ¹H NMR (600 MHz, CDCl₃) δ 8.26 (m, 1H), 7.67 (s, 1H), 7.27 (brs, 1H), 4.40 - 4.21 (m, 2H), 4.15 - 4.01 (m, 2H), 3.69 - 3.30 (m, 2H), 1.25 (td, J = 7.3, 1.2Hz, 3H), 1.17 (dt, J = 16.7, 7.3 Hz, 3H). [M+H]⁺ 573.2 e-18 ¹H NMR (600 MHz, CDCl₃) δ 8.33 (dd, J = 4.9, 1.9 Hz, 1H), 7.68 (d, J = 1.6 Hz, 1H), 6.86 (brs, 1H), 4.41 - 4.21 (m, 2H), 3.62 (s, 3H), 3.52 - 3.30 (m, 2H), 1.24 (td, J = 7.0, 3.0 Hz, 3H). [M+H]⁺ 559.0 e-19 ¹H NMR (600 MHz, CDCl₃) δ 8.20 (s, 1H), 7.77 (s, 1H), 7.05 (brs, 1H), 3.82 (s, 3H), 3.64 (s, 3H), 3.57 - 3.25 (m, 2H). [M+H]⁺ 545.1 e-20 ¹H NMR (600 MHz, CDCl₃) δ 8.23 (s, 1H), 7.77 (s, 1H), 6.84 (brs, 1H), 4.11 - 3.99 (m, 2H), 3.81 (s, 3H), 3.48 (d, J = 2.2 Hz, 2H), 1.16 (t, J = 7.1 Hz, 3H). [M+H]⁺ 545.1 e-21 ¹H NMR (600 MHz, CDCl₃) δ 8.26 (s, 1H), 7.87 (s, 1H), 7.54 (t, J = 2.3 Hz, 1H), 4.78 - 4.63 (m, 2H), 4.49 - 4.29 (m, 2H), 3.82 (s, 3H), 3.71 - 3.46 (m, 2H). [M+H]⁺ 559.0 e-22 ¹H NMR (600 MHz, CDCl₃) δ 8.34 (s, 1H), 7.69 (s, 1H), 6.92 (brs, 1H), 5.87 (tdt, J = 54.7, 24.2, 3.9 Hz, 1H), 4.35 - 4.12 (m, 2H), 3.83 (s, 3H), 3.63 - 3.35 (m, 2H). [M+H]⁺ 612.9 e-23 ¹H NMR (600 MHz, CDCl₃) δ 8.25 (s, 1H), 7.57 (s, 1H), 7.27 (brs, 1H), 4.38 - 4.21 (m, 2H), 4.15 - 4.00 (m, 2H), 3.69 - 3.30 (m, 2H), 1.25 (td, J = 7.1, 1.4 Hz, 3H), 1.17 (dt, J = 16.7, 7.1 Hz, 3H). [M+H]⁺ 594.9 e-24 ¹H NMR (600 MHz, CDCl₃) δ 8.23 (s, 1H), 7.88 (s, 1H), 6.86 (s, 1H), 4.40 - 4.20 (m, 2H), 3.63 (s, 3H), 3.53 - 3.31 (m, 2H), 1.25 (td, J = 7.1, 3.0 Hz, 3H). [M+H]⁺ 573.2 Embodiment 9: Insecticidal activity embodiment(1) Insecticidal activity on 2^nd-instar larvae of Plutella xylostella
[0114] Plutella xylostella (L.) is a lepidoptera pest with a chewing mouthpart and is a common vegetable pest. The 2^nd-instar larvae of Plutella xylostella were used as test objects and tested by using a leaf immersion feeding method.
[0115] Operation process: Samples were weighed accurately, and respectively added with 200 µL of dimethyl sulfoxide to prepare 10 g/L mother liquor which was diluted into a concentration of 500 ppm with an aqueous solution containing 0.05% of Tween-80 during the test. A hole puncher with a diameter of 1.0 cm was used to make cleaned cabbage leaves into leaf discs. The leaf discs were immersed in a liquid medicine, taken out after 5 seconds, air-dried naturally, and transferred into a clean vessel. About 35 2^nd-instar larvae of Plutella xylostella were put into the vessel and fed at a constant temperature of 28°C. Each concentration was repeated 3 times, and an aqueous solution containing 0.05% of Tween-80 was used as a control group. After being treated for 24 hours, a number of dead Plutella xylostella was counted, and a mortality (%) was calculated according to a formula that mortality (%) = (number of live larvae in the control group - number of treated live larvae) / number of live larvae in the control group ^∗ 100%. The results were shown in Table 17 to Table 24. (2) Insecticidal activity on 2^nd-instar larvae of Spodoptera exigua
[0116] Spodoptera exigua is a lepidoptera pest with a chewing mouthpart and is a common vegetable pest. The 2^nd-instar larvae of Spodoptera exigua were used as test objects and tested by using a leaf immersion feeding method.
[0117] Operation process: Samples were weighed accurately, and respectively added with 200 µL of dimethyl sulfoxide to prepare 10 g/L mother liquor which was diluted into a concentration of 500 ppm with an aqueous solution containing 0.05% of Tween-80 during the test. A hole puncher with a diameter of 1.0 cm was used to make cleaned cabbage leaves into leaf discs. The leaf discs were immersed in a liquid medicine, taken out after 5 seconds, air-dried naturally, and transferred into a clean vessel. About 35 2^nd-instar larvae of Spodoptera exigua were put into the vessel and fed at a constant temperature of 28°C. Each concentration was repeated 3 times, and an aqueous solution containing 0.05% of Tween-80 was used as a control group. After being treated for 24 hours, a number of dead Plutella xylostella was counted, and a mortality (%) was calculated according to a formula that mortality (%) = (number of live larvae in the control group - number of treated live larvae) / number of live larvae in the control group ^∗ 100%. The results were shown in Table 17 to Table 24. (3) Insecticidal activity on aphid adults
[0118] Aphid is a homoptera pest with a piercing-sucking mouthpart and is a common vegetable pest. Aphis craccivora were taken as test objects and tested by using an impregnation method.
