CN109761989B - Preparation method of fused heterocyclic compound - Google Patents

Preparation method of fused heterocyclic compound Download PDF

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CN109761989B
CN109761989B CN201910068917.8A CN201910068917A CN109761989B CN 109761989 B CN109761989 B CN 109761989B CN 201910068917 A CN201910068917 A CN 201910068917A CN 109761989 B CN109761989 B CN 109761989B
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heterocyclic compound
heteroaryl
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CN109761989A (en
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徐汉虹
江薰垣
赵晨
赖秋勤
邓成菊
张志祥
林菲
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South China Agricultural University
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Abstract

The invention discloses a preparation method of a condensed heterocyclic compound. The preparation method is to take 5-amino-1H-arylpyrazole substrates
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Reacting a raw material A with a raw material B in an alkali assistant and a solvent to prepare the condensed heterocyclic compound; wherein Y is
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，
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Or
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(ii) a The raw material B
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Or

Description

Preparation method of fused heterocyclic compound
Technical Field
The invention belongs to the field of heterocyclic compound synthesis, and particularly relates to a preparation method of a fused heterocyclic compound.
Background
The inventors found that the fused heterocyclic compounds listed in CN201711069917.7 and CN201810219338.4 have high pesticidal activity against agricultural and forestry pests, sanitary pests and the like. However, the existing synthetic method has the disadvantages of complicated steps, more reagents, complicated separation and purification, and the need of using expensive or toxic metal catalysts, which further limits the wide application of the existing method. Therefore, it is necessary to develop a more convenient preparation method. The carbon-hydrogen bond activation catalyzed by transition metals has been widely studied in recent decades, wherein the carbon-hydrogen bond activation reaction of amine-containing compounds followed by the intramolecular tandem addition reaction can rapidly construct nitrogen-containing heterocycles containing pyrrole or piperidine structures and rapidly construct complex molecular frameworks (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, 1009, J.Am. chem. Soc.,2014,136,5267.). Based on the above research, we designed a similar synthetic route: the nitrogen-containing heterocyclic compound can be quickly constructed by carrying out aza addition reaction between the amino-containing aryl pyrazole compound and the olefin compound and then carrying out intramolecular aromatic nucleophilic substitution reaction in series, and the method does not need to use a transition metal catalyst and has the characteristics of mild conditions and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a fused heterocyclic compound. The method can simply realize the synthesis of the condensed heterocyclic compound.
The above object of the present invention is achieved by the following technical solutions:
a process for the preparation of a fused heterocyclic compound having the formula:
Figure BDA0001956643560000021
the preparation method comprises the following steps:
with 5-amino-1H-arylpyrazole substrates
Figure BDA0001956643560000022
Reacting a raw material A with a raw material B in an alkali assistant and a solvent, and then separating to obtain the condensed heterocyclic compound;
wherein Y is
Figure BDA0001956643560000023
The raw material B
Figure BDA0001956643560000024
R1Selected from hydrogen, halogen, -CN, -CO2R8、-CONR8R9Alkyl, aryl or heteroaryl; wherein the alkyl, aryl or heteroaryl radical is unsubstituted or substituted by one or more substituents R10Substitution;
