CN107311967B - N- [3- (2- furyl)] allylidene -2- cyano -3- heterocycle propylene hydrazide derivative and its application - Google Patents

N- [3- (2- furyl)] allylidene -2- cyano -3- heterocycle propylene hydrazide derivative and its application Download PDF

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CN107311967B
CN107311967B CN201710486915.1A CN201710486915A CN107311967B CN 107311967 B CN107311967 B CN 107311967B CN 201710486915 A CN201710486915 A CN 201710486915A CN 107311967 B CN107311967 B CN 107311967B
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added
cyano
antioxidant
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CN107311967A (en
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唐孝荣
刘辉
杨建�
高扬
严映坤
李唯一
曾义
张燕
陈绍玲
万云龙
吴茜
夏旭文
王兰
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Jiangsu Hokia Pneumatic Tools Co ltd
Shanghai Ningjing Intellectual Property Agency Co ltd
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Xihua University
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Abstract

The present invention relates to heterocyclic Schiff base class compound and application thereof, in particular to N- [3- (2- furyl)] allylidene -2- cyano -3- heterocycle propylene hydrazide derivative and its application.The technical problem to be solved by the present invention is to provide a kind of heterocyclic Schiff base class compounds that can be used as antioxidant and agricultural insecticide and use, and structural formula is as shown in formula I.The present invention splices principle using bio-active group, heterocyclic compound is introduced into Schiff class compound, the reactive compound or active lead compound for having found some structure novels, superior activity, so that preferable basis has been established in the initiative for novel antioxidant and insecticide.

Description

N- [3- (2- furyl)] allylidene -2- cyano -3- heterocycle propylene hydrazides are spread out Biology and its application
Technical field
The present invention relates to heterocyclic Schiff base class compound and application thereof, in particular to N- [3- (2- furyl)] allylidenes Base -2- cyano -3- heterocycle propylene hydrazide derivative and its application.
Background technique
Antioxidant effectively can delay or inhibit many substances, especially big point of the biology such as sugar, rouge, protein, nucleic acid The oxidation deterioration of son, very extensive application is suffered from many fields: (1) in terms of food processing, antioxidant can inhibit Oxidation of Fat and Oils prevents its rancid, frequently as food oxydating resistance additive;(2) in life science and medical domain, antioxidant energy Interior free yl is removed, the formation of peroxidation state is slowed down, prevents and treats various diseases caused by free radical, improves machine Body immunocompetence, to protect human health;(3) in chemical industrial field, antioxidant adds as the stability of chemical products Add agent, improve the antioxygenic property of product, to prolong its service life.Since antioxidant is in industrial and agricultural production and daily life Irreplaceable role is all played in work, therefore, the research and development of efficient, economic, low toxicity antioxidant have very Important meaning.
On the other hand, long-term a large amount of use of pesticide especially insecticide not only polluted environment, destroy the ecological balance, Also result in serious " 3R " (residual, resistance and pest resurgence) and " three cause " (carcinogenic, teratogenesis shape and mutagenesis) problem.This A little problems cause the mankind and widely pay close attention to, and how to efficiently solve these problems is the one long-term and arduous of facing mankind Task.In this way, being faced with huge challenge in the case where the too busy to get away pesticide of the mankind in pesticide, find to harmful organism height Effect, to non-target organism safety, degradable in the environment and catabolite to human health and ecological environment security " environment and Humorous pesticide " or " environment friendly agricultural " the hot spot at pesticide research and forward position.
Schiff refer to condensation reaction occurs by primary amine and aldehydes or ketones and generate contain > one kind of C=N- structure has Machine compound, both can be isolated from natural products, can also be obtained by artificial synthesized method.Numerous studies table Bright, Schiff class compound suffers from extremely important in medicine, catalysis, analytical chemistry, corrosion and the fields such as photochromic Effect.Meanwhile Schiff class compound also has good bioactivity, for example, desinsection, antimycotic, antibacterium, anti- Cancer, anti parasitic, weeding etc..Therefore, in recent decades, people, which research and develop it, shows great interest, special Not being is even more to have received widespread attention, and constantly have structure novel, have excellent performance, make in the fields such as biology, medicine, pesticide It is come out with unique, the environmental-friendly kind of mode.
In recent years, during the research and development of bioactive compound, heterocyclic compound shows more and more important Effect.Due to its selective good, active height, dosage is few, toxicity is low and special in harmful organism biochemical reactions Property and become research main body.Wherein, the compounds such as furans, thiophene, pyridine, pyrimidine, pyrazoles, imidazoles, thiazole, triazole, because not It is disconnected to emerge some novel agents having an epoch-marking significance and attract people's attention, it also has become bioactive compound and grinds The hot spot studied carefully and forward position.
