CN106172418B - A kind of application of hydrazone compounds of the structure of benzopyrazines containing chlorine as fungicide - Google Patents
A kind of application of hydrazone compounds of the structure of benzopyrazines containing chlorine as fungicide Download PDFInfo
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- CN106172418B CN106172418B CN201610605481.8A CN201610605481A CN106172418B CN 106172418 B CN106172418 B CN 106172418B CN 201610605481 A CN201610605481 A CN 201610605481A CN 106172418 B CN106172418 B CN 106172418B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
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Abstract
A kind of application the invention discloses hydrazone compounds of the structure of benzopyrazines containing chlorine as fungicide.Compound 1 is made with 5- chlorine ortho-nitraniline and hydrazine hydrate in it；Compound 2 is made in compound 1 and BMF effects；Compound 3 is made with phosphorus oxychloride reaction in compound 2；Compound 4 is made with hydration hydrazine reaction in compound 3；Compound 4 is reacted with substitution aldehyde compound is made compound (I).Its raw material is simple and easy to get, preparation method is simple, convenient post-treatment, and product yield is high, and the compound is with antifungal activity, there is good bactericidal effect especially for point spore anthrax bacteria, Strawberry anthracnose bacterium and matrimony vine anthrax bacteria, provide the foundation for novel pesticide research and development.
Description
Technical field
A kind of application the present invention relates to hydrazone compounds of the structure of benzopyrazines containing chlorine as fungicide.
Background technology
Heterocycle structure is synthetic drug, the important key factor of the substances such as pesticide, this is because heterocycle is efficient, low toxicity and
What the characteristics of can carrying out diversification substitution, was determined.It has become medicine, a research hotspot in the field of pesticide.Hydrazone class
Compound has the extensive bioactivity such as good weeding, desinsection, sterilization, while being tied because containing the Asias C=N in its molecular structure
Structure makes it have stronger coordination ability and various coordination mode, can synthesize the new compound of many high activities, and hydrazone
Class compound and its complex also have good antitumor and oxidation resistant activity, therefore are led in pesticide, medicine, detection and material
There is application in domain.The extensive concern for the person that even more receives pesticide research, is studied more and more deep in terms of New pesticides discovery.Previous generation
Record the existing commercialization fifties kind, E.I.Du Pont Company reported at 1973 Benzophenonehydrazones analog derivative have well kill
Worm activity, especially has lepidoptera pest high-efficiency activated；The benquinox that Beyer Co., Ltd develops is in prevention pythium spp and soil fungi
Caused seed and sprout term disease have better effects；Schiff bases and fatty acylhydrazone are right by apparent activity of weeding
Broad leaved weed and barnyard grass have excellent activity, but are had not been reported in terms of fungicide.
Invention content
A kind of application it is an object of the present invention to provide hydrazone compounds of the structure of benzopyrazines containing chlorine as fungicide.
Application of the hydrazone compounds of a kind of structure of benzopyrazines containing chlorine as fungicide, it is characterised in that it is tied
Structure formula is such as shown in (I)：
Wherein:R1It is 3,4,5- trimethoxyphenyls, 2,4- dichlorophenyls, 3- aminomethyl phenyls, 2- bromophenyls, 3- chlorobenzenes
Base, 3- nitrobenzophenones, 2- fluorophenyls, 4- bromophenyls, 4- trifluoromethyls, 2- methoxyphenyls, 4- fluorophenyls, 3,4- diformazans
Phenyl, 4- aminomethyl phenyls, phenyl.
A kind of hydrazone compounds of structure containing benzopyrazines are as the sharp spore anthrax-bacilus of prevention, strawberry anthrax-bacilus, Chinese holly
The application of the fungicide of Qi anthrax bacteria.
The application, it is characterised in that R1For 3- chlorphenyls, 3- aminomethyl phenyls or phenyl compound to sharp spore anthrax
Bacterium, strawberry anthrax-bacilus, matrimony vine anthrax bacteria have bactericidal activity.
The application, it is characterised in that R1For 2- bromophenyls, 2- methoxyphenyls compound to matrimony vine anthrax bacteria
With bactericidal activity.
The application, it is characterised in that R1It is 3- nitrobenzophenones, 2- fluorophenyls, 4- aminomethyl phenyls or 4- fluorophenyls to grass
Certain kind of berries anthrax bacteria has bactericidal activity.