R2selected from hydrogen, halogen, -CN, -CO2R8、-CONR8R9、-S(O)R8、-S(O)2R8Alkyl, aryl or heteroaryl; wherein the alkyl, aryl or heteroaryl radical is unsubstituted or substituted by one or more substituents R10Substitution;
R3and X are leaving groups;
R4selected from hydrogen, halogen, -NO2、-CF3、-COR8、-CO2R8or-CN;
R5is-NO2、-CF3、-CHF2、-CN、-COR8、-CO2R8、-S(O)R8or-S (O)2R8；
R6、R7Independently selected from hydrogen, halogen, -COR8、-CN、-CO2R8、-CONR8R9、-OR8、-NR8R9Alkyl or heteroalkyl, wherein alkyl is unsubstituted or substituted with one or more substituents R10Substitution; and R is6、R7At least one is an electron withdrawing group;
R8and R9Each independently is hydrogen, alkyl, heteroalkyl, C2～C6Alkenyl radical, C3～C8Cycloalkyl radical, C3～C8Cycloalkenyl, heterocyclyl, aryl or heteroaryl; wherein the alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl or heteroaryl is unsubstituted or substituted by one or more substituents R10Substitution;
R10is 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 ' where R ' and R ' are independently hydrogen, C1～C6Alkyl radical, C2～C6Alkenyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocyclyl;
R11、R12independently selected from hydrogen, halogen, -NO2、-COR8、-CN、-CO2R8、-OR8、-NR8R9、C1～C6Alkyl or C1～C6A heteroalkyl group; wherein the alkyl radical is unsubstituted or substituted by one or more substituents R10Substitution; and when said aryl group is a pyridine ring, R11、R12Not being electron-donating groups, i.e. R11、R12Is not-OR8、-NR8R9、C1～C6Alkyl or C1～C6A heteroalkyl group; and when said aryl is a phenyl ring, R4When it is hydrogen, R11、R12Are electron withdrawing groups.
The inventor finds that the 5-amino-1H-aryl pyrazole substrate can react with olefin with an electron-withdrawing group or specific alkane, and the structure of a reaction product can undergo rotational rearrangement under specific conditions, and particularly:
1) when the aryl group is a benzene ring, a strong electron-withdrawing group is present at the 4-position of the benzene ring, i.e., R is present5When the current is over;
or 2) when the aryl group is a pyridine ring, the N on the pyridine ring is para or ortho to the carbon atom attached to the pyrazole ring;
under the conditions of 1) or 2) which satisfy the above, a fused heterocyclic compound having the following structure can be produced:
Figure BDA0001956643560000031
preferably, said R is6Or R7Preferably, the electron withdrawing group is selected from: -CO2R8、-COR8-CN, halogen or-CF3。
Preferably, the leaving group is preferably selected from fluorine, chlorine, bromine, iodine, -OMs or-OTs.
Preferably, said R is1Selected from-CN, -CO2R8、-CONR8R9Aryl or heteroaryl; aryl or heteroaryl unsubstituted or substituted by one or more substituents R10And (4) substitution.
Preferably, said R is2Selected from hydrogen, halogen, -CO2R8、-CONR8R9、-S(O)R8、-S(O)2R8Aryl or heteroaryl; wherein the alkyl, aryl or heteroaryl radical is unsubstituted or substituted by one or more substituents R10And (4) substitution.
Preferably, said R is5Is selected from-NO2、-CF3、-CHF2、-CO2R8or-S (O) R8。
Preferably, said R is11Or R12Independently selected from hydrogen, halogen, -NO2、-COR8-CN or-CO2R8。
Preferably, said R is8、R9Or R10Independently selected from hydrogen, halogen, C1～C6Alkyl, aryl or heteroaryl.
Preferably, the solvent is one or a mixture of several of tetrahydrofuran, N-dimethylformamide, N-dimethyl propylene urea, N-methyl pyrrolidone, dimethyl sulfoxide, dioxane, acetonitrile, water or alcohols. More preferably, the solvent is any one of N, N-dimethylformamide, acetonitrile and water or a mixed solvent of acetonitrile and water; in the mixed solvent of acetonitrile and water, the volume ratio of acetonitrile to water can be 1: 0.1-1: 10.
Preferably, the reaction time is 0.2 to 48 hours. More preferably, the reaction time is 3 to 24 hours.
The reaction temperature is not limited, and preferably, the reaction temperature is-20 to 120 ℃. More preferably 30 to 80 ℃.