Up to the present, it yet there are no what heterocyclic Schiff base class compound was used as antioxidant and agricultural insecticide Report.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of heterocycles that can be used as antioxidant and agricultural insecticide and use Schiff class compound.
N- [3- (2- furyl)] allylidene -2- cyano -3- heterocycle propylene hydrazide derivative of the invention, knot Structure formula is as shown in formula I:
Wherein, R1ForR2For hydrogen, C1-C4 alkyl or halogen;R3For hydrogen, C1-C4 alkyl or halogen;X is O or S.
Preferably, R1ForPreferred R1For
The present invention also provides the compounds of this invention to prepare the application in antioxidant.
The compound of the present invention has excellent antioxygenic property, can be used as antioxidant.
The present invention also provides application of the compounds of this invention in prevention and treatment agricultural pests.
The compound of the present invention, it is also possible to make insecticide, to the agricultural evil such as mythimna separata, corn borer, Tetranychus cinnabarinus, Culex pipiens pallens Worm has preferable cytotoxicity.It is therefore preferable that the agricultural pests are mythimna separata, corn borer, Tetranychus cinnabarinus or Culex pipiens pallens.
The present invention splices principle using bio-active group, and heterocyclic compound is introduced into Schiff class compound, sends out The reactive compound or active lead compound of some structure novels, superior activity are showed, to be novel antioxidant and kill Preferable basis has been established in the initiative of worm agent.
Specific embodiment
The present invention provides structural formula such as I compound represented of formula:
Wherein, R1ForR2For hydrogen, C1-C4 alkyl or halogen;R3For hydrogen, C1-C4 alkyl or halogen;X is O or S.
Preferably, R1ForPreferred R1For
It is currently preferred structural formula below.
The compound of the present invention can be obtained using conventional preparation method.
The compound of the present invention has excellent antioxygenic property, can be used as antioxidant.
The compound of the present invention, it is also possible to make insecticide, to the agricultural evil such as mythimna separata, corn borer, Tetranychus cinnabarinus, Culex pipiens pallens Worm has preferable cytotoxicity.
A specific embodiment of the invention is further described below with reference to embodiment, is not therefore limited the present invention System is among the embodiment described range.
The synthesis of 1 compound 1~4 of embodiment
Composition principle:
1, the synthesis of compound 1
(1) synthesis of intermediate
The cyano acethydrazide of 0.01mol is placed in three-necked bottle, 15mL methylene chloride is added and makees solvent, 3mL acetic acid is urged Agent stirs under room temperature.It takes the 2- furylacrolein of 0.01mol to be added in 5mL methylene chloride, after completely dissolution, uses constant pressure Dropping funel is added dropwise in three-necked bottle, reacts 5h, detects terminal with thin layer silica gel plate (TLC).It places reaction liquid into beaker, It is washed till neutrality repeatedly with distilled water.Liquid separation is simultaneously evaporated under reduced pressure, and is dried after suction filtration, is obtained intermediate.
(2) synthesis of target compound
It taking intermediate 0.01mol to be placed in three-necked bottle, 15mL dehydrated alcohol is added and makees solvent, 3mL triethylamine makees catalyst, It is stirred under conditions of 50 DEG C.It takes the furfural of 0.01mol to be added in 5mL methylene chloride, after completely dissolution, uses constant pressure funnel It is added dropwise in three-necked bottle, reacts 1h, terminal is detected with thin layer silica gel plate (TLC).After fully reacting, reaction solution is poured into In 500mL beaker, the petroleum ether of 300mL and stirring is added, there is solid matter precipitation.After being filtered and being dried, with acetonitrile: nothing Water-ethanol=1:10 mixed solution recrystallizes crude product, obtains target product.
Yellow powder;IR(KBr)νmax(cm-1):3439,2209,1693,1584,1551,958;1H NMR(400MHz, DMSO-d6) δ (ppm): 11.70 (1H, s), 8.18 (2H, s), 8.08 (1H, s), 7.80 (1H, s), 7.44 (1H, d, J= 3.2Hz), 6.99 (1H, d, J=16.0Hz), 6.86 (1H, dd, J1=1.6Hz, J2=1.6Hz), 6.76-6.67 (2H, m), 6.61(1H,s);13C NMR(100MHz,DMSO-d6)δ(ppm):158.40(1C),152.11(1C),151.15(1C), 149.53(1C),148.89(1C),145.06(1C),137.05(1C),127.57(1C),123.25(1C),122.79(1C), 116.28(1C),114.48(1C),112.99(1C),112.77(1C),100.13(1C);HRMS(ESI)m/z:Calcd for C15H12N3O3[M+H]+:282.0873,Found:282.0870.
