CN108484572A - Novel bisamide class compound and its preparation method and application - Google Patents
Novel bisamide class compound and its preparation method and application Download PDFInfo
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- CN108484572A CN108484572A CN201810405584.9A CN201810405584A CN108484572A CN 108484572 A CN108484572 A CN 108484572A CN 201810405584 A CN201810405584 A CN 201810405584A CN 108484572 A CN108484572 A CN 108484572A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
The invention discloses a kind of novel bisamide class compounds and its preparation method and application, the novel bisamide class compound is first to obtain the compound of general formulae IV through chlorination reaction by the compound of general formula V, then by the compound of general formulae IV the compound of general formula III is obtained through dehydrogenation reaction, then the compound of general formula II is obtained through Basic fluxing raction by the compound of general formula III, is finally obtained through condensation reaction by the compound of general formula II and the compound of general formula I.The novel bisamide class compound dosage of the present invention is low, good to people, animal, environmental safety, notable to crop common insect pests control effect, especially has excellent insecticidal activity to preventions such as diamondback moth, beet tops moth, mythimna separata, snout moth's larvas, has good foreground；Especially, compared to existing chlorantraniliprole and cyanogen insect amide, insecticidal effect is close, but production cost substantially reduces, to be suitble to industrialized production.
Description
Technical field
The invention belongs to technical field of insecticide, and in particular to a kind of novel bisamide class compound and preparation method thereof and
Using.
Background technology
Bisamide insecticides are the hot spots of insecticide research field in recent years, it acts on the ryanodine receptor of insect,
It is novel with mechanism of action, efficiently, with traditional pesticide no interactions resistance, it is good etc. to non-target organism safety and to Environmental compatibility
Feature is attract attention, some external big pesticide companies have subsequently entered bisamide insecticides research field, join
With the study on the synthesis of such compound, to become insecticide research and development a big hot spot.
Bisamide insecticides divided from structure mainly include phthalic amide, anthranilic diamides and
Between benzamido benzamide three categories.The bisamide insecticides being commercialized share 8 kinds, including：2 kinds of phthalyls
Amine insecticide fluorobenzene insect amide and chlorine fluorine cyanogen insect amide；1 inter-species benzamido benzamide insecticides bromine worm fluorobenzene is double
Amide；5 kinds of O-formammidotiazol-benzamide insecticide Rynaxypyrs（Also referred to as chlorantraniliprole）, bromine cyanogen insect amide（Also referred to as
Cyanogen insect amide）, four chlorantraniliproles, ring bromine insect amide and chlorine fluorine cyanogen insect amide.
Wherein, chlorantraniliprole and cyanogen insect amide are the most widely used two kinds domestic and international at present, but are also gradually generated
Resistance, it is not once and for all that this, which illustrates any type insecticide,.Their structural formula difference is as follows：
；。
In addition, there is also the higher problems of production cost for both insecticides, because needing to use in its preparation process
Expensive bromide reagent tribromo oxygen phosphorus（40000/ton or so）.
Invention content
It is an object of the invention to solve the above problems, provide that a kind of insecticidal effect is preferable, production cost is lower novel
Bisamide class compound and its preparation method and application.
Realizing the technical solution of above-mentioned purpose of the present invention is：A kind of novel bisamide class compound, general structure are as follows
It is shown：
。
In formula：
R1Indicate C1-4Straight chained alkyl or halogen；Preferably C1-4Straight chained alkyl；More preferably CH3。
R2Indicate CN, S=CNH2Or halogen；Preferably CN or S=CNH2；More preferably CN.
R3Indicate C1-4Straight chained alkyl；Preferably CH3。
R4Indicate Cl.
R5Indicate Cl or Br；Preferably Cl.
R6Indicate Cl or H；Preferably Cl.
X indicates O or S；Preferably O.
Above-mentioned novel bisamide class compound is preferably：
、、。
More preferably：。
The preparation method of above-mentioned novel bisamide class compound, includes the following steps：
1. first obtaining the compound of general formulae IV through chlorination reaction by the compound of general formula V；
2. the compound of the general formulae IV then 1. obtained by step obtains the compound of general formula III through dehydrogenation reaction；
3. the compound of the general formula III then 2. obtained by step obtains the compound of general formula II through Basic fluxing raction；
4. the compound of the general formula II finally 3. obtained by step and the compound of general formula I obtain above-mentioned novel pair through condensation reaction
Amides compound.