Preferably, the alkali assistant is selected from one or more of potassium carbonate, potassium bicarbonate, sodium carbonate, cesium fluoride, potassium tert-butoxide, lithium carbonate, potassium hydroxide, pyridine, DBU or DABCO.
More preferably potassium carbonate, potassium bicarbonate, cesium carbonate, cesium fluoride, potassium tert-butoxide or DABCO.
Preferably, the molar ratio of the 5-amino-1H-phenylpyrazole substrate to the alkali auxiliary agent is 1: 0.5-1: 5; the molar ratio of the 5-amino-1H-phenylpyrazole to the raw material B is 1: 0.5-1: 2.
More preferably, the molar ratio of the 5-amino-1H-phenylpyrazole substrate to the base auxiliary agent is 1: 1-1: 2.5.
According to the preparation method, a small amount of byproducts can be generated when a target product is prepared, and according to analysis such as nuclear magnetism and mass spectrometry, the byproducts are believed to be caused by a small amount of unrearranged products, and a relatively pure target product can be obtained through column chromatography separation; for samples with larger amount of byproducts, the target product can be obtained by separation by a preparative liquid chromatography method in addition to the column chromatography method. The specific conditions can be grasped by those skilled in the art according to actual conditions.
In the present invention, unless otherwise indicated by context, the following words, phrases and symbols are to be used, and the meanings to be expressed are defined as follows. The following abbreviations and terms have the meanings as set forth throughout:
the term "halogen" refers to fluorine, chlorine, bromine and iodine.
The term "alkyl" refers to a hydrocarbon group selected from saturated straight or branched chain hydrocarbon groups. It preferably comprises 1 to 12 carbon atoms (i.e., C)1～C12) More preferably 1 to 6 carbon atoms (i.e., C)1～C6) For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or the like.
The term "heteroalkyl" refers to an alkyl group that includes at least one heteroatom, which is a non-C atom. The heteroatom is preferably N, O or S, etc.
When the heteroalkyl group contains one O atom, i.e., an alkoxy group, the hydrocarbyloxy group is selected from saturated, straight or branched chain hydrocarbyloxy groups. It contains 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, or the like.
The term "aryl" refers to a group selected from: 5-and 6-membered carbocyclic aromatic rings, for example, phenyl, furan or thiophene rings; the term "heteroaryl" refers to a group selected from: a 5-7 membered aromatic monocyclic ring comprising 1, 2, 3 or 4 heteroatoms selected from N, O and S, the remaining ring atoms being carbon.
The term "cycloalkyl" refers to a hydrocarbon group selected from saturated or partially unsaturated cyclic hydrocarbon groups, including monocyclic or polycyclic groups. The cycloalkyl group may have 3 to 12 carbon atoms. For example, the cycloalkyl group may be a monocyclic group having 3 to 12 carbon atoms, and examples of the monocyclic cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, 1-cyclopent-1-enyl, 1-cyclopent-2-enyl, 1-cyclopent-3-enyl, cyclohexene, 1-cyclohex-1-enyl, 1-cyclohex-2-enyl, 1-cyclohex-3-enyl, cyclohexadiene, cycloheptene, cyclooctene, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl. The cycloalkyl group may also be a bicyclic group having 3 to 12 carbon atoms, and examples of the bicycloalkane group include a bicyclic ring having an arrangement composition selected from [4,4], [4,5], [5,6] and [6,6] ring systems or a bridged bicyclic ring selected from bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane and bicyclo [3.2.2] nonane. The ring may be saturated or have at least one double bond, but is not fully conjugated and is not aromatic (as defined herein).
The term "alkenyl" refers to a hydrocarbon group selected from straight and branched chain hydrocarbon groups, including at least one C ═ C double bond, typically comprising 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms. Examples of alkenyl groups may be selected from vinyl, prop-1-enyl, prop-2-enyl, 2-methylprop-1-enyl, but-2-enyl, but-3-enyl, but-1, 3-dienyl, 2-methyl-1, 3-butadiene, hex-1-enyl, hex-2-enyl, hex-3-enyl, hex-4-enyl and hex-1, 3-dienyl groups.