[0119] Operation process: Samples were weighed accurately, and respectively added with 200 µL of dimethyl sulfoxide to prepare 10 g/L mother liquor which was diluted into a concentration of 500 ppm with an aqueous solution containing 0.05% of Tween-80 during the test. After the wingless Aphis craccivora adults stably sucked on bean sprouts, the wingless Aphis craccivora adults together with the bean sprouts were immersed into a liquid medicine with a concentration of 500 ppm, taken out after 5 seconds, air-dried naturally, transferred into a clean vessel, and fed at a constant temperature of 23°C. Each concentration was repeated 3 times, and an aqueous solution containing 0.05% of Tween-80 was used as a control group. After being treated for 24 hours, a number of dead Aphis craccivora was counted, and a mortality (%) was calculated according to a formula that mortality (%) = (number of live Aphis craccivora in the control group - number of treated live Aphis craccivora) / number of live Aphis craccivora in the control group ^∗ 100%. The results were shown in Table 17 to Table 24. (4) Insecticidal activity on Solenopsis invicta
[0120] As a hymenoptera pests and a social insect, Solenopsis invicta is one of the most destructive invasive organisms. Solenopsis invicta were used as test objects and tested by using a water test tube poison-feeding method.
[0121] Operation process: Samples were weighed accurately, and respectively added with 200 µL of dimethyl sulfoxide to prepare 10 g/L mother liquor which was diluted into a concentration of 100 ppm with a mixed aqueous solution containing 0.05% of Tween-80 and 5% of honey during the test. Solenopsis invicta were placed in a raising test tube, and a liquid medicine was injected into a silica gel plug of the raising test tube by a syringe as long as the liquid medicine did not seep out. The raising test tube was placed in a raising box horizontally, and a small amount of ham sausages were added to the raising test tube as food to raise the Solenopsis invicta at a constant temperature of 25°C. After being treated for 24 hours and 72 hours, a number of live Solenopsis invicta and a number of dead Solenopsis invicta were counted, and a mortality (%) was calculated according to a formula that mortality (%) = (number of live Solenopsis invicta in the control group - number of treated live Solenopsis invicta) / number of live Solenopsis invicta in the control group ^∗ 100%. The results were shown in Table 17 to Table 24. Table 17: Insecticidal Activity of Compounds of Formula (I) on Test Pests Compoun d No. Insecticidal activity Compoun d No. Insecticidal activityPlutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invicta Plutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invictaMortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 100 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 100 ppm 24h 72h 24h 72h A1 95 90 100 20 87 A25 100 100 100 38 100A2 97 100 100 19 93 A26 100 100 100 45 100A3 90 100 100 25 100 A27 100 100 100 30 100A4 86 100 100 20 87 A28 100 90 100 29 97A5 100 100 100 34 100 A29 100 100 100 26 95A6 100 100 100 44 100 A30 100 100 100 40 100A7 100 100 100 20 100 A31 100 100 100 20 100A8 100 90 100 26 93 A32 100 90 100 26 93A9 100 100 100 24 100 A33 100 100 100 24 100A10 86 100 100 20 87 A34 96 100 100 28 97A11 100 100 100 34 100 A35 100 100 100 31 99A12 100 100 100 44 100 A36 100 100 100 44 100A13 100 100 100 20 100 A37 100 100 100 20 100A14 100 90 100 26 93 A38 100 90 100 26 93A15 100 100 100 24 100 A39 100 100 100 24 100A16 86 100 100 20 87 A40 96 100 100 20 97A17 100 100 100 34 100 A41 100 100 100 24 100A18 100 100 100 44 100 A42 100 100 100 44 100A19 100 100 100 20 100 A43 100 100 100 20 100A20 100 90 100 26 93 A44 100 90 100 26 93A21 100 100 100 24 100 A45 100 100 100 24 100A22 96 100 100 30 97 A46 86 100 100 20 87A23 100 100 100 34 100 A47 100 100 100 34 100A24 100 100 100 44 100 Table 18: Insecticidal Activity of Some Compounds of Formula (I) on Test Pests Compoun d No. Insecticidal activity Compoun d No. Insecticidal activityPlutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invicta Plutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invictaMortality (%) 500 ppm Mortality (%) 500ppm Mortality (%) 500 ppm Mortality (%) 100 ppm Mortality (%) 500 ppm Mortality (%) 500ppm Mortality (%) 500 ppm Mortality (%) 100 ppm 24h 72h 24h 72h