CN109761989A - The preparation method of a kind of fused heterocyclic compound - Google Patents
The preparation method of a kind of fused heterocyclic compound Download PDFInfo
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- CN109761989A CN109761989A CN201910068917.8A CN201910068917A CN109761989A CN 109761989 A CN109761989 A CN 109761989A CN 201910068917 A CN201910068917 A CN 201910068917A CN 109761989 A CN109761989 A CN 109761989A
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Abstract
The invention discloses a kind of preparation methods of condensed heterocyclic compouds.The preparation method is with 5- amino -1HArylpyrazole substrateFor raw material A, is reacted in base agent, solvent with raw material B and the condensed heterocyclic compouds are made；Wherein Y is,Or；The raw material BOr
Description
Technical field
The invention belongs to heterocyclic compounds to synthesize field, the in particular to preparation method of a kind of condensed heterocyclic compouds.
Background technique
Inventor is found to have condensed heterocyclic compouds listed by CN201711069917.7 and CN201810219338.4
There is high killing activity to agriculture and forestry pest and sanitary insect pest etc..But in existing synthetic method, complex steps, the examination of use
Agent is more, isolates and purifies complexity, and needs further to limit existing method using expensive or toxic metallic catalyst
It is widely used.It is therefore desirable to develop a kind of more convenient and fast preparation method.Consulting literatures discovery, transition metal-catalyzed C-H bond
Activation, receives extensive research, wherein the carbon-hydrogen bond activation containing aminated compounds reacts, in subsequent tandem molecule nearly ten years
Addition reaction, the nitrogen-containing heterocycle of pyrroles or piperidine structure can be contained with rapid build, rapidly the complicated molecular skeleton of building
(Angew.Chem.Int.Ed.,2017,56,5336；Chem.Sci.,2017,8,3586；Organometallics,2017,
36,911；J.Am.Chem.Soc.,2016,138,2055；Acs Catal.,2016,6,1971；Nat.Chem.,2015,7,
1009；J.Am.Chem.Soc.,2014,136,5267.).Based on the above Research foundation, we design similar synthesis road
Line: azepine addition reaction, virtue in subsequent tandem molecule are carried out between aryl pyrazole compound and olefin(e) compound containing amino
Fragrant nucleophilic substitution equally can have item with rapid build nitrogen-containing heterocycle compound, and without using transition-metal catalyst
The features such as part is mild.
Summary of the invention
The purpose of the present invention is to provide the preparation methods of a kind of condensed heterocyclic compouds.This method can easily be realized thick
Close the synthesis of heterocyclic compound.
Above-mentioned purpose of the invention is achieved by following technical solution:
The preparation method of a kind of condensed heterocyclic compouds, the fused heterocyclic compound have the following structure formula:
The preparation method includes the following steps:
With 5- amino -1H- arylpyrazole substrateFor raw material A, reacted in base agent, solvent with raw material B,
Then it is separated, obtains the condensed heterocyclic compouds；
Wherein Y is
The raw material B
R1Selected from hydrogen, halogen ,-CN ,-CO2R8、-CONR8R9, alkyl, aryl or heteroaryl；Wherein alkyl, aryl or heteroaryl
Base is unsubstituted or through one or more substituent R10Replace；
R2Selected from hydrogen, halogen ,-CN ,-CO2R8、-CONR8R9、-S(O)R8、-S(O)2R8, alkyl, aryl or heteroaryl；Its