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing chlorine, it is characterised in that include the following steps：
1) in organic solvent, 5- chlorine ortho-nitraniline and hydrazine hydrate are obtained by the reaction such as 1 institute of formula under the action of Raney Ni
The compound 4-chloro o-phenylenediamine shown；
2) in organic solvent, 4- chlorine o-phenylenediamine that step 1) obtains is obtained by the reaction under ethyl alcohol effect with MBF as
2 compound represented 7- chlorine-2-hydroxyl -3- phenyl quinoxalines of formula；
3) the 7- chlorine-2-hydroxyls -3- phenyl quinoxaline for obtaining step 2) is generated with phosphorus oxychloride action-reaction such as 3 institute of formula
The bis- chloro- 2- phenyl quinoxalines of compound 3,6- shown；
4) the bis- chloro- 2- phenyl quinoxalines of 3,6- for obtaining step 3) generate as shown in Equation 4 with hydrazine hydrate action-reaction
Compound (the chloro- 3- phenyl quinoxaline -2- bases of 6-) hydrazine；
5) under ethyl alcohol effect, (the chloro- 3- phenyl quinoxaline -2- bases of 6-) hydrazine and substitution aldehydes chemical combination that step 4) is obtained
Object reaction generates the target hydrazone compounds as shown in formula (I), and it is 3,4,5- trimethoxies to replace the substituent group in aldehyde compound
Base phenyl, 2,4- dichlorophenyls, 3- aminomethyl phenyls, 2- bromophenyls, 3- chlorphenyls, 3- nitrobenzophenones, 2- fluorophenyls, 4- bromobenzenes
Base, 4- trifluoromethyls, 2- methoxyphenyls, 4- fluorophenyls, 3,4- Dimethoxyphenyls, 4- aminomethyl phenyls, phenyl；
Preparation process is as follows：
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing chlorine, it is characterised in that 5- chlorine is adjacent in step 1)
The amount of the substance of nitroaniline and the mass ratio of Raney Ni are 1:2.5~4.5, consumption of organic solvent is with 5- chlorine ortho-nitrophenyls
The amount of the substance of amine is calculated as 0.3~0.5ml/mmol, and the hydrazine hydrate that hydrazine hydrate is 85%, volumetric usage is with 5- chlorine ortho-nitrophenyls
The amount of the substance of amine is calculated as 0.7~0.8ml/mmol.
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing chlorine, it is characterised in that 4- chlorine is adjacent in step 2)
The ratio between amount of substance of phenylenediamine and MBF is 1:1.5~3.5.
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing chlorine, it is characterised in that organic molten in step 2)
Agent dosage is calculated as 0.9~1.1ml/mmol with the amount of the substance of 4- chlorine o-phenylenediamines.
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing chlorine, it is characterised in that trichlorine oxygen in step 3)
Phosphorus dosage is calculated as 0.3~0.5ml/mmol with the amount of the substance of bis- chloro- 2- phenyl quinoxalines of 3,6-.
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing chlorine, it is characterised in that 3,6- bis- in step 4)
The ratio between amount of substance of chloro- 2- phenyl quinoxaline and hydrazine hydrate is 1:1.5~4.5.
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing chlorine, it is characterised in that (6- is chloro- in step 5)
3- phenyl quinoxaline -2- bases) the ratio between amount of substance of hydrazine and substitution aldehyde compound is 1:0.9~1.1.
The preparation method of the hydrazone compounds of the structure of benzopyrazines containing chlorine, it is characterised in that organic molten in step 5)
Agent dosage is to replace the amount of the substance of aldehyde compound to be calculated as 7.0~8.0ml/mmol.
Application of the hydrazone compounds of the structure of benzopyrazines containing chlorine as herbicide.
Compared with prior art, the beneficial effects are mainly as follows：The present invention provides one kind containing benzopyrazines
Application of the hydrazone compounds of structure as fungicide, raw material is simple and easy to get, and preparation method is simple, convenient post-treatment, product
High income, the compound are with antibacterial activity, especially in the sharp spore anthrax-bacilus of prevention, strawberry anthrax-bacilus, matrimony vine anthrax bacteria
With good preventive and therapeutic effect, provide the foundation for the research and development of novel pesticide.