B1 100 100 100 20 100 B7 100 100 100 38 100B2 100 90 93 26 93 B8 100 100 100 45 100B3 100 100 100 24 100 B9 100 100 100 38 100B4 86 100 100 20 88 B10 100 95 100 30 90B5 100 100 100 34 100 B11 100 100 100 33 95B6 90 100 100 44 100 B12 100 100 100 40 100 Table 19: Insecticidal Activity of Compounds of Formula (I) in Table 3 on Test Pests Compound No. Insecticidal activity Compound No. Insecticidal activityPlutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invicta Plutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invictaMortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 100 ppm Mortality (%) 500 ppm Mortality (%) 500ppm Mortality (%) 500 ppm Mortality (%) 100 ppm 24h 72h 24h 72h C1 89 100 100 20 100 C33 100 100 100 36 100C2 100 90 100 26 93 C34 100 100 100 40 100C3 100 100 100 24 100 C35 100 100 100 38 100C4 86 76 89 20 87 C36 90 90 100 10 90C5 100 100 100 34 100 C37 100 100 100 20 100C6 100 100 100 44 100 C38 100 90 100 25 90C7 100 100 100 38 100 C39 90 100 98 24 87C8 91 85 95 36 92 C40 100 95 100 28 90C9 100 100 100 39 100 C41 89 94 100 19 90C10 100 85 100 27 100 C42 91 94 100 20 70C11 100 100 100 46 100 C43 86 89 95 18 80C12 100 91 100 18 95 C44 90 100 100 36 90C13 100 100 100 32 100 C45 93 97 86 25 71C14 100 100 100 30 100 C46 89 91 90 21 80C15 89 100 100 29 90 C47 77 86 80 27 87C16 100 95 99 23 89 C48 76 85 79 26 86C17 88 89 100 15 68 C49 87 89 90 20 81C18 90 86 98 20 70 C50 81 86 90 26 86C19 90 90 100 18 70 C51 87 85 79 19 86C20 100 100 100 28 99 C52 90 91 100 22 90C21 90 95 100 19 99 C53 78 89 90 28 97C22 99 94 89 20 70 C54 77 78 87 17 84C23 86 88 95 18 80 C55 88 80 91 19 83C24 100 100 100 36 100 C56 82 87 91 27 80C25 92 97 86 25 71 C57 78 76 80 20 89C26 89 90 100 20 80 C58 100 100 100 29 98C27 76 86 100 27 86 C59 100 90 100 29 100C28 100 100 100 30 98 C60 90 92 100 25 92C29 100 93 100 30 100 C61 88 100 90 28 100C30 100 90 92 24 100 C62 80 85 97 27 100C31 100 100 100 34 100 C63 98 90 96 29 98C32 100 90 95 25 100 C64 92 97 100 17 90 Table 20: Insecticidal Activity of Some Compounds of General Formula (a) on Test Pests Compound Insecticidal activity Compound Insecticidal activityPlutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invicta Plutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invictaMortality (%) 500ppm Mortality (%) 500 ppm Mortality (%) 500ppm Mortality (%)100 ppm Mortality (%) 500ppm Mortality (%) 500 ppm Mortality (%) 500ppm Mortality (%) 100 ppm 24h 72h 24h 72h a-1 100 100 100 20 100 a-43 86 81 99 20 94 a-2 97 97 100 19 98 a-44 100 95 100 15 95 a-3 90 90 100 25 100 a-45 100 91 100 20 90 a-4 86 95 100 20 97 a-47 100 90 100 19 97 a-5 90 89 100 24 96 a-51 91 89 100 16 95 a-6 100 100 100 34 100 a-52 100 89 91 20 89 a-7 95 91 100 20 90 a-53 100 96 100 20 100 a-8 95 90 95 10 90 a-56 100 90 100 16 93 a-9 100 100 100 14 100 a-57 100 100 100 24 100 a-10 100 100 100 20 97 a-59 96 91 100 28 97 a-11 100 100 100 24 100 a-62 100 100 100 21 99 a-12 100 100 100 19 100 a-63 100 100 100 24 100 a-13 100 100 100 20 100 a-64 100 99 100 20 99 a-14 100 100 100 26 100 a-65 100 100 100 26 100 a-15 100 100 100 21 100 a-71 100 99 100 24 100 a-16 96 86 100 20 87 a-72 96 89 100 20 91 a-17 96 89 100 24 90 a-76 95 85 91 24 80 a-18 96 86 100 20 87 a-77 90 86 96 44 90 a-19 95 91 100 20 90 a-80 91 85 100 10 100 a-20 100 90 100 26 93 a-83 100 90 100 26 93 a-21 91 79 100 24 90 a-86 100 89 100 24 89 a-22 100 100 100 30 100 a-87 96 100 100 20 97 a-26 100 100 100 34 100 a-88 100 100 100 34 100 a-27 100 100 100 25 100 a-95 96 89 100 21 92 a-28 100 95 100 23 99 a-100 91 90 100 20 90 a-29 100 91 100 14 96 a-109 95 89 100 20 90 a-30 96 90 100 20 97 a-111 100 100 100 19 97 a-36 100 96 100 14 91 a-112 100 96 100 16 99 a-37 100 96 100 15 99 a-118 96 95 100 25 100 a-38 90 90 100 26 100 a-122 91 89 100 20 90 a-39 90 89 100 25 93 a-132 90 90 100 26 94 a-40 90 89 100 19 90 a-133 100 100 100 24 100 a-41 86 81 99 20 94 a-134 100 100 100 27 100 a-42 96 96 100 21 96 a-136 100 100 100 11 100 Table 21: Insecticidal Activity of Some Compounds of General Formula (b) on Test Pests Compound Insecticidal activity Compound Insecticidal activityPlutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invicta Plutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invictaMortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 100 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 100 ppm 24h 72h 24h 72h b-1 100 100 100 20 97 