Middle alkyl, aryl or heteroaryl are unsubstituted or through one or more substituent Rs10Replace；
R3, X be leaving group；
R4Selected from hydrogen, halogen ,-NO2、-CF3、-COR8、-CO2R8Or-CN；
R5For-NO2、-CF3、-CHF2、-CN、-COR8、-CO2R8、-S(O)R8Or-S (O)2R8；
R6、R7It is independently selected from hydrogen, halogen ,-COR8、-CN、-CO2R8、-CONR8R9、-OR8、-NR8R9, alkyl or miscellaneous alkyl,
Wherein alkyl is unsubstituted or through one or more substituent R10Replace；And R6、R7In at least one be electron-withdrawing group；
R8And R9It is each independently hydrogen, alkyl, miscellaneous alkyl, C2~C6Alkenyl, C3~C8Naphthenic base, C3~C8It is cycloalkenyl, miscellaneous
Ring group, aryl or heteroaryl；Wherein alkyl, alkenyl, naphthenic base, cycloalkenyl, aryl, heterocycle or heteroaryl be unsubstituted or
Through one or more substituent Rs10Replace；
R10For halogen, alkyl, C2~C6Alkenyl ,-CN ,-NH2、-OR’、-NR’R”、-COR’、-CO2R’、-CONR’R”、-
NR’COR”、-NR’CONR’R”、-NR’CO2R”、-S(O)2R ' or-NR ' S (O)2R ", wherein R ' and R " is independently hydrogen, C1
~C6Alkyl, C2~C6Alkenyl, naphthenic base, cycloalkenyl, aryl, heteroaryl, heterocycle；
R11、R12It is independently selected from hydrogen, halogen ,-NO2、-COR8、-CN、-CO2R8、-OR8、-NR8R9、C1~C6Alkyl or C1~
C6Miscellaneous alkyl；Wherein alkyl is unsubstituted or through one or more substituent R10Replace；And when the aryl is pyridine ring,
R11、R12It cannot be electron-donating group, i.e. R11、R12It is not-OR8、-NR8R9、C1~C6Alkyl or C1~C6Miscellaneous alkyl；And when described
Aryl is phenyl ring, R4When for hydrogen, R11、R12For electron-withdrawing group.
Inventors have found that 5- amino -1H- arylpyrazole substrate can be with the alkene with electron-withdrawing group or specific alkane
React, and have it is specific under the conditions of, the structure of reaction product can rotate rearrangement, specifically:
1) when aryl is phenyl ring, when having strong electron-withdrawing group group on the position 4- of phenyl ring, that is, the R is had5When；
Or 2) when aryl is pyridine ring, the N on pyridine ring is located at contraposition or the ortho position for the carbon atom being connected with pyrazole ring
When；
Meeting above-mentioned 1) or 2) under the conditions of, the condensed heterocyclic compouds that can be prepared have the following structure:
Preferably, the R6Or R7In, the electron-withdrawing group preferably is selected from :-CO2R8、-COR8,-CN, halogen or-CF3。
Preferably, the leaving group preferably is selected from fluorine, chlorine, bromine, iodine ,-OMs or-OTs.
Preferably, the R1Selected from-CN ,-CO2R8、-CONR8R9, aryl or heteroaryl；Aryl or heteroaryl are unsubstituted
Or through one or more substituent Rs10Replace.
Preferably, the R2Selected from hydrogen, halogen ,-CO2R8、-CONR8R9、-S(O)R8、-S(O)2R8, aryl or heteroaryl；
Wherein alkyl, aryl or heteroaryl are unsubstituted or through one or more substituent Rs10Replace.
Preferably, the R5Selected from-NO2、-CF3、-CHF2、-CO2R8Or-S (O) R8。
Preferably, the R11Or R12It is independently selected from hydrogen, halogen ,-NO2、-COR8,-CN or-CO2R8。
Preferably, the R8、R9Or R10It is independently selected from hydrogen, halogen, C1~C6Alkyl, aryl or heteroaryl.
Preferably, wherein the solvent be selected from tetrahydrofuran, n,N-Dimethylformamide, N, N- dimethyl propylene alkenyl urea,
The mixtures of the one or more of N-Methyl pyrrolidone, dimethyl sulfoxide, dioxane, acetonitrile, water or alcohols.More preferably
For the mixed solvent of any or acetonitrile and water in, n,N-Dimethylformamide, acetonitrile, water；The mixing of the acetonitrile and water
In solvent, the volume ratio of acetonitrile and water can be 1:0.1~1:10.