The term "cycloalkenyl" refers to a cyclic hydrocarbon group selected from unsaturated, and which contains at least one C ═ C double bond, but is not fully conjugated, and is not aromatic, and which includes monocyclic or polycyclic groups. Preferred cycloalkenyl groups are cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, pentalene, or similar groups.
Compared with the prior art, the invention has the following beneficial effects:
the present invention provides a novel method for preparing the fused heterocyclic compound. Compared with the disclosed method, the preparation method has the characteristics of simple steps, easily obtained reagents, high yield and the like, and is suitable for large-scale production of the fused heterocyclic compound.
Detailed Description
The present invention will be further explained with reference to specific examples, which are not intended to limit the present invention in any way. Reagents, methods and equipment referred to in the examples are conventional reagents, methods and equipment commonly used in the art, unless otherwise indicated.
Example 1: starting materials A
Figure BDA0001956643560000061
Adding 0.25 mmol of 5-amino-1- (2, 6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfinylpyrazole-3-nitrile and 0.275 mmol of dimethyl butenedioate into a 50 ml reaction bottle, reacting under the conditions shown in Table 1, cooling to room temperature after the reaction is finished, adding water, extracting for three times by using ethyl acetate, drying over anhydrous magnesium sulfate, filtering, decompressing, carrying out rotary evaporation to remove the solvent, and carrying out separation and purification by column chromatography to obtain a product, wherein the eluent of the column chromatography is petroleum ether with the volume ratio of 10: 1-5: 1: and (3) mixing the ethyl acetate and the solvent.
TABLE 1
Figure BDA0001956643560000062
Figure BDA0001956643560000071
a:MeCN/H2O＝1:1(v/v)；b:The molar ratio of the 5-amino-1H-phenyl pyrazole substrate to the alkali auxiliary agent is 1: 0.5;
c:the molar ratio of the 5-amino-1H-phenyl pyrazole substrate to the alkali auxiliary agent is 1: 2.0;d:the reaction time was 8 hours.
The reaction feed B and feed A were expanded under the preferred reaction conditions identified above (i.e., condition 3), and the results are shown in tables 2 to 5:
TABLE 2 expansion of feedstock B
Figure BDA0001956643560000072
Figure BDA0001956643560000081
In table 2, the compounds No. 4, No. 5 and No. 13 are compounds disclosed in the patent prior to the invention, and the rearrangement structure can be confirmed by comparing the nuclear magnetic and related data of No. 4 and No. 5.
TABLE 3 structural formula of raw material A
Figure BDA0001956643560000082
Substrate development
Figure BDA0001956643560000083
Figure BDA0001956643560000091
TABLE 4 structural formula of raw material A
Figure BDA0001956643560000092
Substrate development
Figure BDA0001956643560000093
Figure BDA0001956643560000101
TABLE 5 structural formula of raw material A
Figure BDA0001956643560000102
Substrate development
Figure BDA0001956643560000103
Figure BDA0001956643560000111
Table 6: NMR and Mass Spectroscopy data for the Compounds shown in Table 2
Figure BDA0001956643560000112
Figure BDA0001956643560000121
Table 7: NMR and Mass Spectroscopy data for the Compounds shown in Table 3
Figure BDA0001956643560000122
Figure BDA0001956643560000131
Figure BDA0001956643560000141
Table 8: NMR and Mass Spectroscopy data for the Compounds shown in Table 4
Figure BDA0001956643560000142
Figure BDA0001956643560000151
Figure BDA0001956643560000161
Table 9: NMR and Mass Spectroscopy data for the Compounds shown in Table 5
Figure BDA0001956643560000162
Figure BDA0001956643560000171
Figure BDA0001956643560000181
The structures of the related compounds are identified by mass spectra and hydrogen spectra, and the specific hydrogen spectra and mass spectra are shown in tables 6 to 9.