b-47 95 85 100 18 90 b-2 100 95 100 19 93 b-48 100 89 100 15 90 b-3 90 90 95 25 90 b-50 99 90 100 10 100 b-4 90 89 96 20 90 b-54 100 90 100 25 97 b-5 89 80 100 14 100 b-56 100 100 100 26 100 b-6 100 100 100 20 100 b-57 100 100 100 30 100 b-7 100 90 100 17 97 b-59 100 100 100 20 100 b-8 100 96 100 26 92 b-62 100 96 100 26 93 b-9 100 100 100 19 100 b-63 100 100 100 24 100 b-10 100 100 100 20 100 b-66 96 91 100 28 97 b-11 100 100 100 34 100 b-68 99 100 100 21 99 b-12 100 100 100 14 100 b-70 100 95 100 44 100 b-13 100 100 100 20 100 b-73 89 85 100 20 90 b-14 100 100 100 26 100 b-76 95 90 100 26 93 b-15 100 100 100 24 100 b-80 95 90 100 14 90 b-16 96 90 100 20 97 b-86 96 89 100 20 97 b-17 100 92 100 14 100 b-87 95 95 100 14 100 b-18 99 89 98 14 100 b-88 100 100 100 25 100 b-19 100 95 100 20 100 b-94 100 90 100 20 100 b-20 100 90 100 21 93 b-96 100 93 100 26 98 b-21 90 81 90 24 86 b-99 91 85 100 24 90 b-23 96 95 100 10 97 b-104 96 96 100 20 96 b-25 100 100 100 26 100 b-111 100 100 100 24 100 b-27 91 89 100 19 100 b-116 100 98 100 20 100 b-28 100 99 100 16 100 b-118 99 91 100 14 99 b-30 90 85 100 25 94 b-123 99 95 100 24 100 b-34 90 87 100 10 100 b-131 95 95 100 11 100 b-37 86 90 99 20 94 b-134 100 100 100 26 100 b-38 90 85 99 32 90 b-135 100 100 100 23 100 b-39 96 85 97 24 90 b-136 100 100 100 20 97 b-43 89 80 89 19 90 b-138 100 100 100 14 100 Table 22: Insecticidal Activity of Some Compounds of General Formula (c) on Test Pests Compound Insecticidal activity Compound Insecticidal activityPlutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invicta Plutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invictaMortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 100 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 100 ppm 24h 72h 24h 72h c-2 95 90 100 20 97 c-114 96 89 100 18 100 c-4 97 100 100 29 93 c-117 100 100 100 25 100 c-7 100 100 100 20 100 c-118 95 85 100 20 90 c-8 100 100 100 20 100 c-121 100 90 100 19 97 c-9 99 100 100 14 100 c-123 100 96 100 26 99 c-10 99 95 100 24 100 c-126 100 100 100 35 100 c-13 100 95 100 21 100 c-128 91 89 100 20 90 c-14 100 96 100 26 100 c-131 90 84 92 26 94 c-15 95 90 100 24 100 c-135 90 79 96 24 89 c-19 100 100 100 20 100 c-139 96 91 100 28 87 c-20 100 100 100 14 100 c-145 100 95 100 11 99 c-34 100 100 100 34 100 c-149 100 100 100 31 100 c-36 92 90 95 21 100 c-150 95 87 91 20 90 c-37 96 90 100 21 93 c-152 100 89 100 16 93 c-39 95 89 100 24 90 c-154 89 71 91 24 80 c-42 86 80 100 20 97 c-159 96 100 100 20 97 c-47 90 89 100 35 99 c-164 100 80 100 24 90 c-49 100 95 100 44 100 c-166 100 100 100 25 100 c-53 100 96 100 20 100 c-169 100 100 100 20 99 c-54 100 90 100 26 96 c-173 95 90 100 25 93 c-57 95 89 100 24 95 c-180 95 82 100 21 91 c-61 96 100 100 26 97 c-186 89 81 99 20 87 c-64 96 90 100 14 100 c-188 100 100 100 14 100 c-67 100 100 100 25 100 c-196 100 90 100 20 97 c-72 100 90 100 23 99 c-203 97 100 100 29 100 c-73 100 100 100 14 90 c-210 100 100 100 20 100 c-77 96 90 100 20 97 c-217 100 100 100 20 100 c-80 100 100 100 13 90 c-221 99 100 100 14 100 c-84 99 96 100 25 95 c-224 99 95 100 25 100 c-86 100 99 100 16 100 c-231 100 100 100 21 100 c-91 90 82 100 25 94 c-238 100 96 100 26 100 c-93 90 89 100 30 100 c-245 95 94 100 14 100 c-96 86 90 99 20 84 c-253 96 100 100 20 97 c-97 100 100 100 32 100 c-258 100 100 100 14 100 c-98 96 90 100 24 90 c-262 100 100 100 34 100 c-101 89 80 100 19 99 c-266 92 90 95 21 100 c-105 96 100 100 25 100 c-273 96 90 100 21 93 c-106 99 95 100 27 100 c-286 95 89 100 24 90 c-107 99 90 100 26 99 c-306 96 80 100 20 97 c-110 100 100 100 14 100 c-317 90 89 100 20 100 c-111 98 99 100 17 99 c-327 100 95 100 34 100 c-113 98 91 99 14 98 c-346 100 96 100 20 100 Table 23: Insecticidal Activity of Some Compounds of General Formula (d) on Test Pests Compound Insecticidal activity Compound Insecticidal activityPlutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invicta Plutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invictaMortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 100 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 100 ppm 24h 72h 24h 72h d-3 100 98 100 21 87 d-58 76 70 96 21 99 d-7 100 100 100 20 99 d-60 96 90 90 24 90 d-8 85 82 90 15 65 d-63 100 95 100 20 90 d-9 82 79 96 21 77 d-64 100 90 100 26 93 d-10 55 50 90 34 80 d-65 100 100 100 24 90 d-11 76 70 99 14 76 d-67 100 90 100 41 99 d-12 86 96 100 20 100 d-69 90 86 100 44 100 d-13 82 