Specific synthetic route is as follows：
；
；
；
。
The R occurred in above-mentioned V~general formula of general formula I1~R6And X is defined as above.
The chlorination reagent that the chlorination reaction of above-mentioned steps 1. uses is phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, protochloride
One kind in sulfone；Preferably phosphorus oxychloride.
The molar ratio of chlorination reagent that the chlorination reaction of above-mentioned steps 1. uses and the compound of formula V is 0.3: 1~1: 1.
The chlorination reaction of above-mentioned steps 1. carries out in presence of organic solvent；The organic solvent is acetonitrile, third
One kind in ketone, butanone, tetrahydrofuran.
The chlorination reaction temperature of above-mentioned steps 1. is reflux temperature.
The condensation reaction of above-mentioned steps 4. carries out in presence of organic solvent；The organic solvent is acetonitrile, third
One kind in ketone, butanone, tetrahydrofuran.
The condensation reaction of above-mentioned steps 4. carries out in the presence of connecing sour agent；It is described that connect sour agent be triethylamine, anhydrous
One kind in sodium carbonate, Anhydrous potassium carbonate, pyridine, substituted pyridines.
The condensation reaction of above-mentioned steps 4. further includes that mesyl chloride is added dropwise in -5~0 DEG C.
The Basic fluxing raction of dehydrogenation reaction and step 3. of above-mentioned steps 2. uses this field conventional method.
For example, dehydrogenation reaction uses 2,3-, bis- chloro- 5,6- dicyan 1,4-benzoquinone（Abbreviation DDQ）, tetrachloroquinone etc. is as oxidation
Agent, it is room temperature to be used as reaction dissolvent, dehydrogenation reaction temperature using dichloromethane, dichloroethanes etc., and the reaction time is 20~30h.
For the alkali that Basic fluxing raction uses for sodium hydroxide, potassium hydroxide etc., reaction temperature is 20~60 DEG C, and the reaction time is 2~8h.
Application of the above-mentioned novel bisamide class compound on preparing insecticide.
Above-mentioned novel bisamide class compound can be prepared separately when preparing insecticide as desinsection single dose, can also be with
Other bioactive compounds are mixed with as Pesticidal combination.
Above-mentioned novel bisamide class compound is when preparing insecticide, either single dose or composition, and dosage form can be with
For any one of modern preparation dosage form, solid carrier, liquid flux or auxiliary agent selected by corresponding dosage form are prepared
Belong to the field versatile material；Such as solid carrier can be kaolin, precipitated calcium carbonate, organobentonite；Liquid flux
Can be the common solvents such as benzene class, alcohols, ketone, esters.
Above-mentioned novel bisamide class compound when preparing insecticide, effective content be 0.1~99.9wt%, preferably 30
~99wt%, more preferable 70~99wt%.
Above-mentioned novel bisamide class compound is when preparing insecticide, with 1~5g/ mus of effective dose best results.
Above-mentioned novel bisamide class compound especially does harm to crops, sanitary insect pest, forestry pest, fruit tree as insecticide
The prevention of worm has higher activity and excellent preventive effect.
The good effect that the present invention has：
（1）The novel bisamide class compound dosage of the present invention is low, good to people, animal, environmental safety, to crop common insect pests
Control effect is notable, especially has excellent insecticidal activity to preventions such as diamondback moth, beet tops moth, mythimna separata, snout moth's larvas, has fine
Foreground.
（2）The novel bisamide class compound of the present invention is as the new product in O-formammidotiazol-benzamide insecticide
Kind, compared to existing chlorantraniliprole and cyanogen insect amide, insecticidal effect is close, but production cost substantially reduces, because preparing
The chlorination reagent phosphorus oxychloride used in the process only has 5000 yuan/ton or so, the bromination examination well below 40000 yuan/ton or so
Agent tribromo oxygen phosphorus, so that cheap compared to chlorantraniliprole and cyanogen insect amide 2~30,000 yuan of production cost per ton, to suitable
Close industrialized production.
Specific implementation mode
（Embodiment 1）
The novel bisamide class structural formula of compound of the present embodiment is as follows：
。
The preparation method of the compound is as follows：
1. first obtaining compounds Ⅳ -1 through chlorination reaction by compound V -1.