2, the synthesis of compound 2
(1) synthesis of intermediate
The cyano acethydrazide of 0.01mol is placed in three-necked bottle, 15mL methylene chloride is added and makees solvent, 3mL acetic acid is urged Agent stirs under room temperature.It takes the 2- furylacrolein of 0.01mol to be added in 5mL methylene chloride, after completely dissolution, uses constant pressure Dropping funel is added dropwise in three-necked bottle, reacts 5h, detects terminal with thin layer silica gel plate (TLC).It places reaction liquid into beaker, It is washed till neutrality repeatedly with distilled water.Liquid separation is simultaneously evaporated under reduced pressure, and is dried after suction filtration, is obtained intermediate.
(2) synthesis of target compound
It taking intermediate 0.01mol to be placed in three-necked bottle, 15mL dehydrated alcohol is added and makees solvent, 3mL triethylamine makees catalyst, It is stirred under conditions of 50 DEG C.It takes the 5 methyl furfural of 0.01mol to be added in 5mL methylene chloride, after completely dissolution, is dripped with constant pressure Liquid funnel is added dropwise in three-necked bottle, reacts 1h, detects terminal with thin layer silica gel plate (TLC).After fully reacting, reaction solution is fallen Enter in 500mL beaker, the petroleum ether of 300mL and stirring is added, there is solid matter precipitation.After being filtered and being dried, with acetonitrile: Dehydrated alcohol=1:10 mixed solution recrystallizes crude product, obtains target product.
Orange crystal;IR(KBr)νmax(cm-1):3447,2207,1677,1626,1555,971;1H NMR(400MHz, DMSO-d6) δ (ppm): 11.62 (1H, s), 8.18 (1H, d, J=9.2Hz), 7.97 (1H, s), 7.79 (1H, s), 7.37 (1H, D, J=2.8Hz), 6.97 (1H, d, J=16.0Hz), 6.75-6.60 (2H, m), 6.53 (1H, d, J=2.8), 6.60 (1H, dd,J1=1.6Hz, J2=1.6Hz), 2.44 (3H, s);13C NMR(100MHz,DMSO-d6)δ(ppm):159.86(1C), 158.69(1C),152.14(1C),150.92(1C),147.74(1C),145.00(1C),136.62(1C),127.38(1C), 124.77(1C),123.31(1C),116.51(1C),112.97(1C),112.66(1C),111.57(1C),97.93(1C), 14.34(1C);HRMS(ESI)m/z:Calcd for C16H14N3O3[M+H]+:296.1030,Found:296.1022.
3, the synthesis of compound 3
(1) synthesis of intermediate
The cyano acethydrazide of 0.01mol is placed in three-necked bottle, 15mL methylene chloride is added and makees solvent, 3mL acetic acid is urged Agent stirs under room temperature.It takes the 2- furylacrolein of 0.01mol to be added in 5mL methylene chloride, after completely dissolution, uses constant pressure Dropping funel is added dropwise in three-necked bottle, reacts 5h, detects terminal with thin layer silica gel plate (TLC).It places reaction liquid into beaker, It is washed till neutrality repeatedly with distilled water.Liquid separation is simultaneously evaporated under reduced pressure, and is dried after suction filtration, is obtained intermediate.
(2) synthesis of target compound
It taking intermediate 0.01mol to be placed in three-necked bottle, 15mL dehydrated alcohol is added and makees solvent, 3mL triethylamine makees catalyst, It is stirred under conditions of 50 DEG C.It takes the 5- bromothiophene -2- formaldehyde of 0.01mol to be added in 5mL methylene chloride, after completely dissolution, uses Constant pressure funnel is added dropwise in three-necked bottle, reacts 1h, detects terminal with thin layer silica gel plate (TLC).It, will be anti-after fully reacting It answers liquid to pour into 500mL beaker, the petroleum ether of 300mL and stirring is added, there is solid matter precipitation.After being filtered and being dried, With acetonitrile: dehydrated alcohol=1:10 mixed solution recrystallizes crude product, obtains target product.