81 99 26 89 d-70 91 90 99 20 98 d-14 90 89 100 24 100 d-72 90 85 99 26 76 d-15 96 100 100 19 97 d-73 81 66 96 24 85 d-16 85 93 96 34 100 d-74 100 100 100 21 99 d-17 99 95 100 42 100 d-77 100 99 100 44 100 d-18 81 80 100 15 85 d-81 99 90 100 35 100 d-19 100 90 100 23 99 d-82 95 89 100 25 90 d-20 100 100 100 14 100 d-85 100 100 100 30 100 d-26 100 100 100 20 100 d-86 100 90 100 29 97 d-27 100 100 100 14 100 d-90 82 80 90 16 85 d-28 100 96 100 25 100 d-94 89 90 99 20 90 d-33 100 99 100 26 100 d-98 100 100 100 20 99 d-34 90 95 100 25 93 d-103 100 98 100 26 93 d-35 90 89 100 30 100 d-107 100 100 100 24 100 d-38 86 9 99 30 84 d-109 96 85 99 28 85 d-42 100 100 100 31 100 d-112 96 80 100 36 99 d-46 95 90 100 14 90 d-114 100 87 100 24 90 d-47 100 100 100 29 99 d-115 99 90 100 20 100 d-48 96 90 100 26 100 d-119 89 90 92 26 83 d-49 100 100 100 29 100 d-122 91 84 90 24 95 d-50 100 90 100 26 93 d-127 96 100 100 20 97 d-52 100 100 100 24 100 d-129 95 100 100 24 100 d-54 100 99 100 21 99 d-133 70 86 100 21 95 d-56 90 89 99 14 80 d-141 90 95 100 11 91 d-57 89 80 90 20 70 Table 24: Insecticidal Activity of Some Compounds of General Formula (e) on Test Pests Compound Insecticidal activity Compound Insecticidal activityPlutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invicta Plutella xylostella Spodoptera exigua Aphis craccivora Solenopsis invictaMortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 100 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 500 ppm Mortality (%) 100 ppm 24h 72h 24h 72h e-1 100 100 100 33 100 e-13 100 100 100 20 100 e-2 100 100 100 25 100 e-14 100 100 100 34 100 e-3 100 95 100 20 98 e-15 90 89 100 32 100 e-4 100 100 100 32 100 e-16 100 100 100 32 99 e-5 100 100 100 34 100 e-17 100 100 100 30 100 e-6 100 100 100 34 100 e-18 100 100 100 29 100 e-7 100 100 100 29 99 e-19 100 100 100 31 90 e-8 100 100 100 35 100 e-20 100 100 100 31 100 e-9 96 90 100 40 96 e-21 100 100 100 30 100 e-10 100 100 100 37 100 e-22 100 100 100 35 100 e-11 100 100 100 33 100 e-23 100 100 100 34 93 e-12 100 100 100 34 100 e-24 100 100 100 34 100
[0122] It can be seen from the tables that the compounds illustrated in the present invention have a high killing activity on agroforestry pests, animal parasitic pests, sanitary insect pest and the like, have an good activity on lepidoptera, homoptera, hymenoptera pests and the like, have a delayed working effect on Solenopsis invicta, and have a better killing effect on a whole Solenopsis invicta nest and a queen Solenopsis invicta. Embodiment 10: Environmental safety embodiment
[0123] Results of toxicity tests of some compounds of the present invention on environmental non-target organisms were shown in the table below: (1) Toxicity test on 2^nd-instar larvae of Bombyx mori L.
[0124] Bombyx mori L. is an important economic insect sensitive to pesticides in an agricultural ecosystem, and is also one of the non-target organisms of environmental ecology listed in pesticide registration of China. The 2^nd-instar larvae of Bombyx mori L. were used as test objects and tested by using a leaf immersion feeding method.
[0125] Operation process: Samples were weighed accurately, and respectively added with 200 µL of dimethyl sulfoxide to prepare 10 g/L mother liquor which was diluted into a concentration of 1000 ppm with an aqueous solution containing 0.05% of Tween-80 during the test. Young cotyledons of mulberries were collected, washed and air-dried, immersed in a liquid medicine, taken out after 5 seconds, naturally air-dryed, and then transferred into a clean vessel. About 35 2^nd-instar larvae of Bombyx mori L. were put into the vessel and fed at a constant temperature of 25°C. Each concentration was repeated 3 times, and an aqueous solution containing 0.05% of Tween-80 was used as a control group. After being treated for 24 hours, a number of dead Plutella xylostella was counted, and a mortality (%) was calculated according to a formula that mortality (%) = (number of live larvae in the control group - number of treated live larvae) / number of live larvae in the control group ^∗ 100%. The results were shown in Table 10. (2) Toxicity test on adult worker bees of Apis cernan
[0126] Adult worker bees of Apis cernan having the same size were selected for test. The worker bees were collected from beekeeping boxes in the daystart of the test day and tested by using a small beaker method.