Specific implementation mode
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
The hydrazone compounds (I) of the structure containing benzopyrazines of the present invention can synthesize in the following manner：
In 250mL single-necked flasks, 0.1mol 5- chlorine ortho-nitraniline, 40mL methanol, 75mL hydrazine hydrates are sequentially added
(85%), 0.25~0.45Raney Ni (weight in wet base), is heated to reflux, and is tracked to raw material and is disappeared with TCL, is cooled to after reaction
Room temperature, is filtered to remove Raney Ni, and vacuum distillation removes solvent and obtains filbert crystal to get to compound as shown in Equation 1
14- methyl-o-phenylenediamines.In 250mL single-necked flasks, 0.1mol substituted o-phenylenediamines are added, are dissolved with 100mL ethyl alcohol,
MBF is slowly added dropwise again, has yellow solid appearance during being added dropwise, according to substituent R1Variation, the reaction time is different, normal
Warm section of lower reaction time is 30-120min, after the reaction was complete, is filtered to remove solvent, is flushed three times with ethyl alcohol, is obtained such as 2 institute of formula
The compound 7- chlorine-2-hydroxyl -3- phenyl quinoxalines shown.40mLPOCl is added in compound 23Solvent is made, item is heated to reflux
Chlorination is carried out under part, is tracked to raw material and is disappeared with TLC, is cooled to room temperature, be poured slowly into 500g ice water, immediately after reaction
A large amount of yellow solids are precipitated, filters, washing drying, obtains compound 3 as shown in Equation 3.In 250mL three-necked flasks, it is added
Compound 3 simultaneously makees solvent with 60mL ethyl alcohol, and the hydrazine hydrate of 18g (0.3mol) 85% is slowly added dropwise, is warming up to back after being added dropwise
Stream reacts 4-5h, is cooled to room temperature, is poured into 300g ice water after reaction, a large amount of white solids are precipitated immediately, through filtering,
Washing and dry, obtained crude product, compound 4 as shown in Equation 4 is obtained by recrystallizing.0.377g is added in 50mL round-bottomed flasks
(0.002mol) hydrazine is added 15mL ethyl alcohol and makees solvent, and 0.002mol substitution aldehyde compounds, raw material are slowly added dropwise under stirring condition
Rapid dissolving, then has solid precipitation, is stirred overnight at room temperature, contact plate monitoring, and raw material is filtered, uses petroleum ether after the reaction was complete
Mixed liquor washing with ethyl alcohol obtains reddish yellow solid powder, i.e. the hydrazone class of the structure containing benzopyrazines as shown in formula (I) three times
Close object.
The structural formula of embodiment 1~14, particular compound is as shown in table 2, and other synthesis conditions do not change.
Embodiment 1
3- (2- (2- bromophenyls) hydrazine) chloro- 2- phenyl quinoxalines of -6-, reddish yellow solid, yield 77.5%, m.p.145-
148℃；1H NMR(400MHz,CDCl3/TMS),δ7.26-7.29(m,1H,Ph-H),7.37-7.41(m,2H,Ph-H),
7.58-7.61 (m, 5H, Ph-H), 7.84 (s, 1H, Ph-H), 7.94 (s, 1H, CH), 8.19 (t, J=4.0Hz, 1H, Ph-H)
.HRMS(ESI)m/z:Calculated,437.0163,Found,437.0002[M+H]+.
Embodiment 2
The chloro- 3- of 6- (2- (3- nitrobenzophenones) diazanyl) -2- phenyl quinoxalines, reddish yellow solid, yield 65.4%,
m.p.195-198℃；1H NMR(400MHz,CDCl3/TMS),δ7.36(S,1H,Ph-H),7.60-7.64(m,6H,Ph-H),
7.83 (s, 1H, Ph-H), 7.93 (s, 1H, CH), 8.11 (d, J=5.6Hz, 1H, Ph-H), 8.25 (d, J=4.8Hz, 1H, Ph-
H),8.60(s,1H,Ph-H).HRMS(ESI)m/z:Calculated,404.0909,Found,404.0917[M+H]+.
Embodiment 3
The chloro- 3- of 6- (2- (3- chlorphenyls) diazanyl) -2- phenyl quinoxalines, reddish yellow solid, yield 62.8%, m.p.143-
146℃；1H NMR(400MHz,CDCl3/ TMS), δ 7.37 (d, J=6.8Hz, 3H, Ph-H), 7.58-7.62 (m, 5H, Ph-H),
7.75(s,1H,Ph-H),7.83(s,2H,Ph-H),7.92(s,1H,CH),7.87(m,2H,Ph-H),7.98(s,1H,Ph-
H).HRMS(ESI)m/z:Calculated,393.0668,Found,393.0675[M+H]+.