Yellow powder;IR(KBr)νmax(cm-1):3424,2211,1682,1632,1552,966;1H NMR(400MHz, DMSO-d6) δ (ppm): 11.74 (1H, s), 8.45 (1H, s), 8.19 (1H, d, J=8.8Hz), 7.80 (2H, s), 7.52 (1H, S), 7.00 (1H, d, J=15.6Hz), 6.76-6.67 (2H, m), 6.61 (1H, s);13C NMR(100MHz,DMSO-d6)δ (ppm):158.03(1C),152.10(1C),151.30(1C),145.08(1C),144.38(1C),139.83(1C), 137.99(1C),132.47(1C),127.66(1C),123.21(1C),122.44(1C),116.68(1C),112.99(1C), 112.82(1C),101.44(1C);HRMS(ESI)m/z:Calcd for C15H11BrN3O2S[M+H]+:375.9750, Found:375.9745.
4, the synthesis of compound 4
(1) synthesis of intermediate
The cyano acethydrazide of 0.01mol is placed in three-necked bottle, 15mL methylene chloride is added and makees solvent, 3mL acetic acid is urged Agent stirs under room temperature.It takes the 2- furylacrolein of 0.01mol to be added in 5mL methylene chloride, after completely dissolution, uses constant pressure Dropping funel is added dropwise in three-necked bottle, reacts 5h, detects terminal with thin layer silica gel plate (TLC).It places reaction liquid into beaker, It is washed till neutrality repeatedly with distilled water.Liquid separation is simultaneously evaporated under reduced pressure, and is dried after suction filtration, is obtained intermediate.
(2) synthesis of target compound
It taking intermediate 0.01mol to be placed in three-necked bottle, 15mL dehydrated alcohol is added and makees solvent, 3mL triethylamine makees catalyst, It is stirred under conditions of 50 DEG C.The 2- furylacrolein of 0.01mol is taken to be added in 5mL methylene chloride, after completely dissolution, with perseverance Pressure dropping funel is added dropwise in three-necked bottle, reacts 1h, detects terminal with thin layer silica gel plate (TLC).After fully reacting, it will react Liquid pours into 500mL beaker, and the petroleum ether of 300mL and stirring is added, and has solid matter precipitation.After being filtered and being dried, use Acetonitrile: dehydrated alcohol=1:10 mixed solution recrystallizes crude product, obtains target product.
Orange powder;IR(KBr)νmax(cm-1):3444,2209,1652,1627,1542,930;1H NMR(400MHz, DMSO-d6) δ (ppm): 11.70 (1H, s), 8.17 (1H, d, J=9.6Hz), 8.09 (1H, d, J=11.6Hz), 7.96 (1H, D, J=1.6Hz), 7.80 (1H, s), 7.42 (1H, d, J=14.8Hz), 7.04-6.93 (3H, m), 6.76-6.61 (4H, m);13CNMR(100MHz,DMSO-d6)δ(ppm):158.14(1C),152.39(1C),152.13(1C),151.59(1C), 150.95(1C),147.40(1C),145.06(1C),133.79(1C),127.50(1C),123.30(1C),120.81(1C), 117.53(1C),115.65(1C),113.91(1C),113.00(1C),112.74(1C),105.65(1C);HRMS(ESI)m/ z:Calcd forC17H14N3O3[M+H]+:308.1030,Found:308.1027.
The measurement of 1 the compounds of this invention insecticidal activity of test example
1. test pest
3 instar larvae of mythimna separata, 3 instar larvae of corn borer, Tetranychus cinnabarinus adult mite, 3 instar larvae of Culex pipiens pallens, they are indoor normal The sensitive strain that year for many generations raises.