[0127] Operation process: A small amount of absorbent cotton was put into a 5 mL small beaker, 5 mL of a test liquid medicine (a concentration of 500 ppm) was dropped into the absorbent cotton, and stirred gently to make the absorbent cotton completely wet but not leached obviously, then the small beaker was put into a 500 mL large beaker, then 15 worker bees were put into the large beaker, and finally the large beaker was sealed with gauze. After treatment, the large beaker was placed in a dark room of an artificial climate box. After taking the medicine for 48 hours, a number of live and dead worker bees were investigated. The results were shown in Table 25. Table 25: Toxicity of Some Compounds of Formula (I) Shown in Table 1 to Table 3 on Environmental Non-target Organisms Compound No. Toxicity determination Compound No. Toxicity determinationBombyx mori L. Apis cernan Bombyx mori L. Apis cernanMortality (%) 1000 ppm Mortality (%) 500 ppm Mortality (%) 1000 ppm Mortality (%) 500 ppm A1 9 12 A22 0 3A4 10 8 A23 0 5A5 2 9 A26 7 10A7 6 6 A27 10 15A8 12 10 A30 8 8A10 15 12 A32 10 4A12 13 12 A36 3 0A13 17 17 A43 3 8A15 8 5 A44 8 8A19 7 5 A45 10 11A21 0 6 A46 7 2B1 0 0 B7 6 6B2 3 4 B8 5 4B3 0 3 B9 0 5B4 0 0 B10 3 3B5 6 4 B11 7 3B6 4 5 B12 5 6C1 7 7 C32 6 9C2 5 10 C35 4 4C3 12 10 C36 2 3C4 3 0 C37 6 8C9 8 9 C38 4 0C10 10 9 C40 4 4C13 12 10 C43 0 4C14 10 10 C45 6 3C15 8 7 C46 5 3C18 6 5 C50 5 2C20 8 10 C51 9 5C24 11 10 C52 10 7C25 3 0 C56 6 8C26 4 4 C58 4 4C29 0 4 C61 9 10C30 0 0 C62 10 11C31 3 8 C64 7 9 Embodiment 11: Preparation of insecticide composition containing the compound of the present invention(1) Oily suspension
[0128] The following components were prepared in proportion: 25% (weight percentage, same below) of any one of the above compounds; 5% of polyoxyethylene sorbitan hexaoleate; and 70% of higher aliphatic hydrocarbon oil. The components were ground together in a sand mill until sizes of solid particles were 5 µm or less. The viscous suspension obtained could either be used directly, or used after being emulsified in water. (2) Aqueous suspension
[0129] The following components were prepared in proportion: 25% of any one of the above compounds; 3% of hydrated attapulgite; 10% of calcium lignosulfonate; 0.5% of sodium dihydrogenphosphate; and 61.5% of water. The components were ground together in a ball mill until sizes of solid particles were approximately 10 µm or less. The aqueous suspension could be used directly. (3) Bait
[0130] The following components were prepared in proportion: 0.1 o 10% of any one of the above compounds; 80% of wheat flour; and 19.9 to 10% of molasses. These components were completely mixed to form a bait shape as required. The edible baits could be dispersed to places infested by sanitary insect pests, for example, furniture or industrial places, such as kitchens, hospitals or shops or outdoor areas, so as to control the pests by oral ingestion.
[0131] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but are not intended to limit the scope of protection of the present invention. Those of ordinary skill in the art can make other different forms of transformations or changes based on the above description and ideas. All the embodiments need not and cannot be exhaustive here. Any modifications, equivalent substitutions, and improvements made within the spirit and principle of the present invention shall all fall within the scope of protection of the claims of the present invention.

权利要求:
Claims (17)
[0001] A fused heterocyclic compound, and an optical isomer, cis and trans isomers or an agromedically acceptable salt thereof, characterized in that, the fused heterocyclic compound has a structure shown in formula (I):
[0002] The compound according to claim 1, or the optical isomer, the cis and trans isomers or the agromedically acceptable salt of the compound, characterized in that, when Y is N or CH;R¹¹ is halogen, -CN, -COR¹⁷, -CONR¹⁷R¹⁸, -S(O)R¹⁷, -NR¹⁷R¹⁸, -NR¹⁷COR¹⁸, aryl, heterocyclyl or heteroaryl; wherein the aryl, the heterocyclyl or the heteroaryl is unsubstituted or substituted with one or more substituents R¹⁰;R¹² is hydrogen, -COR¹⁷, -CONR¹⁷R¹⁸, -S(O)R¹⁷, -S(O)₂R¹⁷, -NR¹⁷R¹⁸, -N R¹⁷COR¹⁸, -NR¹⁷CONR¹⁸R¹⁹, -NR¹⁷CO₂R¹⁸, aryl, heterocyclyl or heteroaryl; wherein the aryl, the heterocyclyl or the heteroaryl is unsubstituted or substituted with one or more substituents R¹⁰;R¹³ is hydrogen, -COR¹⁷, alkyl, heteroalkyl or alkenyl;R¹⁴ is halogen, -CN, -NR¹⁷R¹⁸, -OR¹⁷, -COR¹⁷, -CO₂R¹⁷, -CONR¹⁷R¹⁸, -N R¹⁷COR¹⁸, -NR¹⁷CO₂R¹⁸, alkyl, heteroalkyl or alkenyl; wherein the alkyl, the heteroalkyl or the alkenyl is unsubstituted or substituted with one or more substituents R¹⁰; andR¹⁵ is hydrogen, halogen, -CN, -NR¹⁷R¹⁸, -OR¹⁷, -COR¹⁷, -CO₂R¹⁷,-CONR¹⁷R¹⁸, -NR¹⁷COR¹⁸, -NR¹⁷CO₂R¹⁸, alkyl, heteroalkyl or alkenyl; wherein the alkyl, the heteroalkyl or the alkenyl is unsubstituted or substituted with one or more substituents R¹⁰.