Embodiment 4
The chloro- 3- of 6- (2- (2- methoxyphenyls) diazanyl) -2- phenyl quinoxalines, reddish yellow solid, yield 76.8%,
m.p.124-1127℃；1H NMR(400MHz,CDCl3/TMS),δ3.89(s,3H,OCH3),6.93-6.95(m,1H,Ph-H),
7.03-7.07 (m, 2H, Ph-H), 7.38-7.42 (m, 2H, Ph-H), 7.60 (s, 3H, Ph-H), 7.64 (d, J=2.6Hz, 1H,
Ph-H),7.81-7.97(m,3H,Ph-H),8.15(s,1H,CH).HRMS(ESI)m/z:Calculated,389.1164,
Found,389.1172[M+H]+.
Embodiment 5
The chloro- 3- of 6- (2- (2- fluorophenyls) diazanyl) -2- phenyl quinoxalines, reddish yellow solid, yield 77.8%, m.p.138-
141℃；1H NMR(400MHz,CDCl3/TMS),δ7.08-7.13(m,1H,Ph-H),7.21-7.25(m,1H,Ph-H),
7.38-7.43 (m, 2H, Ph-H), 7.60 (d, J=2.8Hz, 4H, Ph-H), 7.84 (s, 1H, Ph-H), 7.93 (s, 2H, Ph-
H),8.12-8.16(m,1H,Ph-H),8.43(s,1H,CH).HRMS(ESI)m/z:Calculated,377.0964,Found,
377.0977[M+H]+.
Embodiment 6
The chloro- 3- of 6- (2- (3- aminomethyl phenyls) diazanyl) -2- phenyl quinoxalines, reddish yellow solid, yield 60.8%,
m.p.127-130℃；1H NMR(400MHz,CDCl3/TMS),δ2.42(S,3H,CH3), 7.24 (d, J=5.2Hz, 1H, Ph-
), H 7.32 (t, J=6.0Hz, 2H, Ph-H), 7.50-7.58 (m, 5H, Ph-H), 7.65 (s, 1H, Ph-H), 7.74-7.80 (m,
2H, Ph-H), 7.90 (d, J=6.4Hz, 1H, Ph-H), 7.98 (s, 1H, CH) .HRMS (ESI) m/z:Calculated,
373.1215,Found,373.1227[M+H]+.
Embodiment 7
The chloro- 3- of 6- (2- (3,4,5- trimethoxyphenyl) diazanyl) -2- phenyl quinoxalines, reddish yellow solid, yield
76.3%, m.p.122-125 DEG C；HRMS(ESI)m/z:Calculated,449.1375,Found,449.1383[M+H]+.
Embodiment 8
The chloro- 3- of 6- (2- (4- aminomethyl phenyls) diazanyl) -2- phenyl quinoxalines, reddish yellow solid, yield 56.0%,
m.p.102-105℃；HRMS(ESI)m/z:Calculated,373.1215,Found,373.1220[M+H]+.
Embodiment 9
The chloro- 3- of 6- (2- (2,4- dichlorophenyl) diazanyl) -2- phenyl quinoxalines, reddish yellow solid, yield 93.9%,
m.p.152-155℃；HRMS(ESI)m/z:Calculated,427.0279,Found,427.0114[M+H]+.
Embodiment 10
The chloro- 3- of 6- (2- (3,4- Dimethoxyphenyl) diazanyl) -2- phenyl quinoxalines, reddish yellow solid, yield 49.9%,
m.p.100-103℃；HRMS(ESI)m/z:Calculated,419.1269,Found,419.1274[M+H]+.
Embodiment 11
The chloro- 3- of 6- (2- (4- bromophenyls) diazanyl) -2- phenyl quinoxalines, reddish yellow solid, yield 76.0%, m.p.159-
162℃；HRMS(ESI)m/z:Calculated,437.0163,Found,437.0006[M+H]+.
Embodiment 12
The chloro- 2- phenyl quinoxalines of 3- (2- phenyl diazanyl) -6-, reddish yellow solid, yield 88.6%, m.p.119-122 DEG C；
HRMS(ESI)m/z:Calculated,359.1058,Found,359.1072[M+H]+.