Example 2: examples of pesticidal Activity
(1) Insecticidal activity against diamondback moth 2-instar larvae
Plutella xylostella (L.) belongs to lepidopteran pests, has a chewing mouthpart, and is a common vegetable pest. The 2 nd larva of diamondback moth is taken as a test object and is tested by a dipping method.
The operation process is as follows: accurately weighing each sample, adding 200 microliter of dimethyl sulfoxide to prepare 10g/L mother liquor, and diluting the mother liquor to a concentration of 500ppm by using an aqueous solution containing 0.5 thousandth of tween-80 during experiment. Preparing cleaned cabbage leaves into leaf disks by using a puncher with the diameter of 1.0 cm, soaking the leaf disks into the liquid medicine, taking out after 5 seconds, naturally drying, and transferring into a clean vessel. Inoculating about 35-40 larvae of diamondback moth of 2 th instar into the vessel, and feeding at a constant temperature of 28 ℃. Each concentration was repeated 3 times, and the control group was an aqueous solution containing 0.5 part per thousand of Tween-80. After 24 hours of treatment, the number of dead diamondback moth insects is counted, and the death rate is calculated according to the formula: mortality (%) - (number of control live insects-number of treated live insects)/number of control live insects × 100%. The results are shown in tables 10 to 11.
(2) Insecticidal activity against 2-instar larvae of beet armyworm
Spodoptera exigua belonging to Lepidoptera pests, having chewing mouthparts, is a common vegetable pest. The 2 nd instar larvae of the asparagus caterpillars are taken as a test object and tested by a leaf soaking feeding method.
The operation process is as follows: accurately weighing each sample, adding 200 microliter of dimethyl sulfoxide to prepare 10g/L mother liquor, and diluting the mother liquor to a concentration of 500ppm by using an aqueous solution containing 0.5 thousandth of tween-80 during experiment. Preparing cleaned cabbage leaves into leaf disks by using a puncher with the diameter of 1.0 cm, soaking the leaf disks into the liquid medicine, taking out after 5 seconds, naturally drying, and transferring into a clean vessel. Inoculating about 35-40 larvae of beet armyworm of 2 years old into the vessel, and feeding at 28 deg.C under constant temperature. Each concentration was repeated 3 times, and the control group was an aqueous solution containing 0.5 part per thousand of Tween-80. After 24 hours of treatment, the number of dead diamondback moth insects is counted, and the death rate is calculated according to the formula: mortality (%) - (number of control live insects-number of treated live insects)/number of control live insects × 100%. The results are shown in tables 10 to 11.
(3) Insecticidal activity against adult aphids
The aphid belongs to the same-wing suborder pests, has a piercing-sucking mouthpart and is a common vegetable pest. Aphis fabae (Aphisscarcivora) is taken as a test object and tested by adopting a dipping method.
The operation process is as follows: accurately weighing each sample, adding 200 microliter of dimethyl sulfoxide to prepare 10g/L mother liquor, and diluting the mother liquor to a concentration of 500ppm by using an aqueous solution containing 0.5 thousandth of tween-80 during experiment. After the wingless adult aphids are stably sucked on the bean sprouts, the wingless adult aphids and the bean sprouts are immersed into liquid medicine with the concentration of 500ppm, taken out after 5 seconds, naturally dried, transferred into a clean vessel, and raised at the constant temperature of 23 ℃. Each concentration was repeated 3 times, and the control group was an aqueous solution containing 0.5 part per thousand of Tween-80. After 24 hours of treatment, the number of dead aphids was counted and the mortality was calculated according to the formula: mortality (%) - (number of control live insects-number of treated live insects)/number of control live insects × 100%. The results are shown in tables 10 to 11.