[0003] The compound according to claim 1, or the optical isomer, the cis and trans isomers or the agromedically acceptable salt of the compound according to claim 1, characterized in that, when Z¹, Z², Z³ and Z⁴ are all C, one or more R¹⁶ are provided, and each R¹⁶ is independently hydrogen, halogen, alkyl, heteroalkyl, alkenyl, -S(O) R¹⁷, -S(O)₂R¹⁷, -COR¹⁷, -NR¹⁷R¹⁸, -CONR¹⁷R¹⁸, -NR¹⁷COR¹⁸ or -NR¹⁷S(O)₂R¹⁸;R¹¹ is halogen, -CN, -COR¹⁷, -CONR¹⁷R¹⁸, -S(O)R¹⁷, -NR¹⁷R¹⁸, -NR¹⁷COR¹⁸, aryl, heterocyclyl or heteroaryl; wherein the aryl, the heterocyclyl or the heteroaryl is unsubstituted or substituted with one or more substituents R¹⁰;R¹² is -CONR¹⁷R¹⁸, -S(O)R¹⁷, -S(O)₂R¹⁷, -NR¹⁷R¹⁸, -NR¹⁷COR¹⁸, -NR¹⁷CON R¹⁸R¹⁹, aryl, heterocyclyl or heteroaryl; wherein the aryl, the heterocyclyl or the heteroaryl is unsubstituted or substituted with one or more substituents R¹⁰;R¹³ is hydrogen, -COR¹⁷, alkyl or alkenyl; andR¹⁴ and R¹⁵ are each independently halogen, -CN, -N R¹⁷ R¹⁸, -O R¹⁷, -CO R¹⁷,-CO₂R¹⁷, -CONR¹⁷R¹⁸, -NR¹⁷COR¹⁸, -NR¹⁷CO₂R¹⁸, alkyl, heteroalkyl and alkenyl; wherein the alkyl, the heteroalkyl and the alkenyl is unsubstituted or substituted with one or more substituents R¹⁰.
[0004] The compound according to claim 1, or the optical isomer, the cis and trans isomers or the agromedically acceptable salt of the compound, characterized in that,when Y is N or CH;R¹¹ is halogen, -CN, -COR¹⁷, -CONR¹⁷R¹⁸, -S(O)R¹⁷, -NR¹⁷R¹⁸ or -NR¹⁷CO R¹⁸;R¹² is -S(O)R¹⁷, -S(O)₂R¹⁷, -NR¹⁷R¹⁸, -NR¹⁷COR¹⁸, aryl or heteroaryl; wherein the aryl or the heteroaryl is unsubstituted or substituted with one or more substituents R¹⁰;R¹³ is hydrogen, -COR¹⁷, alkyl or alkenyl;R¹⁴ and R¹⁵ are each independently halogen, -CN, -N R¹⁷ R¹⁸, -O R¹⁷, -CO R¹⁷,-CO₂ R¹⁷, -CONR¹⁷R¹⁸, -NR¹⁷COR¹⁸, -NR¹⁷CO₂R¹⁸, alkyl, heteroalkyl or alkenyl; wherein the alkyl or the alkenyl is unsubstituted or substituted with one or more substituents R¹⁰; andZ¹, Z², Z³ and Z⁴ are all C, one or more R¹⁶ are provided, and each R¹⁶ is independently halogen, alkyl, heteroalkyl, -S(O) R¹⁷, -S(O)₂R¹⁷, -COR¹⁷, -NR¹⁷R¹⁸, -N R¹⁷COR¹⁸ or -NR¹⁷S(O)₂R¹⁸.
[0005] The compound according to claim 4, or the optical isomer, the cis and trans isomers or the agromedically acceptable salt of the compound, characterized in that,R¹¹ is halogen, -CN, -COR¹⁷ or -CONR¹⁷R¹⁸;R¹² is -S(O)R¹⁷, -S(O)₂R¹⁷, -NR¹⁷COR¹⁸, aryl or heteroaryl; wherein the aryl or the heteroaryl is unsubstituted or substituted with one or more substituents R¹⁰;R¹³ is hydrogen, -COR¹⁷ or alkyl; andZ¹, Z², Z³ and Z⁴ are all C, one or more R¹⁶ are provided, and each R¹⁶ is independently halogen, heteroalkyl, -S(O)R¹⁷, -NR¹⁷R¹⁸ or -NR¹⁷COR¹⁸.
[0006] The compound according to claim 4, or the optical isomer, the cis and trans isomers or the agromedically acceptable salt of the compound, characterized in that,R¹¹ is -CN or -COR¹⁷;R¹² is -S(O)R¹⁷ or aryl; wherein the aryl is substituted with one or more substituents R¹⁰;R¹³ is hydrogen, -COR¹⁷, methyl or ethyl;R¹⁴ and R¹⁵ are each independently halogen, -OR¹⁷, -COR¹⁷, -CO₂R¹⁷,-CONR¹⁷R¹⁸, -NR¹⁷COR¹⁸, -NR¹⁷CO₂R¹⁸, alkyl, heteroalkyl or alkenyl; wherein the alkyl or the alkenyl is unsubstituted or substituted with one or more substituents R¹⁰; andZ¹, Z², Z³ and Z⁴ are all C, one or more R¹⁶ are provided, and each R¹⁶ is independently halogen or heteroalkyl.