2. the measuring method of mythimna separata
Sample to be tested is dissolved in dimethyl sulfoxide and is diluted to certain concentration with 0.1% Tween-80 aqueous solution, to be not added The corresponding solution of sample to be tested is negative control.Maize leaf is cut into the segment of 2 × 4cm, is taken after soaking 5s in solution to be measured It opens, bottom is put into after draining and is covered in the culture dish (6cm) of filter paper, access 15 3 instar larvaes, then placing it in temperature is 22 ~24 DEG C, relative humidity 60%, light application time records death condition, often to continue to raise in the laboratory of 14:10h afterwards for 24 hours One experiment is repeated 3 times, and calculates corrected mortality with following equation:
3. the measuring method of corn borer
Sample to be tested is dissolved in dimethyl sulfoxide and is diluted to certain concentration with 0.1% Tween-80 aqueous solution, to be not added The corresponding solution of sample to be tested is negative control.The tender fringe of corn and tender bract are cut into segment, taken after soaking 10s in solution to be measured It opens, diameter is put into after draining as 6cm, in the glass culture dish of high 9cm, accesses 3 age of the corn borer children that 15 sizes are neat, healthy Worm, then placing it in temperature is 22~24 DEG C, relative humidity 60%, continues to raise in the laboratory that light application time is 14:10h It supports, records death condition afterwards for 24 hours, each experiment is repeated 3 times, and calculates corrected mortality with following equation:
4. the measuring method of Tetranychus cinnabarinus
Sample to be tested is dissolved in dimethyl sulfoxide and is diluted to certain concentration with 0.1% Tween-80 aqueous solution, to be not added The corresponding solution of sample to be tested is negative control.Acquire the big Kidney bean leaf of insect density, carefully choose make health adult mite (30~ 50) it stays on blade face, it is taken away after the Kidney bean leaf with worm is immersed solution 5s to be measured, the training that bottom is covered with filter paper is put into after draining It supports in ware (6cm), being placed on temperature is 22~24 DEG C, relative humidity 60%, and the laboratory that light application time is 14:10h relays Continuous raising, records death condition afterwards for 24 hours, and each experiment is repeated 3 times, and calculates corrected mortality with following equation:
5. the measuring method of Culex pipiens pallens
Using the method for world health organisation recommendations, sample to be tested is dissolved in dimethyl sulfoxide and with 0.1% Tween-80 water Solution is diluted to certain concentration, the corresponding solution of sample to be tested is not added as negative control.Take every kind of solution 1mL, respectively plus Enter into the 118mL wax dixie cup equipped with 99mL distilled water and 20 3 instar larvaes of Culex pipiens pallens, these dixie cups are placed on temperature It is 22~24 DEG C, relative humidity 60%, light application time records dead feelings to continue to raise in the laboratory of 14:10h afterwards for 24 hours Condition, each experiment are repeated 3 times, and calculate corrected mortality with following equation:
6. test result
The desinsection of the compounds of this invention the results are shown in Table 1.
Table 1
a: duplicate average value three times.
There is preferable cytotoxicity to these pests from the compounds of this invention known to upper table 1.
The measurement of the antioxygenic property of 2 the compounds of this invention of test example
1. instrument and reagent
721B type spectrophotometer, 1,1- diphenyl -2- picryl hydrazine (DPPH), 95% ethyl alcohol.
2. determination step
(1) preparation of DPPH and sample solution
0.0130 gram of DPPH is accurately weighed with assay balance, is settled in 500mL volumetric flask with 95% ethyl alcohol, obtains concentration For the solution of 26mg/L;0.0100g sample to be tested is accurately weighed, is settled in 100mL volumetric flask with 95% ethyl alcohol, obtains concentration For the sample solution of 100mg/L.
(2) the DPPH solution and 1mL95% ethanol solution of 4mL are sequentially added in 10mL conical flask, mix stable reaction Afterwards, using 95% ethyl alcohol as reference solution, its absorbance value is measured at λ max=518nm, is denoted as A0
(3) the DPPH solution and 1mL solution to be measured that 4mL is sequentially added in 10mL conical flask, shake up, react at room temperature After 40min stablizes, using 95% ethyl alcohol as reference solution, its absorbance value is measured at wavelength X max=518nm, is denoted as AS.Often One tests in triplicate, and the free radical scavenging activity Y (%) of antioxidant is calculated with following equation:
3. the measurement result of antioxygenic property
Table 2 is when concentration is 100mg/L, clearance rate of the compound to DPPH free radical
Compound Clearance ratea(%)
Compound 1 87.6
Compound 2 90.3
Compound 3 95.1
Compound 4 93.6
a: duplicate average value three times.
From upper table 2 it is found that the compounds of this invention to the clearance rate of DPPH free radical all 87% or more, i.e., they have compared with Good antioxygenic property.

Claims (5)

1. structural formula such as I compound represented of formula:
Wherein, R1For
R2For hydrogen, C1-C4 alkyl or halogen;R3For hydrogen, C1-C4 alkyl or halogen;X is O or S.
2. compound according to claim 1, it is characterised in that: R1For
3. compound according to claim 2, it is characterised in that: R1For
4. application of the described in any item compounds of claims 1 to 3 in prevention and treatment agricultural pests.
5. application of the compound according to claim 4 in prevention and treatment agricultural pests, it is characterised in that: the agricultural pests For mythimna separata, corn borer, Tetranychus cinnabarinus or Culex pipiens pallens.
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