Reaction equation is as follows：
。
Ⅴ-1 Ⅳ-1
The specific method is as follows：The compound V -1 of 30.4g is added in the four-hole boiling flask of 500mL（0.10mol）And 150mL
Acetonitrile, stirring are warming up to reflux, and the phosphorus oxychloride of 9.2g is then added dropwise（0.06mol）, continuing back flow reaction to conversion ratio is more than
98%.After reaction, solvent is evaporated off under first vacuum, then raffinate is slowly added into ice water, with the hydroxide of 20wt%
Sodium water solution is neutralized to pH=7, is then extracted again with dichloromethane, finally removes solvent, obtains the compounds Ⅳ -1 of 28.4g, receives
Rate is 88.1%.
2. then obtaining compound III -1 through dehydrogenation reaction by compounds Ⅳ -1.
Reaction equation is as follows：
。
Ⅳ-1 Ⅲ-1
The specific method is as follows：25.8g compounds Ⅳs -1 are added in the four-hole boiling flask of 500mL（0.08mol）With the dichloro of 250mL
The DDQ of 27.2g is added after stirring and dissolving for methane（0.12mol）, then react at room temperature for 24 hours.After reaction, anhydrous ether is used
Recrystallization, obtains the compound III -1 of 23.5g, yield 91.7%.
3. then obtaining compound ii -1 through Basic fluxing raction by compound III -1.
Reaction equation is as follows：
。
Ⅲ-1 Ⅱ-1
The specific method is as follows：The compound III -1 of 19.23g is added in the four-hole boiling flask of 500mL（0.06mol）With 60g concentration
For the sodium hydrate aqueous solution of 30wt%, it is warming up to 40 ± 2 DEG C of temperature control reaction 4h.After reaction, it is adjusted with the hydrochloric acid of 1mol/L
PH to 4~5 is filtered, and is washed, dry.Obtain the compound ii -1 of 16.66g, yield 94.9%.
4. finally obtaining above-mentioned novel bisamide class compound through condensation reaction by chemical compounds I -1 and compound ii -1.
Reaction equation is as follows：
。
Ⅰ-1 Ⅱ-1
The specific method is as follows：The chemical compounds I -1 of 9.45g is added in the four-hole boiling flask of 250mL（0.05mol）, 14.625g change
Close object II -1（0.05mol）, 0.5g tetrabutylammonium bromide and 100mL second it is fine, stir lower ice-water bath and be cooled to -5~0
DEG C, the triethylamine of 8.08g is first added, is stirred for down that the mesyl chloride of 6.87g is slowly added dropwise, ice-water bath is removed in 1h recession, at room temperature
React 1h.After reaction, add water to stir, then adjust acid, finally filter, is dry, obtaining the target product of 21.30g, yield is
91.9%。
1HNMR（400MHz, DMSO）ppm：2.15(s.3H),2.79(d.3H),7.27(s.1H),7.32(d.1H),
7.41(s.1H),7.73(m.1H),7.99(d.1H),8.24(d.1H),10.59(s.1H)。
（Embodiment 2）
The novel bisamide class structural formula of compound of the present embodiment is as follows：
。
The preparation method of the novel bisamide class compound other than the starting material of use and 1 difference of embodiment,
Remaining reference embodiment 1.
（Embodiment 3）
The novel bisamide class structural formula of compound of the present embodiment is as follows：
。
The preparation method of the novel bisamide class compound other than the starting material of use and 1 difference of embodiment,
Remaining reference embodiment 1.
（Test example）
This test example is biological activity determination of the novel bisamide class compound to diamondback moth, mythimna separata of the present invention.
1, test medicine：
Test medicament 1：90% embodiment, 1 active compound.
Test medicament 2：95% embodiment, 2 active compound.
Test medicament 3：95% embodiment, 3 active compound.
Comparison medicament 1：Commercially available 96% cyanogen insect amide active compound.
Comparison medicament 2：Commercially available 95% chlorantraniliprole active compound.
The above sample is provided by Jiangsu Agricultural Hormone Engineering Technology Research Centre Co., Ltd..
2, test method：It takes diameter 6cm culture dishes, ware bottom to cover one layer of filter paper, chooses cabbage leaves from greenhouse, remove surface
Wax coat, the wild cabbage leaf butterfly of diameter 3cm is made of card punch, and spraying treatment is carried out with Airbrub（Atomisation pressure：10psi；Phase
When in 6.7kg/cm2）, after leaf natural is dried in the shade, access test object.