Preferably, the reaction time is 0.2~48 hour.It is highly preferred that the reaction time is 3~24 hours.
The temperature of the reaction is unlimited, it is preferable that the temperature of the reaction is preferably -20~120 DEG C.More it is selected as 30~
80℃。
Preferably, the base agent is selected from potassium carbonate, saleratus, sodium carbonate, cesium carbonate, cesium fluoride, potassium tert-butoxide, carbon
The one or more of sour lithium, potassium hydroxide, pyridine, DBU or DABCO.
More preferably potassium carbonate, saleratus, cesium carbonate, cesium fluoride, potassium tert-butoxide or DABCO.
Preferably, the molar ratio of 5- amino -1H- Phenylpyrazole substrate and base agent is 1:0.5~1:5；5- amino -1H-
The molar ratio of Phenylpyrazole and raw material B are 1:0.5~1:2.
It is highly preferred that the molar ratio of 5- amino -1H- Phenylpyrazole substrate and base agent is 1:1~1:2.5.
For preparation method of the present invention, it is certain prepare target product when, might have a small amount of by-product and generate, root
According to nuclear-magnetism, mass spectrum etc. analyze, it is believed that may be as caused by a small amount of not rearrangement product, can by column chromatography for separation obtain compared with
Pure target product；The sample bigger for the amount of by-product can also be with other than the method separation that column chromatography can be used
Purer target product is obtained by preparing the method separation of phase liquid chromatography.Specific condition those skilled in the art can root
It is grasped according to actual conditions.
In the present invention, unless be otherwise noted in context, below word, phrase and the symbol to be used, to be expressed
Meaning has following regulation.It abridges below and the meaning of term runs through whole text:
Term " halogen " refers to fluorine, chlorine, bromine and iodine.
Term " alkyl " refers to that alkyl, the alkyl select self-saturating linear chain or branched chain alkyl.It preferably includes 1~12
Carbon atom (i.e. C1~C12), more preferable 1~6 carbon atom (i.e. C1~C6), such as methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, isobutyl group, sec-butyl, tert-butyl or similar group.
Term " miscellaneous alkyl " refers to that, including at least one heteroatomic alkyl, hetero atom refers to non-C atom.Hetero atom is preferred
N, O or S etc..
When miscellaneous alkyl, which contains an O atom, is alkoxy, the oxyl selects self-saturating linear chain or branched chain hydrocarbon oxygen
Base.It includes 1~12 carbon atom, preferably 1~6 carbon atom, for example, methoxyl group, ethyoxyl, positive propoxy, isopropoxy,
N-butoxy, isobutoxy, sec-butoxy, tert-butoxy or similar group.
Term " aryl " refers to group chosen from the followings: 5 yuan and 6 yuan of carbocyclic aromatic rings, for example, phenyl, furan nucleus or thiophene
Pheno ring；Term " heteroaryl " refers to group chosen from the followings: 5~7 yuan of aromatic monocyclics, and it includes 1,2,3 or 4 to be selected from N, O
With the hetero atom of S, remaining annular atom is carbon.
Term " naphthenic base " refers to the alkyl selected from saturation or the unsaturated cyclic hydrocarbon radical in part comprising monocycle or polycyclic group
Group.It can have 3~12 carbon atoms in naphthenic base.For example, naphthenic base can be the monocycle base with 3~12 carbon atoms
Group, the example of monocyclic naphthenes base includes cyclopropyl, cyclobutyl, cyclopenta, the amyl- 1- alkenyl of 1- ring, the amyl- 2- alkenyl of 1- ring, 1-
The amyl- 3- alkenyl of ring, cyclohexene, 1- hexamethylene -1- alkenyl, 1- hexamethylene -2- alkenyl, 1- hexamethylene -3- alkenyl, cyclohexadiene, cycloheptene,
Cyclo-octene, cyclononyl, cyclodecyl, ring undecyl and cyclo-dodecyl.Naphthenic base can also be with 3~12 carbon atoms
Bicyclic radicals, the example of bicyclic cycloalkyl group include rearranging selected from [4,4], [4,5], [5,5], [5,6] and [6,6] ring body
Bicyclic or selected from bicyclic [2.2.1] heptane, bicyclic [2.2.2] octane and bicyclic [3.2.2] nonane the bridging of system is bicyclic.It is described
It is that ring can be saturation or there is at least one double bond, but be not completely to be conjugated, it and is not aromatic (as defined herein
Aromatic series).