(4) Insecticidal activity against ergates of Solenopsis invicta
The red imported fire ant belongs to hymenoptera pests, social insects, and is one of destructive invasive organisms. The method is characterized in that the ergate of Solenopsis invicta is used as a test object and is tested by a water test tube feeding method.
The operation process is as follows: accurately weighing each sample, adding 200 microliters of dimethyl sulfoxide to prepare 10g/L mother solution respectively, and diluting the mother solution to a concentration of 100ppm by using a mixed aqueous solution containing 0.5 thousandth of tween-80 and five percent of honey during an experiment. Placing the red imported fire ant into the ant-raising test tube, injecting the liquid medicine into the silica gel plug of the ant-raising test tube by using an injector, and preferably ensuring that the liquid medicine does not seep out. The test tube for raising the ants is flatly placed in an ant raising box, a small amount of ham sausages are added into the test tube to serve as food, and the test tube is raised at the constant temperature of 25 ℃. The treatment was carried out for 24h and 72h to investigate the number of live and dead insects, and the mortality was calculated according to the formula: mortality (%) - (number of control live insects-number of treated live insects)/number of control live insects × 100%. The results are shown in tables 10 to 11.
TABLE 10 insecticidal Activity of some of the compounds shown in Table 2 against test pests
Figure BDA0001956643560000201
TABLE 11 insecticidal Activity of some of the Compounds shown in tables 3 to 5 against test pests
Figure BDA0001956643560000202
Figure BDA0001956643560000211
As can be seen from the table, the compounds listed in the present invention have activities similar to those in CN201711069917.7 and CN201810219338.4 of the previously disclosed patents. The pesticide composition has high killing activity on agricultural and forestry pests, animal parasitic pests, sanitary pests and the like, particularly has good activity on lepidoptera pests, homoptera pests, hymenoptera pests and the like, has a delayed effect on the solenopsis invicta, and has a better killing effect on the whole nest and postformity of the solenopsis invicta.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it will be appreciated that various changes or modifications may be made by those skilled in the art after reading the above teachings of the present invention, and such equivalents are intended to fall within the scope of the appended claims.

Claims (9)

1. A preparation method of a fused heterocyclic compound is characterized in that the fused heterocyclic compound has the following structural formula:
Figure 539161DEST_PATH_IMAGE001
or is or
Figure 282995DEST_PATH_IMAGE002
Or
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；
The preparation method comprises the following steps:
with 5-amino-1H-arylpyrazole substrates
Figure 280087DEST_PATH_IMAGE004
Reacting a raw material A with a raw material B in an alkali assistant and a solvent, and then separating to obtain the condensed heterocyclic compound;
wherein Y is
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，
Figure 676750DEST_PATH_IMAGE006
Or
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；
The raw material B is of a structural formula
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Of cis-structure, trans-structure or a mixture of cis-trans-structures, or
Figure 98001DEST_PATH_IMAGE009
；
R1Selected from hydrogen, halogen, -CN, -CO2R8、-CONR8R9、C1~C6Alkyl, phenyl or heteroaryl; wherein C is1~C6Alkyl, phenyl or heteroaryl unsubstituted or substituted by one or more substituents R10Substitution;
R2selected from hydrogen, halogen, -CN, -CO2R8、-CONR8R9、-S(O)R8、-S(O)2R8、C1~C6Alkyl, phenyl or heteroaryl; wherein C is1~C6Alkyl, phenyl or heteroaryl unsubstituted or substituted by one or more substituents R10Substitution;
R3and X are leaving groups; said leaving group is selected from fluorine, chlorine, bromine, iodine, -OMs or-OTs;