Then processing examination material is moved in standard sight room（Temperature is 23~25 DEG C, and relative humidity is 40~60%, illumination
Time L/D is 13h/11h）, test worm response situation is observed, dead borer population is recorded after handling 48h, calculates the death rate, the results are shown in Table 1.
Table 1
As can be seen from Table 1：
The novel bisamide class compound insecticidal activity of embodiment 1 and the best bisamide insecticides chlorine worm of existing insecticidal effect
Amide is substantially suitable, and is better than cyanogen insect amide.
Then cyanogen insect amide is substantially suitable for the novel bisamide class compound insecticidal activity of embodiment 2.
The novel bisamide class compound insecticidal activity of embodiment 3 is relatively less better.
But the production cost of the novel bisamide class compound of 1~embodiment of embodiment 3 will be significantly lower than cyanogen insect amide
And chlorantraniliprole.
Claims (10)
1. a kind of novel bisamide class compound, it is characterised in that its general structure is as follows：
；
Wherein, R4Indicate Cl.
2. novel bisamide class compound according to claim 1, it is characterised in that：R1Indicate C1-4Straight chained alkyl or halogen
Element；R2Indicate CN, S=CNH2Or halogen；R3Indicate C1-4Straight chained alkyl；R5Indicate Cl or Br；R6Indicate Cl or H；X is indicated
O or S.
3. novel bisamide class compound according to claim 2, it is characterised in that：R1Indicate CH3；R3Indicate CH3；R5Table
Show Cl；X indicates O.
4. novel bisamide class compound according to claim 3, it is characterised in that：R6Indicate Cl.
5. novel bisamide class compound according to claim 4, it is characterised in that：R2Indicate CN.
6. the preparation method of the novel bisamide class compound described in one of claim 1 to 5, it is characterised in that including following step
Suddenly：
1. first obtaining the compound of general formulae IV through chlorination reaction by the compound of general formula V；
2. the compound of the general formulae IV then 1. obtained by step obtains the compound of general formula III through dehydrogenation reaction；
3. the compound of the general formula III then 2. obtained by step obtains the compound of general formula II through Basic fluxing raction；
4. the compound of the general formula II finally 3. obtained by step and the compound of general formula I obtain above-mentioned novel pair through condensation reaction
Amides compound；
Specific synthetic route is as follows：
；
；
；
。
7. the preparation method of novel bisamide class compound according to claim 6, it is characterised in that：1. above-mentioned steps
Chlorination reaction carries out in presence of organic solvent；The organic solvent is in acetonitrile, acetone, butanone, tetrahydrofuran
It is a kind of；The chlorination reagent that chlorination reaction uses is one kind in phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride；Chlorination
The molar ratio of reagent and the compound of formula V is 0.3: 1~1: 1.
8. the preparation method of novel bisamide class compound according to claim 6, it is characterised in that：4. above-mentioned steps
Condensation reaction carries out in presence of organic solvent；The organic solvent is in acetonitrile, acetone, butanone, tetrahydrofuran
It is a kind of；The condensation reaction of above-mentioned steps 4. carries out in the presence of connecing sour agent；It is described to connect sour agent as triethylamine, Carbon Dioxide
One kind in sodium, Anhydrous potassium carbonate, pyridine, substituted pyridines.
9. the preparation method of novel bisamide class compound according to claim 6, it is characterised in that：4. above-mentioned steps
Condensation reaction further includes that mesyl chloride is added dropwise in -5~0 DEG C.
10. application of the novel bisamide class compound on preparing insecticide described in one of claim 1 to 5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111170987A (en) * | 2019-12-30 | 2020-05-19 | 江苏省农用激素工程技术研究中心有限公司 | Novel 3-chloropyrazole bisamide compound and application thereof |
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| CN101611711A (en) * | 2004-10-08 | 2009-12-30 | 辛根塔参与股份公司 | Fungicidal compositions |
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| CN111170987A (en) * | 2019-12-30 | 2020-05-19 | 江苏省农用激素工程技术研究中心有限公司 | Novel 3-chloropyrazole bisamide compound and application thereof |
| CN111170987B (en) * | 2019-12-30 | 2021-04-02 | 江苏省农用激素工程技术研究中心有限公司 | Novel 3-chloropyrazole bisamide compound and application thereof |
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