Term " alkenyl " refers to the alkyl selected from straight chain and branched hydrocarbyl, including at least one C=C double bond, leads to
Often include 2~12 carbon atoms, preferably includes 2~6 carbon atoms.The example of alkenyl can selected from vinyl, propyl- 1- alkenyl,
Propyl- 2- alkenyl, 2- methyl propyl- 1- alkenyl, but-1-ene base, but-2-ene base, butyl- 3- alkenyl, butyl- 1,3- dialkylene, 2- methyl-
1,3- butadiene, hex- 1- alkenyl, hex- 2- alkenyl, hex- 3- alkenyl, hex- 4- alkenyl and hex- 1,3- dialkylene group.
Term " cycloalkenyl " refers to selected from unsaturated cyclic hydrocarbon radical, and it contains at least one C=C double bond, but has not been
Full conjugation, and be not aromatic series comprising monocycle or polycyclic moiety.Cyclopentene, cyclopentadiene, hexamethylene in cycloalkenyl
Alkene, cyclohexadiene, pentalene or similar group.
Compared with prior art, the invention has the following beneficial effects:
The present invention provides the new preparation method of the condensed heterocyclic compouds.The more published method tool of the preparation method
There is the features such as step is simple, and reagent is easy to get, high income, is suitble to the large-scale production to condensed heterocyclic compouds.
Specific embodiment
Explanation that the present invention will be further explained combined with specific embodiments below, but specific embodiment is not to the present invention
It is limited in any way.Unless stated otherwise, reagent, method and apparatus involved in embodiment are conventional examination commonly used in the art
Agent, method and apparatus.
Embodiment 1: raw material A
In 50 milliliters of reaction flasks, 0.25 mM of 5- amino -1- (2,6- bis- chloro- 4- fluoroform phenyl) -4- three is added
Methyl fluoride sulfinyl pyrazoles -3- nitrile, 0.275 mM of butene dioic acid dimethyl ester are reacted under the conditions of table 1, have been reacted
Cheng Hou is cooled to room temperature, and water is added and is extracted with ethyl acetate three times, and it is molten that anhydrous magnesium sulfate dries, filters vacuum rotary steam removing
Agent obtains product by column chromatographic isolation and purification, and the column chromatographic eluate used is the petroleum ether that volume ratio is 10:1~5:1:
Ethyl acetate mixed solvent.
Table 1
a:MeCN/H2O=1:1 (v/v)；b:The molar ratio of 5- amino -1H- Phenylpyrazole substrate and base agent is 1:0.5；
c:The molar ratio of 5- amino -1H- Phenylpyrazole substrate and base agent is 1:2.0；d:Reaction time is 8 hours.
Under the preferred reaction conditions (i.e. condition 3) of above-mentioned determination, reaction raw materials B and raw material A are expanded respectively, is tied
Fruit is as shown in 2~table of table 5:
The expansion of 2 raw material B of table
In table 2, the compound that patent disclosure is crossed before the compound of serial number 4, serial number 5 and serial number 13 is invention passes through sequence
Numbers 4, the nuclear-magnetism of serial number 5 and related data comparison, can be confirmed the structure for rearrangement.
3 raw material A structural formula of table isSubstrate expand
4 raw material A structural formula of table isSubstrate expand
5 raw material A structural formula of table isSubstrate expand
Table 6: the nuclear magnetic resonance spectroscopy and mass spectrometric data of compound shown in table 2
Table 7: the nuclear magnetic resonance spectroscopy and mass spectrometric data of compound shown in table 3
Table 8: the nuclear magnetic resonance spectroscopy and mass spectrometric data of compound shown in table 4
Table 9: the nuclear magnetic resonance spectroscopy and mass spectrometric data of compound shown in table 5
Compound structure involved in aforementioned is shown in Table 6~table 9 by mass spectrum, hydrogen spectrum identification, specific hydrogen spectrum and mass spectrum.