Embodiment 13
The chloro- 3- of 6- (2- (4- trifluoromethyls) diazanyl) -2- phenyl quinoxalines, reddish yellow solid, yield 69.9%,
m.p.131-133℃；HRMS(ESI)m/z:Calculated,427.0932,Found,427.0949[M+H]+.
Embodiment 14
The chloro- 3- of 6- (2- (4- fluorophenyls) diazanyl) -2- phenyl quinoxalines, reddish yellow solid, yield 71.8%, m.p.148-
150℃；HRMS(ESI)m/z:Calculated,377.0964,Found,377.0973[M+H]+.
15 antifungal activity of embodiment is tested
Subjects：Sharp spore anthrax-bacilus, strawberry anthrax-bacilus, matrimony vine anthrax bacteria.
Inoculation method：The conidium of each fungal species is gently brushed into lamellae with a L-shaped glass bar.
Direct bioautography：After Deng test, the radius size of thin-layer chromatography version is measured.
Antibacterial activity test result is as shown in table 1
The bactericidal activity data of 1 compound D1-D14 of table
From 1 antibacterial activity of table show compound D3, D6, D12 under the conditions of microtitration to fungi point spore anthrax bacteria,
Strawberry anthracnose bacterium and matrimony vine anthrax bacteria have good activity, and compound D1, D4 has sterilization to matrimony vine anthrax bacteria
Activity, compound D2, D5, D8, D14 have certain bactericidal activity to Strawberry anthracnose bacterium.
Particular compound structure is as shown in table 2
The concrete structure of 2 compound D1-D14 of table
Claims (3)
1. a kind of hydrazone compounds of structure of benzopyrazines containing chlorine are as the sharp spore anthrax-bacilus of prevention, strawberry anthrax-bacilus, matrimony vine anthrax
The hydrazone compounds structural formula such as (I) of the application of the fungicide of germ, the structure of benzopyrazines containing chlorine is shown：
Wherein:R1For 3- chlorphenyls, 3- aminomethyl phenyls or phenyl.
2. a kind of application of hydrazone compounds of the structure of benzopyrazines containing chlorine as the fungicide of prevention matrimony vine anthrax bacteria, contains chlorine
The hydrazone compounds structural formula of benzopyrazines structure is such as shown in (I)：
Wherein:R1For 2- bromophenyls, 2- methoxyphenyls.
3. a kind of application of hydrazone compounds of the structure of benzopyrazines containing chlorine as the fungicide of prevention Strawberry anthracnose bacterium, contains chlorine
The hydrazone compounds structural formula of benzopyrazines structure is such as shown in (I)：
Wherein:R1For 3- nitrobenzophenones, 2- fluorophenyls, 4- aminomethyl phenyls or 4- fluorophenyls.
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| Title |
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| 1,4-二喹喔啉甲醛亚胺的合成和抑菌活性;马敬中等;《应用化学》;20060630;第23卷(第6期);第637页图1，640页表3、第1段 * |
| A versatile synthetic route to chiral quinoxaline derivatives from amino acids precursors;Ayman El-Faham等;《Letters in Peptide Science》;20020720;第49–54页 * |
| Synthesis, Characterization and Biological Evaluation of Some Quinoxaline Derivatives: A Promising and Potent New Class of Antitumor and Antimicrobial Agents;Aisha R. Al-Marhabi等;《Molecules》;20151130;第20卷;第19808页图2、19812页表2 * |
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Application publication date: 20161207 Assignee: Hangzhou baibeiyou Biotechnology Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980033594 Denomination of invention: Application of a hydrazone compound containing a chlorobenzopyrazine structure as a fungicide Granted publication date: 20181113 License type: Common License Record date: 20230315 Application publication date: 20161207 Assignee: Hangzhou Guangyoujiu Enterprise Management Partnership (L.P.) Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980033595 Denomination of invention: Application of a hydrazone compound containing a chlorobenzopyrazine structure as a fungicide Granted publication date: 20181113 License type: Common License Record date: 20230316 Application publication date: 20161207 Assignee: Hangzhou Zhiguo Enterprise Service Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980033596 Denomination of invention: Application of a hydrazone compound containing a chlorobenzopyrazine structure as a fungicide Granted publication date: 20181113 License type: Common License Record date: 20230316 |