[0007] The compound according to claim 4, or the optical isomer, the cis and trans isomers or the agromedically acceptable salt of the compound, characterized in that,R¹¹ is -CN or -COR¹⁷, and R¹⁷ is alkyl or heteroalkyl;R¹² is -S(O)R¹⁷, and R¹⁷ is alkyl or heteroalkyl;R¹³ is hydrogen, -COR¹⁷, methyl or ethyl, and R¹⁷ is alkyl;R¹⁴ and R¹⁵ are each independently halogen, -OR¹⁷, -COR¹⁷, -CO₂R¹⁷,-CONR¹⁷R¹⁸, -NR¹⁷COR¹⁸, -NR¹⁷CO₂R¹⁸, alkyl, heteroalkyl or alkenyl; wherein the alkyl or the alkenyl is unsubstituted or substituted with one or more substituents R¹⁰; andZ¹, Z², Z³ and Z⁴ are all C, one or more R¹⁶ are provided, and each R¹⁶ is independently halogen or heteroalkyl.
[0008] A pyrazole-ring-containing fused heterocyclic compound, and an optical isomer, cis and trans isomers or an agromedically acceptable salt thereof, characterized in that the pyrazole-ring-containing fused heterocyclic compound has a structure shown in formula (II):
[0009] The compound according to claim 8, or the optical isomer, the cis and trans isomers or the agromedically acceptable salt of the compound, characterized in that,when Z¹ is N and Z² is C, R⁶ is a monosubstituent -CF₃ at a 5-position of a pyridine ring, and the general formula of the compound is shown in formula (a):
[0010] The compound according to claim 9, or the optical isomer, the cis and trans isomers or the agromedically acceptable salt of the compound, characterized in that, R⁴ and R⁵ are each independently hydrogen, halogen, -CN, -COR⁷, -CO₂R⁷,-CH₂COR⁷, -CH₂COOR⁷, amino, alkyl or heteroalkyl; wherein R⁷ is hydrogen, halogen, hydroxyl, C_1-4 alkyl, C_1-4 haloalkyl, C_1-4 alkenyl, C_1-4 haloalkenyl, amino or substituted amino.
[0011] The compound according to claim 9, or the optical isomer, the cis and trans isomers or the agromedically acceptable salt of the compound, characterized in that, when the compound is shown in the formula (a) or the formula (b), and any one of R⁴ and R⁵ is hydrogen, R¹ is -CN, and R² is -SOCF₃ or -OCF₃; or R¹ is -CF₃, and R² is-SOCF₃;or, when neither R⁴ nor R⁵ is hydrogen, R¹ is -CN or -CF₃; and R² is -SOCF₃,-SOCH₂CH₃, -OCF₃, -CF₃, -CN or halogen.
[0012] The compound according to claim 9, or the optical isomer, the cis and trans isomers or the agromedically acceptable salt of the compound, characterized in that, when the compound is shown in the formula (c), R³ is -CH₃, -Ac or -CH₂CH₂Cl, R² is -SOCF₃, R¹ is -CN, and both R⁴ and R⁵ are -CO₂Me;or, when R³ is hydrogen, and R² is -CN, -CF₃ or -SOCH₂CH₃, R¹ is -CN or -CF₃, and R⁴ and R⁵ are each independently -CO₂Me or- -CH₂CO₂Me;or, when R³ is hydrogen, and R² is -OCF₃ or -SOCF₃, R¹ is -CN or -CF₃, R⁴ and R⁵ are each independently hydrogen, halogen, -CN, -COR⁷, -CO₂R⁷, -CH₂COR⁷,-CH₂COOR⁷, amino, alkyl, heteroalkyl, aryl or heteroaryl; wherein the amino, the alkyl, the aryl or the heteroaryl is unsubstituted or substituted with one or more substituents R⁹.
[0013] The compound according to claim 9, or the optical isomer, the cis and trans isomers or the agromedically acceptable salt of the compound, characterized in that, when the compound is shown in the formula (d), R³ is hydrogen, and R² is -CN, -CF₃, -SOPh, -SOCH₂Ph, -SOC₆H₁₃, or
[0014] The compound according to claim 9, or the optical isomer, the cis and trans isomers or the agromedically acceptable salt of the compound, characterized in that, when the compound is shown in the formula (e), R⁶ is 3-Cl and 6-CF₃, 3-Cl and 4-CF₃, 4-Cl and 5-CF₃, or 5-Cl and 6-CF₃ on the benzene ring; and R⁴ and R⁵ are each independently -CO₂Me, -CH₂CO₂Me, -CO₂Et, -CH₂CO₂Et, -CH₂CO₂CH₂CF₃ or-CH₂CO₂CH₂CHF₂.
[0015] An agricultural composition, comprising:
(a) 0.001 to 99.99% by weight of the compound according to any one of claims 1 to 14, the optical isomer, the cis and trans isomers or the agromedically acceptable salt thereof, or a combination thereof; and
(b) an agromedically acceptable carrier and/or excipient.
[0016] Use of the agricultural composition according to claim 15 in preparing an insecticide for killing or preventing agroforestry pests, sanitary insect pests and pests harmful to animal health.
[0017] The use according to claim 16, characterized in that, the insecticide is directly applied to the pests or places contacted by the pests.

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同族专利:

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公开号 | 公开日

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JP2021508674A|2021-03-11|

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WO2019086009A1|2019-05-09|

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BR112020008750A2|2020-10-20|

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EP3689877A4|2020-08-19|

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