Embodiment 2: insecticidal activity embodiment
(1) to the insecticidal activity of 2 instar larvae of diamondback moth
Diamondback moth Plutella xylostella (L.) belongs to lepidoptera pest, has biting mouthparts, is a kind of common
Vegetable-crop pest-insect.Using 2 instar larvae of diamondback moth as test object, using leaching leaf feeding method test.
Operating process: precise each sample is separately added into 200 microlitres of dimethyl sulfoxide and is configured to 10g/L mother liquor, real
The concentration of 500ppm is diluted to when testing with the aqueous solution containing 0.5/1000th Tween-80s.It will with 1.0 centimetres of punch of diameter
Leaf dish is made in clean cabbage leaves, and the leaching of leaf dish is into the liquid, takes out, naturally dry, is moved into clean vessel after 5 seconds.Into vessel
2 instar larvae of diamondback moth of access 35-40 or so is raised in 28 degrees Celsius of constant temperature.Every concentration sets 3 repetitions, control group be containing
The aqueous solution of 0.5/1000th Tween-80s.After processing 24 hours, the dead borer population of diamondback moth is counted, and death is calculated according to formula
Rate: the death rate (%)=(compareing borer population-processing living borer population living)/compares borer population × 100% living.It the results are shown in Table 10~table 11.
(2) to the insecticidal activity of 2 instar larvae of beet armyworm
Beet armyworm Spodoptera exigua belongs to lepidoptera pest, has biting mouthparts, is a kind of common vegetable
Dish pest.Using 2 instar larvae of beet armyworm as test object, using leaching leaf feeding method test.
Operating process: precise each sample is separately added into 200 microlitres of dimethyl sulfoxide and is configured to 10g/L mother liquor, real
The concentration of 500ppm is diluted to when testing with the aqueous solution containing 0.5/1000th Tween-80s.It will with 1.0 centimetres of punch of diameter
Leaf dish is made in clean cabbage leaves, and the leaching of leaf dish is into the liquid, takes out, naturally dry, is moved into clean vessel after 5 seconds.Into vessel
2 instar larvae of beet armyworm of access 35-40 or so takes the photograph a degree Celsius constant temperature raising in 28 degrees Celsius.Every concentration sets 3 repetitions,
Control group is the aqueous solution containing 0.5/1000th Tween-80s.After processing 24 hours, the dead borer population of diamondback moth is counted, and according to public affairs
Formula calculates the death rate: the death rate (%)=(compareing borer population-processing living borer population living)/and compares borer population × 100% living.It the results are shown in Table
10~table 11.
(3) to the insecticidal activity of aphid adult
Aphid belongs to Homoptera pest, has sucking mouth parts, is a kind of common vegetable-crop pest-insect.With bean aphid (Aphis
Craccivora it is) test object, is tested using infusion process.
Operating process: precise each sample is separately added into 200 microlitres of dimethyl sulfoxide and is configured to 10g/L mother liquor, real
The concentration of 500ppm is diluted to when testing with the aqueous solution containing 0.5/1000th Tween-80s.Stablize on bean sprouts to aptery adult aphid
After sucking, is immersed together with bean sprouts in the medical fluid that concentration is 500ppm, taken out after 5 seconds, naturally dry, move into clean vessel
In, it is raised in 23 degrees Celsius of constant temperature.Every concentration sets 3 repetitions, and control group is the aqueous solution containing 0.5/1000th Tween-80s.Processing
After 24 hours, the dead borer population of aphid is counted, and the death rate: the death rate (%)=(compare borer population-place living is calculated according to formula
Manage borer population living)/compare borer population × 100% living.It the results are shown in Table 10~table 11.