R4selected from hydrogen, halogen, -NO2、-CF3、-COR8、-CO2R8or-CN;
R5is-NO2、-CF3、-CHF2、-CN、-COR8、-CO2R8、-S(O)R8or-S (O)2R8；
R6、R7Independently selected from hydrogen, halogen, -COR8、-CN、-CO2R8、-CONR8R9、-OR8、-NR8R9、C1~C6Alkyl or heteroalkyl, wherein C1~C6Alkyl unsubstituted or substituted by one or more substituents R10Substitution; and isR6、R7At least one is an electron withdrawing group;
R8and R9Each independently is hydrogen, C1~C6Alkyl, heteroalkyl, C2～C6Alkenyl radical, C3～C8Cycloalkyl radical, C3～C8Cycloalkenyl, phenyl or heteroaryl; wherein C is1~C6Alkyl radical, C2~C6Alkenyl radical, C3~C8Cycloalkyl radical, C3~C8Unsubstituted or substituted by one or more substituents R10Substitution;
R10is halogen, C1-C6Alkyl radical, 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 ' are independently hydrogen, C1～C6Alkyl radical, C2～C6Alkenyl radical, C3～C8Cycloalkyl, cycloalkenyl, phenyl, heteroaryl, cycloalkenyl being cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl or pentalenyl;
the heteroaryl is a 5-7 membered aromatic monocyclic ring comprising 1, 2, 3 or 4 heteroatoms selected from N, O and S, the remaining ring atoms being carbon;
R11、R12independently selected from hydrogen, halogen, -NO2、-COR8、-CN、-CO2R8、-OR8、-NR8R9、C1～C6Alkyl or heteroalkyl; wherein C is1～C6Alkyl unsubstituted or substituted by one or more substituents R10Substitution;
the heteroalkyl group contains an O oxygen atom and includes 1 to 6 carbon atoms;
and when said aryl group is a pyridine ring, R11、R12Cannot be an electron donating group; and when said aryl is a phenyl ring, R4When it is hydrogen, R11、R12Are electron withdrawing groups.
2. A process for producing a fused heterocyclic compound according to claim 1, characterized in that: the R is6Or R7Wherein the electron withdrawing group is selected from: -CO2R8、-COR8-CN, halogen or-CF3。
3. A process for producing a fused heterocyclic compound according to claim 1, characterized in that: the R is1Selected from-CN, -CO2R8、-CONR8R9Phenyl or heteroaryl; phenyl or heteroaryl unsubstituted or substituted by one or more substituents R10And (4) substitution.
4. A process for producing a fused heterocyclic compound according to claim 1, characterized in that: the R is2Selected from hydrogen, halogen, -CO2R8、-CONR8R9、-S(O)R8、-S(O)2R8Phenyl or heteroaryl; wherein the phenyl or heteroaryl radical is unsubstituted or substituted by one or more substituents R10And (4) substitution.
5. A process for producing a fused heterocyclic compound according to claim 1, characterized in that: the R is5Is selected from-NO2、-CF3、-CHF2、-CO2R8or-S (O) R8。
6. A process for producing a fused heterocyclic compound according to claim 1, characterized in that: the R is11Or R12Independently selected from hydrogen, halogen, -NO2、-COR8-CN or-CO2R8。
7. A process for producing a fused heterocyclic compound according to claim 1, characterized in that: the R is8、R9Or R10Independently selected from hydrogen, halogen, C1～C6Alkyl, phenyl or heteroaryl.
8. A process for producing a fused heterocyclic compound according to claim 1, characterized in that: wherein the solvent is one or a mixture of more of tetrahydrofuran, N-dimethylformamide, N-dimethyl propylene urea, N-methyl pyrrolidone, dimethyl sulfoxide, dioxane, acetonitrile, water or alcohols; the reaction time is 0.2-48 hours.
9. A process for producing a fused heterocyclic compound according to claim 1, characterized in that: the alkali assistant is selected from one or more of potassium carbonate, potassium bicarbonate, sodium carbonate, cesium fluoride, potassium tert-butoxide, lithium carbonate, potassium hydroxide, pyridine, DBU or DABCO.
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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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Publication number Priority date Publication date Assignee Title
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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