(4) to the insecticidal activity of red fire ant worker ant
Red fire ant belongs to Hymenoptera pest, social insect, is a kind of one of great destructive power biological invasion.With red fire ant
Worker ant (Solenopsis invicta) is test object, feeds malicious method test using water test tube.
Operating process: precise each sample is separately added into 200 microlitres of dimethyl sulfoxide and is configured to 10g/L mother liquor, real
The concentration of 100ppm is diluted to when testing with the mixed aqueous solution containing 0.5/1000th Tween-80s and 5 percent honey.It takes red
Fiery ant is placed in feeding ant test tube, and medical fluid is injected in the silica gel plug for supporting ant test tube with syringe, and not oozed out with medical fluid is advisable.Rest ant
Test tube is flat in feeding ant box, and a small amount of ham sausage is added as food to test tube, raises in 25 degrees Celsius of constant temperature.Processing for 24 hours and
72h investigates borer population living and dead borer population, and calculates the death rate: the death rate (%)=(compare borer population-processing living worm living according to formula
Number)/compare borer population × 100% living.It the results are shown in Table 10~table 11.
Insecticidal activity of the part of compounds shown in 10 table 2 of table to test pest
Insecticidal activity of the part of compounds shown in 11 table 3 to table 5 of table to test pest
As can be seen from the table, the present invention enumerates compound and the CN201711069917.7 of disclosed patent before and
Activity in CN201810219338.4 is similar.There is height to agriculture and forestry pest, Animal Parasitic pest and sanitary insect pest etc.
Killing activity, especially there is activity well to pests such as Lepidoptera, Homoptera, Hymenopteras, and have to red fire ant and prolong
The effect of Shi Qixiao has better killing effect to entire red fire ant ant nest and queen.
All documents that the present invention refers to are incorporated herein by reference, and are individually drawn just as each document
It is used as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can be with
The present invention is made various changes or modifications, such equivalent forms equally fall into model defined by the application the appended claims
It encloses.
Claims (10)
1. the preparation method of a kind of fused heterocyclic compound, which is characterized in that the fused heterocyclic compound has the following structure formula:
；
The preparation method includes the following steps:
With 5- amino -1HArylpyrazole substrateFor raw material A, reacted in base agent, solvent with raw material B, then
It is separated, obtains the condensed heterocyclic compouds；
Wherein Y is；
The raw material BOr；
R1Selected from hydrogen, halogen ,-CN ,-CO2R8、-CONR8R9, alkyl, aryl or heteroaryl；Wherein alkyl, aryl or heteroaryl be not
It is substituted or through one or more substituent Rs10Replace；
R2Selected from hydrogen, halogen ,-CN ,-CO2R8、-CONR8R9、-S(O)R8、-S(O)2R8, alkyl, aryl or heteroaryl；Wherein alkane
Base, aryl or heteroaryl are unsubstituted or through one or more substituent Rs10Replace；
R3, X be leaving group；
R4Selected from hydrogen, halogen ,-NO2、-CF3、-COR8、-CO2R8Or-CN；
R5For-NO2、-CF3、-CHF2、-CN、-COR8、-CO2R8、-S(O)R8Or-S (O)2R8；
R6、R7It is independently selected from hydrogen, halogen ,-COR8、-CN、-CO2R8、-CONR8 R9、-OR8、-NR8R9, alkyl or miscellaneous alkyl, wherein
Alkyl is unsubstituted or through one or more substituent R10Replace；And R6、R7In at least one be electron-withdrawing group；
R8And R9It is each independently hydrogen, alkyl, miscellaneous alkyl, C2~C6Alkenyl, C3~C8Naphthenic base, C3~C8Cycloalkenyl, heterocycle
Base, aryl or heteroaryl；Wherein alkyl, alkenyl, naphthenic base, cycloalkenyl, aryl, heterocycle or heteroaryl are unsubstituted or pass through
One or more substituent Rs10Replace；
R10For halogen, alkyl, C2~C6Alkenyl ,-CN ,-NH2、-OR’、-NR’R’’、-COR’、-CO2R’、-CONR’R’’、-NR’
COR’’、-NR’CONR’R’’、-NR’CO2R’’、-S(O)2R ' or-NR ' S (O)2R ' ', wherein R ' and R ' ' be independently hydrogen,
C1~C6Alkyl, C2~C6Alkenyl, naphthenic base, cycloalkenyl, aryl, heteroaryl, heterocycle；
R11、R12It is independently selected from hydrogen, halogen ,-NO2、-COR8、-CN、-CO2R8、-OR8、-NR8R9、C1~C6Alkyl or C1~C6It is miscellaneous
Alkyl；Wherein alkyl is unsubstituted or through one or more substituent R10Replace；And when the aryl is pyridine ring, R11、R12
It cannot be electron-donating group；And when the aryl is phenyl ring, R4When for hydrogen, R11、R12For electron-withdrawing group.
2. the preparation method of fused heterocyclic compound according to claim 1, it is characterised in that: the R6Or R7In, the suction electricity
Subbase group is selected from :-CO2R8、-COR8,-CN, halogen or-CF3。
3. the preparation method of fused heterocyclic compound according to claim 1, it is characterised in that: the leaving group be selected from fluorine,
Chlorine, bromine, iodine ,-OMs or-OTs.
4. the preparation method of fused heterocyclic compound according to claim 1, it is characterised in that: the R1Selected from-CN ,-
CO2R8、-CONR8R9, aryl or heteroaryl；Aryl or heteroaryl are unsubstituted or through one or more substituent Rs10Replace.
5. the preparation method of fused heterocyclic compound according to claim 1, it is characterised in that: the R2Selected from hydrogen, halogen ,-
CO2R8、-CONR8R9、-S(O)R8、-S(O)2R8, aryl or heteroaryl；Wherein alkyl, aryl or heteroaryl are unsubstituted or pass through
One or more substituent Rs10Replace.
6. the preparation method of fused heterocyclic compound according to claim 1, it is characterised in that: the R5Selected from-NO2、-CF3、-
CHF2、-CO2R8Or-S (O) R8。
7. the preparation method of fused heterocyclic compound according to claim 1, it is characterised in that: the R11Or R12It is independently selected from
Hydrogen, halogen ,-NO2、-COR8,-CN or-CO2R8。
8. the preparation method of fused heterocyclic compound according to claim 1, it is characterised in that: the R8、R9Or R10It is independently selected from
Hydrogen, halogen, C1~C6Alkyl, aryl or heteroaryl.
9. the preparation method of fused heterocyclic compound according to claim 1, it is characterised in that: wherein, the solvent is selected from four
Hydrogen furans, N,N-dimethylformamide, N, N- dimethyl propylene alkenyl urea, N-Methyl pyrrolidone, dimethyl sulfoxide, dioxy six
The mixtures of the one or more of ring, acetonitrile, water or alcohols；Reaction time is 0.2 ~ 48 hour.
10. the preparation method of fused heterocyclic compound according to claim 1, it is characterised in that: the base agent is selected from carbonic acid
Potassium, saleratus, sodium carbonate, cesium carbonate, cesium fluoride, potassium tert-butoxide, lithium carbonate, potassium hydroxide, pyridine, DBU or DABCO one
Kind is several.
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| WO2016204270A1 (en) * | 2015-06-18 | 2016-12-22 | 日本曹達株式会社 | Diaryl azole compound and pesticide |
| CN108003162A (en) * | 2017-11-03 | 2018-05-08 | 华南农业大学 | Condensed heterocyclic compouds and its application |
| CN108129481A (en) * | 2018-03-16 | 2018-06-08 | 华南农业大学 | Condensed heterocyclic compouds and its application of the one kind containing pyrazole ring |
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| CN109734719A (en) * | 2019-01-24 | 2019-05-10 | 华南农业大学 | The preparation method of fused heterocyclic compound |
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